Conductivity and Impedance

ID=714

General characterization and potential use of Moroccan lizardite clay in ceramics: Technological and dielectric studies

Authors	Youssef Arkame, Achraf Harrati, Yassine Et-Tayea, Ahmed Manni, Fahd Oudrhiri Hassani, Abdeslam El Bouari, Ali Sdiri, Iz-Eddine El Amrani El Hassani, Chaouki Sadik
Source	Open Ceramics Volume: 13, Pages: 100332 Time of Publication: 2023
Abstract	This work focuses on the characterization of lizardite and studying the technological and dielectric features of ceramics based on this geomaterial by experimental measurements. Note that, the physical evaluation (dielectric properties) of magnesian clay has never been studied. Natural lizardite was extracted from the Beni Boussera massif (Rif, Morocco), and was characterized in terms of chemical, physical, mineralogical and thermal aspects. A purification process was carried out to identify the mineral phases present in this material. The results showed that the studied material is mainly composed of silica (47.16 wt%) and magnesia (31.21 wt%), it is also richer in clay minerals such as lizardite and chlorite. The ceramic specimens were prepared by the uniaxial pressing method, followed by sintering to different temperatures (i.e., 900, 1000, 1100, and 1200 °C). The influence of the sintering temperature on porosity, density, shrinkage, water absorption, mechanical and microstructural properties of ceramics was evaluated, as well as chemical resistance and dielectric properties were studied. The evaluation of the optimized ceramic materials shows that good dielectric properties are obtained when sintered at a temperature of 1100 °C with a dielectric constant of 1.33, a dielectric loss of around 0.08, and a conductivity of 4.86 E−8 S/cm, at high frequency. Furthermore, the obtained ceramic specimen has a porosity of 17%, a density of 2.02 g/cm3, a water absorption of 9.86%, and a mechanical strength of 19.3 MPa. As a consequence, the results obtained have provided ceramics based on a natural resource with favorable technological and mechanical properties, and very interesting dielectric properties.
Remark	https://doi.org/10.1016/j.oceram.2023.100332 Link

ID=711

The Role of Strain in Proton Conduction in Multi-Oriented BaZr0.9Y0.1O3−δ Thin Film

Authors	Muhammad Shahrukh Saleem, Qianli Chen, Nick A. Shepelin, Simone Dolabella, Marta D. Rossell, Xuhai Zhang, Coleman X. Kronawitter, Fabio La Mattina, and Artur Braun
Source	ACS Appl. Mater. Interfaces Volume: 14, Issue: 50, Pages: 55915–55924 Time of Publication: 2022
Abstract	Within the emerging field of proton-conducting fuel cells, BaZr0.9Y0.1O3−δ (BZY10) is an attractive material due to its high conductivity and stability. The fundamentals of conduction in sintered pellets and thin films heterostructures have been explored in several studies; however, the role of crystallographic orientation, grains, and grain boundaries is poorly understood for proton conduction. This article reports proton conduction in a self-assembled multi-oriented BZY10 thin film grown on top of a (110) NdGaO3 substrate. The multiple orientations are composed of different lattices, which provide a platform to study the lattice-dependent conductivity through different orientations in the vicinity of grain boundary between them and the substrate. The crystalline stacking of each orientation is confirmed by X-ray diffraction analysis and scanning transmission electron microscopy. The transport measurements are carried out under different gas atmospheres. The highest conductivity of 3.08 × 10–3 S cm–1 at 400 °C is found under a wet H2 environment together with an increased lattice parameter of 4.208 Å, while under O2 and Ar environments, the film shows lower conductivity and lattice parameter. Our findings not only demonstrate the role of crystal lattice for conduction properties but also illustrate the importance of self-assembled strategies to achieve high proton conduction in BZY10 thin films.
Keywords	BaZrO3 thin film; BaZr0.9Y0.1O3−δ strained structure; proton conduction; crystallographic orientation
Remark	https://doi.org/10.1021/acsami.2c12657 Link

ID=710

Low temperature ammonia synthesis by surface protonics over metal supported catalysts

Author	Yasushi Sekine
Source	Faraday Discussions Time of Publication: 2023
Abstract	Low-temperature ammonia synthesis by applying an electric field to a solid heterogeneous catalyst was investigated to realize an on-demand, on-site catalytic process for converting distributed renewable energy into ammonia. By applying an electric field to the catalyst, even at low temperatures, the reaction proceeds efficiently by an "associative mechanism" in which proton-conducting species on the support surface promote the formation of N2Had intermediates through surface protonics. Kinetics, isotope exchange, infrared spectroscopy, X-ray spectroscopy, and AC impedance analysis were performed to clarify the effect of metal and catalyst support structure on the reaction, and an evaluation method for the surface protonics of the support was established to analyze the reaction mechanism, and further analysis using computational chemistry was also conducted. The elementary step determining catalytic activity changed from N2 dissociation to N2H formation, and this difference resulted in high activity for ammonia synthesis at low temperatures even when using base metal catalysts such as Fe and Ni.
Remark	DOI: 10.1039/x0xx00000x Link

ID=707

Surface protonic conductivity in chemisorbed water in porous nanoscopic CeO2

Authors	Xinwei Sun, Einar Vøllestad, Per Martin Rørvik, Sebastian Prodinger, Georgios N. Kalantzopoulos, Athanasios Chatzitakis, Truls Norby
Source	Applied Surface Science Volume: 611, Issue: A, Pages: 155590 Time of Publication: 2023
Abstract	CeO2 surfaces play decisive roles in heterogeneous catalysis of important processes. Here, we investigate adsorption and dissociation of water and migration of protons on internal surfaces of nanoscopic porous CeO2. Sorption and thermogravimetry confirm literature suggestions that the surface is hydrogenated to Ce3+ ions and protons H+. The following chemisorption is dissociative, yet weak, and physisorption sets in only at the very highest relative humidities, reflecting hydrophobic behaviour. We link sample conductivities to surface protonic conductances via a brick layer model and show that behaviours at high, intermediate, and low temperatures with, respectively, positive, close to zero, and negative apparent activation energies and pH2O1/2, pH2O1, and pH2O3/2 dependences, can be attributed to different models of migration all within the chemisorbed layer, without contribution from physisorbed water. While CeO2 may special in this respect due to the effect of the hydrogenated surface, we believe the extended models of transport in the chemisorbed layer may apply also to other oxides. Unsaturated chemisorption may play an important role for CeO2 as catalyst in that the surface is left available for reactant molecules, still with availability of dissociated and mobile protons in the chemisorbed layer and electronic defects by Ce3+ in the surface.
Keywords	Ceria; CeO2; Porous; Hydrogenation; Water adsorption; Chemisorption; Conductivity; Protonic; Surface; Brick layer model
Remark	https://doi.org/10.1016/j.apsusc.2022.155590 Link

ID=704

Ultrafast Crystallization and Sintering of Li1.5Al0.5Ge1.5(PO4)3 Glass and Its Impact on Ion Conduction

Authors	Antonino Curcio, Antonio Gianfranco Sabato, Marc Nuñez Eroles, Juan Carlos Gonzalez-Rosillo, Alex Morata, Albert Tarancón, and Francesco Ciucci
Source	ACS Appl. Energy Mater. Volume: 5, Issue: 11, Pages: 14466–14475 Time of Publication: 2022
Abstract	Li1.5Al0.5Ge1.5(PO4)3 (LAGP) is among the most promising solid electrolytes for the next generation’s all-solid-state lithium batteries. However, preparing LAGP electrolytes is time- and energy-intensive. In this work, LAGP glassy powders were sintered and crystallized in 180 s by ultrafast high-temperature sintering (UHS) under conditions attractive for continuous industrial processes (i.e., ambient pressure and atmosphere). The fast heating rates characteristic of UHS significantly delay crystallization, potentially decoupling crystallization and sintering. Furthermore, electrochemical impedance spectroscopy (EIS) characterizations reveal that LAGP sintered and crystallized by UHS has an ionic conductivity of 1.15 × 10–4 S/cm, slightly lower than conventionally annealed samples (1.75 × 10–4 S/cm). The lower conductivity can be attributed to poorer intergrain contact. To overcome this issue, additives such as B2O3 and Li3BO3 are used, resulting in ∼2 and ∼5 times higher grain boundary conductivity for LAGP+1 wt % B2O3 and LAGP+1 wt % Li3BO3, respectively, compared to LAGP. Overall, this work provides insights into unraveling the impact of UHS sintering on the LAGP Li+ conduction mechanism.
Remark	https://doi.org/10.1021/acsaem.2c03009 Link

ID=703

Development and characterization of highly stable electrode inks for low-temperature ceramic fuel cells

Authors	Sanaz Zarabi Golkhatmi, Muhammad Imran Asghar, Peter D. Lund
Source	Journal of Power Sources Volume: 552, Pages: 232263 Time of Publication: 2022
Abstract	Inkjet printing is a potential contactless and mask-free additive manufacturing approach for solid oxide fuel cells. Here, a highly stable cathode ink using La0.6Sr0.4Co0.2Fe0.8O3 was developed and characterized with particle size analysis, viscosity, surface tension, density, and thermal analysis. Both fresh and 6-months stored inks showed excellent jetability behavior with a Z number of 2.77 and 3.45, respectively. The ink was successfully inkjet-printed on a (LiNaK)2CO3-Gd:CeO2 porous electrolyte substrate to fabricate a symmetric cell. The electrochemical impedance spectroscopy measurements showed that at 550 °C the inkjet printing lowered the ohmic resistance to one-third (from 1.05 Ω cm2 to 0.37 Ω cm2) and the mass diffusion resistance by 4.25 times (from 6.09 Ω cm2 to 1.43 Ω cm2) as compared to drop-casted cell by creating a hierarchical porous structure and increasing reaction sites. Successful inkjet printing of the functional electrode material opens up a new avenue for the fabrication of the low-temperature ceramic fuel cells.
Keywords	Inkjet printing; Ceramics; Electrode; Solid oxide fuel cell; Stability
Remark	https://doi.org/10.1016/j.jpowsour.2022.232263 Link

ID=702

Native point defects and polaron transport in zirconium pyrovanadate

Authors	Linn Katinka Emhjellen, Xin Liu, Jonathan M. Polfus, Reidar Haugsrud
Source	Solid State Ionics Volume: 386, Pages: 116033 Time of Publication: 2022
Abstract	Density functional theory calculations and electrochemical impedance spectroscopy have been combined to derive a defect model for ZrV2O7 to rationalize its electrical conductivity behavior. ZrV2O7 shows slight vanadium over-stoichiometry, yielding the predominant defect pair: V5+ on Zr sites (VZr•) charge-compensated by electron polarons as V4+ on V sites (VV′). Small polaron hopping is the dominating conduction mechanism with a calculated polaron self-trapping energy of −0.22 eV. The polarons can, however, be strongly bound as V4+ substituted on Zr sites (VZr×), with a calculated binding energy of −0.97 eV with respect to free polarons. The temperature dependency of the electrical conductivity exhibits a crossover between two regimes at 550 °C, and the apparent activation energy increases with increasing temperature from 0.3 to 0.86 eV. According to the defect model, which includes the concentration ratio of free and bound polarons, free polaron hopping predominates the electrical conductivity at lower temperatures while the thermally activated transition from bound to free polarons predominates at higher temperatures.
Keywords	Point defects; Free polarons; Bound polarons; Zirconium pyrovanadate
Remark	https://doi.org/10.1016/j.ssi.2022.116033 Link

ID=701

Surface kinetics and bulk transport in La2Ni0.5Cu0.5O4+δ membranes from conductivity relaxation

Authors	Zuoan Li, Reidar Haugsrud
Source	Journal of European Ceramic Society Volume: 43, Issue: 2, Pages: 462-467 Time of Publication: 2023
Abstract	This work reports conductivity relaxation measurements on both uncoated (1.2 mm thick) and coated (2.0 mm thick) La2Ni0.5Cu0.5O4+δ membranes in the temperature range between 550 and 850 °C and oxygen partial pressures from 0.01 to 1.0 atm. The results show that surface kinetics has a significant effect on the relaxation profiles, especially at low temperatures and should not be neglected when extracting transport parameters. Oxygen chemical diffusion and surface exchange coefficients have been determined by transient conductivity with surface modification. Higher activation energy of surface exchange compared to bulk diffusion is observed for La2Ni0.5Cu0.5O4+δ, similar to that for La2NiO4+δ. Based on the oxygen partial pressure dependence of the surface exchange coefficient, it has been revealed that oxygen dissociative adsorption rate-limits the surface exchange.
Keywords	Conductivity relaxation; Surface modification; Surface exchange mechanisms; Oxygen diffusion; La2Ni0.5Cu0.5O4+δ; La2NiO4+δ
Remark	https://doi.org/10.1016/j.jeurceramsoc.2022.10.046 Link

ID=699

Electrospun Ca3Co4−xO9+δ nanofibers and nanoribbons: Microstructure and thermoelectric properties

Authors	Katharina Kruppa, Itzhak I. Maor, Frank Steinbach, Vadim Beilin, Meirav Mann-Lahav, Mario Wolf, Gideon S. Grader, Armin Feldhoff
Source	J Am Ceram Soc. Volume: 106, Pages: 1170–1181 Time of Publication: 2023
Abstract	Oxide-based ceramics offer promising thermoelectric (TE) materials for recy- cling high-temperature waste heat, generated extensively from industrial sources. To further improve the functional performance of TE materials, their power factor should be increased. This can be achieved by nanostructuring and texturing the oxide-based ceramics creating multiple interphases and nanopores, which simultaneously increase the electrical conductivity and the Seebeck coef- ficient. The aim of this work is to achieve this goal by compacting electrospun nanofibers of calcium cobaltite Ca3 Co 4−xO 9+δ, known to be a promising p-type TE material with good functional properties and thermal stability up to 1200 K in air. For this purpose, polycrystalline Ca3 Co 4−xO 9+δ nanofibers and nanorib- bons were fabricated by sol–gel electrospinning and calcination at intermediate temperatures to obtain small primary particle sizes. Bulk ceramics were formed by sintering pressed compacts of calcined nanofibers during TE measurements. The bulk nanofiber sample pre-calcined at 973 K exhibited an improved Seebeck coefficient of 176.5 S cm−1 and a power factor of 2.47 μW cm−1 K−2 similar to an electrospun nanofiber-derived ceramic compacted by spark plasma sintering.
Remark	DOI: 10.1111/jace.18842 Link

ID=698

Effects of Ni-NCAL and Ni–Ag electrodes on the cell performances of low-temperature solid oxide fuel cells with Sm0.2Ce0·8O2-δ electrolyte at various temperatures

Authors	Sea-Fue Wang, Yi-Le Liao, Yung-Fu Hsu, Piotr Jasinski
Source	International Journal of Hydrogen Energy Volume: 47, Issue: 94, Pages: 40067-40082 Time of Publication: 2022
Abstract	Three low-temperature solid oxide fuel cells are built using Sm0.2Ce0·8O2-δ (SDC) as the electrolyte. Cell A is symmetrical and features Ni–LiNi0.8Co0·15Al0·05O2 (Ni–NCAL) electrodes, Cell B comprises a Ni–NCAL anode and a Ni–Ag cathode, and Cell C is fabricated using a Ni–NCAL cathode and a Ni–Ag anode. The ohmic resistance and polarization resistance (Rp) of Cells B and C are significantly higher than those of Cell A. The reduction of NCAL at the anodes of Cells A and B yields LiOH and Li2CO3 phases, and the Ni particles generated on the surfaces of the NCAL particles improve the catalytic activity of the cells. Li2CO3–LiOH melts at temperatures >450 °C and penetrates the porous SDC electrolyte layer, causing its densification and abnormal grain growth and increasing its ionic conductivity to >0.2 S/cm at low temperatures. The high open-circuit voltages (OCVs) (0.970–1.113 V) of the cells during electrochemical measurements are ascribed to the Li2CO3–LiOH phase which serves as an electron-blocking layer for the SDC electrolytes. As the reduction of NCAL approaches completion, the anode comprises only Ni phase, which hinders the charge transfer process. The triple-phase-boundary (TPB) area at cathode of Cell B is significantly lower than that of Cell A; therefore, the catalytic activity of Cell B for the oxygen reduction reaction is lower than that of Cell A. Consequently, the maximum power density (MPD) of Cell B is less than half of that of Cell A. The large Rp value of Cell C is ascribed to its low TPB area at Ni–Ag anode which has no reaction with H2 during operation. No visible sintering of the SDC electrolyte layer is observed for Cell C; therefore, its ionic conductivity is considerably smaller than those of the electrolyte layers of Cells A and B. The OCVs of Cell C (0.281–0.495 V) are significantly lower than the typical OCVs of ceria-based SOFCs. This is attributed to the porous SDC electrolyte layer of Cell C. The large Rp values and the low OCVs contribute to the low MPDs of Cell C at various temperatures.
Keywords	Solid oxide fuel cell; NCAL electrode; Polarization; Cell performance
Remark	https://doi.org/10.1016/j.ijhydene.2022.09.148 Link

ID=697

Tuning the Thermoelectric Performance of CaMnO3-Based Ceramics by Controlled Exsolution and Microstructuring

Authors	Nikola Kanas, Benjamin A. D. Williamson, Frank Steinbach, Richard Hinterding, Mari-Ann Einarsrud, Sverre M. Selbach, Armin Feldhoff, and Kjell Wiik
Source	CS Appl. Energy Mater. Volume: 5, Issue: 10, Pages: 12396–12407 Time of Publication: 2022
Abstract	The thermoelectric properties of CaMnO3−δ/CaMn2O4 composites were tuned via microstructuring and compositional adjustment. Single-phase rock-salt-structured CaO–MnO materials with Ca:Mn ratios larger than unity were produced in reducing atmosphere and subsequently densified by spark plasma sintering in vacuum. Annealing in air at 1340 °C between 1 and 24 h activated redox-driven exsolution and resulted in a variation in microstructure and CaMnO3−δ materials with 10 and 15 vol % CaMn2O4, respectively. The nature of the CaMnO3−δ/CaMn2O4 grain boundary was analyzed by transmission electron microscopy on short- and long-term annealed samples, and a sharp interface with no secondary phase formation was indicated in both cases. This was further complemented by density functional theory (DFT) calculations, which confirmed that the CaMnO3−δ indeed is a line compound. DFT calculations predict segregation of oxygen vacancies from the bulk of CaMnO3−δ to the interface between CaMnO3−δ and CaMn2O4, resulting in an enhanced electronic conductivity of the CaMnO3−δ phase. Samples with 15 vol % CaMn2O4 annealed for 24 h reached the highest electrical conductivity of 73 S·cm–1 at 900 °C. The lowest thermal conductivity was obtained for composites with 10 vol % CaMn2O4 annealed for 8 h, reaching 0.56 W·m–1K–1 at 700 °C. However, the highest thermoelectric figure-of-merit, zT, was obtained for samples with 15 vol % CaMn2O4 reaching 0.11 at temperatures between 800 and 900 °C, due to the enhanced power factor above 700 °C. This work represents an approach to boost the thermoelectric performance of CaMnO3−δ based composites.
Remark	https://doi.org/10.1021/acsaem.2c02012 Link

ID=696

Magnetron sputtered LSC-GDC composite cathode interlayer for intermediate-temperature solid oxide fuel cells

Authors	A.A. Solovyev, A.V. Shipilova, S.V. Rabotkin, E.A. Smolyanskiy, A.N. Shmakov
Source	International Journal of Hydrogen Energy Volume: 47, Issue: 89, Pages: 37967-37977 Time of Publication: 2022
Abstract	The paper investigates the influence of the La0.6Sr0.4CoO3-δ-Gd0.1Ce0.9O1.95 (LSC-GDC) composite cathode interlayer on the operation of solid oxide fuel cells (SOFCs). Thin composite layers with the different GDC content are obtained by the reactive magnetron sputtering. The impact of the high-temperature annealing on the LSC-GDC phase composition is studied by the X-ray diffraction instrument using additionally a synchrotron radiation. The NiO-YSZ anodes with the YSZ electrolyte thin film and GDC barrier layer are used for the SOFC fabrication. The current-voltage curves and impedance spectra of SOFCs are obtained in the temperature range of 700–800°Ð¡. It is shown that not annealed composite layers with ∼50 vol% GDC content possess the most efficient electrochemical activity. The maximum power density of the SOFC with the LSC-GDC interlayer is 1322, 1041 and 796 mW/cm2 at 800, 750 and 700 °C, respectively, which is 20–35% higher than that of the cell without cathode interlayer.
Remark	https://doi.org/10.1016/j.ijhydene.2022.08.281 Link

ID=694

Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3–Ce0.8Sm0.2O2 Heterointerfaces as All-Ceramic Functional Layers for Solid Oxide Fuel Cell Applications

Authors	Juan de Dios Sirvent, Albert Carmona, Laetitia Rapenne, Francesco Chiabrera, Alex Morata, Mónica Burriel, Federico Baiutti, and Albert Tarancon
Source	ACS Appl. Mater. Interfaces Volume: 14, Issue: 37, Pages: 42178–42187 Time of Publication: 2022
Abstract	The use of nanostructured interfaces and advanced functional materials opens up a new playground in the field of solid oxide fuel cells. In this work, we present two all-ceramic thin-film heterostructures based on samarium-doped ceria and lanthanum strontium chromite manganite as promising functional layers for electrode application. The films were fabricated by pulsed laser deposition as bilayers or self-assembled intermixed nanocomposites. The microstructural characterization confirmed the formation of dense, well-differentiated, phases and highlighted the presence of strong cation intermixing in the case of the nanocomposite. The electrochemical propertiesâsolid/gas reactivity and in-plane conductivityâare strongly improved for both heterostructures with respect to the single-phase constituents under anodic conditions (up to fivefold decrease of area-specific resistance and 3 orders of magnitude increase of in-plane conductivity with respect to reference single-phase materials). A remarkable electrochemical activity was also observed for the nanocomposite under an oxidizing atmosphere, with no significant decrease in performance after 400 h of thermal aging. This work shows how the implementation of nanostructuring strategies not only can be used to tune the properties of functional films but also results in a synergistic enhancement of the electrochemical performance, surpassing the parent materials and opening the field for the fabrication of high-performance nanostructured functional layers for application in solid oxide fuel cells and symmetric systems.
Keywords	thin films, hydrogen oxidation reaction, symmetric functional layers, solid oxide cells, nanocomposites
Remark	https://doi.org/10.1021/acsami.2c14044 Link

ID=693

Correlations between structure, microstructure and ionic conductivity in (Gd,Sm)-doped ceria†

Authors	Cristina Artini, Massimo Viviani, Sabrina Presto, Sara Massardo, Maria Maddalena Carnasciali, Lara Gigli, and Marcella Pani
Source	Physical Chemistry Chemical Physics Volume: 24, Issue: Cristina Artini, Massimo Viviani, Sabrina Presto, Sara Massardo, Maria Maddalena Carnasciali, Lara Gigli and Marcella Pani , Pages: 23622-23633 Time of Publication: 2022
Remark	https://doi.org/10.1039/D2CP03255D Link

ID=692

High-temperature electrical conductivity and electrochemical activity in oxygen redox reaction of La-doped Sr2FeCo0.5Mo0.5O6-δ

Authors	M. M. Abdullaev, N. V. Lyskov, S. Ya. Istomin, E. V. Antipov
Source	Journal of Solid State Electrochemistry volume Volume: 26, Pages: 2771–2779 Time of Publication: 2022
Abstract	High-temperature electrical conductivity and electrochemical activity in the oxygen redox reaction of Sr2FeCo0.5Mo0.5O6-δ (SFCM) and Sr1.6La0.4FeCo0.5Mo0.5O6-δ (LSFCM) at variable oxygen partial pressure have been studied. We have found that the partial replacement of Sr2+ by La3+ results in a substantial decrease in the total electrical conductivity due to a decrease in the hole charge carrier concentration. Detailed analysis of the high- and low-frequency parts of the impedance spectra at pO2 = 0.1–1 atm and 873–1173 K has revealed different rate-limiting steps in the oxygen redox reaction for SFCM and LSFCM resulted from different oxygen vacancy concentrations in these materials. For SFCM, the oxygen redox reaction is limited by the processes of adsorption and dissociation of oxygen molecules, while for LSFCM by the charge transfer occurring at the triple phase boundary.
Remark	Link

ID=691

Effects of LiNi0.8Co0.15Al0.05O2 electrodes on the conduction mechanism of Sm0.2Ce0.8O2−δ electrolyte and performance of low-temperature solid oxide fuel cells

Authors	Sea-Fue Wang, Yi-Le Liao, Yung-Fu Hsu, Piotr Jasinski,
Source	Journal of Power Sources Volume: 546, Pages: 231995 Time of Publication: 2022
Abstract	In this study, three low-temperature solid oxide fuel cells are constructed using Ce0.8Sm0.2O2−δ (SDC) as the electrolyte and Ni–LiNi0.8Co0.15Al0.05O2 (Ni–NCAL) and Ni–Ag as the electrodes. Cell A with symmetrical Ni–NCAL electrodes exhibits the best electrochemical performance. During operation, the Ni–NCAL anode is reduced by H2 atmosphere to form LiOH and Li2CO3. The Li2CO3–LiOH melt produced at >450 °C permeates the SDC electrolyte layer, causing its densification and grain growth in addition to the Li+-ion doping of SDC grains. The maximum electrical conductivity of the Li+-ion-doped SDC at 550 °C is at least one order of magnitude smaller than that of the SDC–Li2CO3–LiOH composite electrolyte (0.331 S cm−1). The ohmic and polarization resistances of Cell A at 550 °C are 0.168 and 0.256 Ω cm2, respectively, and its open-circuit voltage is 1.065 V, indicating the presence of dense SDC electrolyte and electron-blocking layers. The maximum power density of the cell at 550 °C is 535.2 mW·cm−2, which is primarily due to the high catalytic activity for the hydrogen oxidation and oxygen reduction reactions at the electrodes and large electrical conductivity of the SDC–Li2CO3–LiOH composite electrolyte at low temperatures.
Remark	https://doi.org/10.1016/j.jpowsour.2022.231995 Link

ID=690

Efficiencies of cobalt- and copper-based coatings applied by different deposition processes for applications in intermediate-temperature solid oxide fuel cells

Authors	M. Tomas, V. Asokan, J. Puranen, J.-E. Svensson, J. Froitzheim
Source	International Journal of Hydrogen Energy Volume: 47, Issue: 76, Pages: 32628-32640 Time of Publication: 2022
Abstract	Solid Oxide Fuel Cells (SOFCs) are electrochemical conversion devices that produce electricity directly by oxidising a fuel. The interconnects between the individual cells need to be coated to limit Cr(VI) evaporation from the steel and to preserve electrical conductivity. Physical Vapour Deposition (PVD)-coated samples with Ce/Co, Ce/Cu, and Ce/MnCu, and Thermal Spray (TS)-coated Mn/Co, Cu and Mn/Cu and AISI 441 steel samples were exposed at 650 °C for up to 1000 h. The PVD Ce/Co and Ce/Cu coatings, as well as the TS Mn/Co coating, exhibited the formation of a thin protective Cr2O3 scales underneath the coating. These samples also exhibited the lowest area-specific resistance (ASR) values. The remainder of the samples exhibited much higher mass gains and higher ASR values. Cr(VI) evaporation measurements showed that all the coatings behaved approximately the same despite the PVD coatings being only about one-tenth of the thickness of the TS coatings.
Remark	https://doi.org/10.1016/j.ijhydene.2022.07.168 Link

ID=689

Synthesis of a Novel Nanoparticle BaCoO2.6 through Sol-Gel Method and Elucidation of Its Structure and Electrical Properties

Authors	Fareenpoornima Rafiq, Parthipan Govindsamy, and Selvakumar Periyasamy
Source	Journal of Nanomaterials Time of Publication: 2022
Abstract	The physical properties of cobalt oxide with varied oxidation states, and coordination numbers, in the transition series, have numerous applications. The present study explores the physical properties of BaCoO2.6 nanoparticles synthesized through the sol-gel method. The X-ray diffraction figure exhibits a 25 nm crystallite size hexagonal phase. The observational data shows the reduction in the real part of impedance (), dielectric constant (), dielectric loss (), and a raise in ac conductivity of mixed type of conduction with an elevation in frequency analyzed through impedance spectroscopy. The conductivity due to grain and grain boundaries is shown foremost in the complex impedance analysis. The plot of (Seebeck coefficient) in the low-temperature range indicates p-type behavior and the metal-insulator transition in the as-synthesized sample. The sample characteristics suggest applications in optical and switching devices. The Seebeck coefficient is the generation of potential difference when subjected to temperature difference. Thermoelectric materials are associated with the concept of high electrical conductivity like crystals and low thermal conductivity to that of glass. Nanothermoelectric materials can decrease further the thermal conductivity through phonon scattering. Electrical characterization suggests the presence of both NTCR and PTCR behavior in the sample, and hence, it explores the application in thermistor/resistance temperature detector’s (RTD) and low dielectric constant and loss to electro-optical and higher conversion efficiency to storage devices. Additionally, impedance spectroscopy helps in the study of electrochemical systems and solid-state devices wherein the transition of metal-insulator is an add-on to the research.
Remark	https://doi.org/10.1155/2022/3877879 Link

ID=688

Conduction mechanism of donor and acceptor doped sodium niobate-based ceramics

Authors	Luting Lu, Linhao Li, Xiuzi Che, Gaoyang Zhao
Source	Ceramics International Volume: 48, Issue: 21, Pages: 32073-32080 Time of Publication: 2022
Abstract	Recently, NaNbO3 (NN) has become a hot topic of current research due to its antiferroelectric energy storage properties, which demand that the ceramics withstand large applied electric fields. The breakdown strength is dependent on conduction properties, but there is limited research on the conduction mechanisms of NN. Here we report that A-site donor-doping of Bi3+ (BixNa1-3xNbO3) and B-site acceptor-doping of Mg2+ (NaNb1-2/5yMgyO3) in NN lead to dramatic changes in the magnitude of the bulk conductivity (σb) and the conduction mechanism of NN ceramics. Undoped NN exhibits mixed conduction behavior with an oxide ion transport number (tion) of ∼0.44, and σb of ∼10−6 S/cm at 600 °C. A low level of Bi3+ doping (x = 0.06) suppresses the NN mixed conduction mechanism to electron conduction (tion ∼ 0), and the bulk conductivity increases significantly, σb > 10−4 S/cm at 600 °C. On the other hand, Mg2+ doping (y = 0.06) samples mainly change the σb, with the mixed ion/hole conduction (tion ∼ 0.43) and σb > 10−4 S/cm at 700 °C. The results show that the conductivity of NN increases and exhibits different conduction mechanisms with the doping of Bi3+ and Mg2+. Aliovalent doping is not beneficial to improving the insulation properties. Thus, this work provides theoretical guidance for the study of energy storage characteristics and the suppression of leakage behavior of high-temperature dielectric capacitors.
Keywords	NaNbO3; Conduction mechanisms; Chemical doping; Defect
Remark	https://doi.org/10.1016/j.ceramint.2022.07.146 Link

ID=686

Characterization of Y and Mn co-substituted BaZrO3 ceramics: Material properties as a function of the substituent concentration

Authors	Maria Balaguer, Yoo Jung Sohn, Dietmar Kobertz, Sergey Kasatikov, Andrea Fantin, Michael Muller, Norbert H. Menzler, Olivier Guillon, Mariya E. Ivanova
Source	Solid State Ionics Volume: 382, Pages: Mariya E. Ivanova Time of Publication: 2022
Abstract	Innovations in materials science are the key element for solving technological challenges. Various energy and environmental applications require designing materials with tailored compositions, microstructures and specific target-oriented performance. Y and Mn co-substituted BaZrO3, e.g. BaZr0.85Y0.15Mn0.05O3-δ, has previously attracted attention as a membrane material for H2 separation from gas mixtures due to its mixed proton-electron conductivity leading to appreciable levels of H2-flux at elevated temperatures and its good thermo-chemical stability under reducing environments. In the present work, we developed ceramic materials within the BaZr0.8Y0.2-xMnxO3-δ series, where x = 0.02–0.15. The study of their functional properties in dependence of the Y-to-Mn ratio disclosed that thermal expansion and hydration decrease by increasing the Mn content as well as the total electrical conductivity. In addition to that, XPS analysis and near edge X-ray absorption fine structure spectra (NEXAFS) in the vicinity of O K-edge and Mn L2,3-edges indicated that the Mn atoms oxidation state in the surface and in the bulk range from Mn2+ to Mn4+ depending on the ambient conditions that can be encountered in MPEC electrodes, which it is suggested to be related with a hydration mechanism mediated by Mn oxidation and subsequent proton attachment to oxygen neighbors, similar to LSM.
Remark	https://doi.org/10.1016/j.ssi.2022.115959 Link

ID=683

Performance of membranes based on novel Ce0.8Sm0.2O2-δ /Ag cermet and molten carbonates for CO2 and O2 separation

Authors	C.G. Mendoza-Serrato, R. Lopez-Juarez, A. Reyes-Montero, J.A. Romero-Serrano, C. Gomez-Yanez, J.A. Fabian-Anguiano, J. Ortiz-Landeros
Source	Chemical Engineering Science Volume: 255, Pages: 117673 Time of Publication: 2022
Abstract	This work proposes a cermet infiltrated with a mixture of Li2CO3/Na2CO3/K2CO3 as a dense membrane to selectively separate CO2 and O2 at high temperatures. The cermet consisted of a mixture of the Ce0.8Sm0.2O2-δ (SDC) ceramic and silver as the metallic phase. This type of membrane is a novel design of the ceramic/carbonates type and represents an improvement of state-of-art designs by avoiding microstructural changes in the metallic phase and improving chemical inertness and wettability with the carbonate phase. First, an SDC nanostructured powder was chemically synthesized by direct combustion of urea: lanthanide nitrates-based deep eutectic solvent; then, SDC and silver powders were mixed in a 50:50 vol% ratio by using high energy ball milling. The mixture was uniaxially pressed and sintered to form a support. This cermet exhibited excellent wettability properties against the ternary molten carbonate phase; therefore, it readily allowed infiltration of the molten salts to form a dense membrane. Hence, the cermet showed excellent electronic conductivity as well as corrosion resistance in contact with carbonates for 200 h of continuous immersion. The cermet-carbonate membrane showed permselectivity by separating CO2 and O2 at high temperatures. It reaches simultaneous permeation values of 0.49 and 0.26 ml·min−1·cm−2, for CO2 and O2, respectively, at 850 °C. Finally, continuous permeation tests at 825 °C for 85 h proved the excellent chemical stability of the cermet-carbonate membrane. Any chemical reactivity was not observed between the cermet and the carbonates.
Keywords	Cermet; Molten carbonate membrane; CO2 separation; O2 separation
Remark	https://doi.org/10.1016/j.ces.2022.117673 Link

ID=681

The effect of alkaline earth metal substitution on thermoelectric properties of A0.98La0.02MnO3-δ (A = Ca, Ba)

Authors	Sathya Prakash Singh, Nikola Kanas, Mari-Ann Einarsrud, Kjell Wiik
Source	Processing and Application of Ceramics Volume: 16, Issue: 1, Pages: 78–82 Time of Publication: 2022
Abstract	The thermoelectric properties of ceramics with composition A0.98La0.02MnO3-δ are anticipated to vary with the basicity and atomic portion of the alkaline earth metal, A. In the present investigation ceramic powder precursors with composition A0.98La0.02MnO3-δ (A = Ca, Ba) were synthesized by the solid-state method and sintered in air at 1400 °C. Seebeck coefficient, electrical and thermal conductivities were characterized for both materials from 100 to 900 °C in air. The highest zT of 0.10 at 900 °C was reached for Ca0.98La0.02MnO3-δ. The high zT is attributed to the enhanced electronic conductivity (∼90 S/cm at 900 °C) due to La doping. zT for Ba0.98La0.02MnO3-δ reached its highest value (0.02) at 800 °C corresponding to a low electronic conductivity (∼2 S/cm), while the thermal conductivity was significantly reduced compared to Ca0.98La0.02MnO3-δ reaching ∼1 W/(m·K) combined with a high Seebeck coefficient, −290 μV/K. The present data represent a valuable basis for further development of these materials with respect to applications in thermoelectric devices.
Remark	https://doi.org/10.2298/PAC2201078S Link

ID=678

Tuning of the microstructural and electrical properties of undoped BaTiO3 by spark plasma sintering

Authors	Jon G. Bell, T. Graule, M. Stuer
Source	Open Ceramics Volume: 9, Pages: 100244 Time of Publication: 2022
Abstract	The distribution of oxygen vacancies in BaTiO3 specimens can greatly affect material electrical properties. Spark plasma sintering followed by annealing in controlled pO2 atmospheres offers the potential to control the oxygen vacancy distribution. Impedance spectroscopy has been used to study the electrical characteristics of undoped BaTiO3 specimens prepared at 1200 °C under a pressing pressure of 5 MPa and 50 MPa using spark plasma sintering (SPS). For both samples, at temperatures greater than 750 °C, the total conductivity is determined by the bulk conductivity (σb), while at temperatures between 550 °C–750 °C the total conductivity is determined by the grain boundary conductivity (σgb). Below 550 °C, the total conductivity is determined by the BaTiO3–Pt interface conductivity (σel). The bulk, grain boundary and electrode interface resistances and activation energies are lower for samples sintered and pressed at 50 MPa, compared to specimens sintered and pressed at 5 MPa. Plots of grain boundary conductivity (σgb) vs. oxygen partial pressure (pO2) (log(σgb) vs. log(pO2)), over the temperature range 517 °C–683 °C, have slopes of approximately 4.0 indicating that doubly charged oxygen vacancies () are located at the grain boundaries. The grain boundary region and BaTiO3–Pt interface conductivities are highly sensitive to the oxygen partial pressure. Therefore, SPS sintered BaTiO3 specimens that have been subjected to controlled annealing could be used to tailor BaTiO3 dielectric properties, as well as have potential applications in high temperature O2 sensing. Furthermore, analysis of a.c. conductivity using the Jonscher model reveals that the governing charge transport mechanism is via quantum mechanical tunneling (QMT), which operates at temperatures when grain boundaries control the total conductivity. The mechanism switches to the correlated barrier hopping (CBH) model at temperatures when the bulk controls the total conductivity.
Remark	https://doi.org/10.1016/j.oceram.2022.100244 Link

ID=673

Tailored and Improved Protonic Conductivity through Ba(ZxCe10−x)0.08Y0.2O3−δ Ceramics Perovskites Type Oxides for Electrochemical Devices

Authors	Dr. Kwati Leonard, Prof. Yuji Okuyama, Dr. Mariya E. Ivanova, Prof. Wilhelm A. Meulenberg, Prof. Hiroshige Matsumoto
Source	ChemElectroChem Time of Publication: 2022
Abstract	Acceptor-doped barium zirconate cerate electrolytes constitute prospective materials for highly efficient and environmentally friendly electrochemical devices. This manuscript employs a systematic approach to further optimize ionic conductivity in Ba(ZrxCe10−x)0.08Y0.2O3−δ, (1≤x≤9) oxides for moderate temperature electrolysis. We found two new composition variants by fixing a cerium/zirconium ratio of 5/4 at the perovskite B-site with incremental zirconium, an observation that contrasts many reports suggesting a linear decrease in conductivity with increasing zirconium. As a result, the composition BaZr0.44Ce0.36Y0.2O3−δ demonstrates a superior ionic conductivity (10.1âmS cm−1 at 500 °C) to stability trade-off whereas, BaZr0.16Ce0.64Y0.2O3−δ exhibits the highest conductivity (11.5âmS cm−1 at 500 °C) among the studied pellets. The high protonic conductivity is associated with a high degree of hydration, as confirmed by thermo-gravimetric analysis. In addition, both compositions as electrolytes allow successful hydrogen production in a steam electrolyzer prototype. Electrolysis voltage as low as 1.3âV is attainable at current densities of 600 and 500âmA/cm2 respectively at 600 °C, achieving 82 % current efficiencies with the later electrolyte.
Keywords	https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/celc.202101663
Remark	https://doi.org/10.1002/celc.202101663 Link

ID=672

On the mechanism of Mn(II)-doping in Scandia stabilized zirconia electrolytes

Authors	Einar Vøllestad, Vegar Øygarden, Joachim Seland Graff, Martin Fleissner Sunding, John D. Pietras, Jonathan M. Polfus, Marie-Laure Fontaine
Source	Acta Materialia Volume: 227, Pages: 117695 Time of Publication: 2022
Abstract	Cubic Scandia-stabilized zirconia (ScSZ) is an attractive electrolyte material for solid oxide cells due to its significant ionic conductivity, provided that the phase transition to its rhombohedral polymorph upon cooling is suppressed. The latter is achieved with addition of a secondary co-dopant, albeit it may be at the detriment of its ionic conductivity Here, we thoroughly investigate how MnO2 (0.5–10 mol%) as a co-dopant impacts on the sinterability, thermal expansion, crystal structure and ionic conductivity of ZrO2 doped with 10 mol% Scandia (10ScSZ), and we provide new insight on the chemistry of dissolved manganese in the fluorite lattice. Reactive sintering of 2 mol% MnO2 mixed with 10ScSZ enables to produce dense electrolyte with significant reduction of the peak sintering temperature and stabilisation of the cubic structure down to room temperature. Combined density functional theory and X-ray photoelectron spectroscopy analyses reveal that manganese predominantly enters the structure as Mn2+ during reactive sintering, with a prevalence of higher valence states at the surface and grain boundaries. The highest oxide ion conductivity is achieved for 2 mol% doped 10ScSZ (120 mScm−1 at 800 °C) and it decreases with increasing Mn concentration. For all compositions, the bulk conductivity remains independent of pO2 – corroborating a limited electronic conductivity contribution from Mn-doping. The grain boundary conductivity is found to decrease with sintering time and pO2, which is attributed to the chemistry and concentration of segregated manganese at the surface and grain boundaries, yielding depletion of oxygen vacancies in the space charge layer.
Keywords	Electrical conductivity; SOFC; Reactive sintering; ScSZ; Stability
Remark	https://doi.org/10.1016/j.actamat.2022.117695 Link

ID=670

Detailed characterization of oxide-ion and proton transport numbers in Sr–Ti layered perovskites using an improved electromotive force method

Authors	Yutaro Yagi, Isao Kagomiya & Ken-ichi Kakimoto
Source	Journal of Materials Research Time of Publication: 2022
Abstract	Numerous Sr–Ti-based layered perovskite-structured compounds exhibit protonic conductivity. In a previous study, we found that a new Sr2Ti0.95Al0.05O4−δ (STA05) layered perovskite also shows evidence of protonic conductivity. However, Sr–Ti-based layered perovskites are also potential oxide-ion conductors. Detailed transport numbers for both protons and oxide-ions in Sr–Ti-based layered perovskites remain unclear. To solve this problem, we here propose an improved approach based on electromotive force (emf) measurements to account for the contributions of thermal emf and polarization to the total conductivity. In the first step of this study, the conditions for investigating actual emfs were evaluated using measurements of yttria-stabilized zirconia as a typical oxide-ion conductor. The optimized emf technique was subsequently used to evaluate the transport numbers of STA05, which was found to exhibit no oxide-ion transport. Thus, STA05 is concluded to be a mixed proton and electron conductor..
Remark	Link

ID=669

Impedance spectroscopy study of Au electrodes on Gd-doped CeO2 (GDC) – Molten Li2CO3+Na2CO3 (LNC) composite electrolytes

Authors	Vijayan Sobhana Dilimon, Ragnar Strandbakke, Truls Norby
Source	Journal of Power Sources Volume: 522, Pages: 230986 Time of Publication: 2022
Abstract	We herein report an impedance spectroscopy study of Au electrodes on Gd-doped CeO2 (GDC) – molten Li2CO3+Na2CO3 (LNC) composite electrolytes in O2 and O2+CO2 atmospheres. Complementary measurements of Au on GDC alone are provided for supporting insight. We find that the adsorption of CO2 on GDC in O2+CO2 atmospheres effectively blocks oxygen adsorption and severely slows oxygen reduction kinetics. The conductivity of the composite is dominated by the GDC phase in the solid-solid temperature region, while the LNC phase dominates above its melting point, and no further enhancement e.g. by interfacial effects are found. The incorporation of LNC melt into GDC results in a significant reduction in the polarisation resistance of Au electrodes in O2 atmospheres, as the melt mediates the reaction by a peroxide mechanism. In O2+CO2 atmospheres, however, the polarisation resistance of Au electrodes on GDC-LNC membranes is significantly higher, higher even than that on GDC. This we assign again to the blocking adsorption of CO2 (or carbonate) on the surfaces of ceria and the sluggish transport and reactions now mediated by carbonate-carried oxide species (CO42−) instead of peroxide species.
Keywords	Molten carbonate fuel cells; MCFC; CeO2; Gd-doped; GDC; GDC-Molten carbonate composite electrolyte; Oxygen electrode; Mechanism
Remark	Link

ID=667

Oxide Ion and Proton Conductivity in a Family of Highly Oxygen-Deficient Perovskite Derivatives

Authors	Chloe A. Fuller, Douglas A. Blom, Thomas Vogt, Ivana Radosavljevic Evans, and John S. O. Evans
Source	J. Am. Chem. Soc. Volume: 144, Issue: 1, Pages: 615–624 Time of Publication: 2022
Abstract	Functional oxides showing high ionic conductivity have many important technological applications. We report oxide ion and proton conductivity in a family of perovskite-related compounds of the general formula A3OhTd2O7.5, where Oh is an octahedrally coordinated metal ion and Td is a tetrahedrally coordinated metal ion. The high tetrahedral content in these ABO2.5 compositions relative to that in the perovskite ABO3 or brownmillerite A2B2O5 structures leads to tetrahedra with only three of their four vertices connected in the polyhedral framework, imparting a potential low-energy mechanism for O2– migration. The low- and high-temperature average and local structures of Ba3YGa2O7 (P2/c, a = 7.94820(5) Å, b = 5.96986(4) Å, c = 18.4641(1) Å, and β = 91.2927(5) ° at 22 °C) were determined by Rietveld and neutron pair distribution function (PDF) analysis, and a phase transition to a high-temperature P1121/a structure (a = 12.0602(1) Å, b = 9.8282(2) Å, c = 8.04982(6) Å, and γ = 107.844(3)° at 1000 °C) involving the migration of O2– ions was identified. Ionic conductivities of Ba3YGa2O7.5 and compositions substituted to introduce additional oxide vacancies and interstitials are reported. Most phases show proton conductivity at lower temperatures and oxide ion conductivity at high temperatures, with Ba3YGa2O7.5 retaining proton conductivity at high temperatures. Ba2.9La0.1YGa2O7.55 and Ba3YGa1.9Ti0.1O7.55 appear to be dominant oxide ion conductors, with conductivities an order of magnitude higher than that of the parent compound.
Remark	https://doi.org/10.1021/jacs.1c11966 Link

ID=665

Reaction Sintering of Ca3Co4O9 with BiCuSeO Nanosheets for High-Temperature Thermoelectric Composites

Authors	Richard Hinterding, Desiree Rieks, Patrick A. Kissling, Lukas Steinbach, Nadja C. Bigall & Armin Feldhoff
Source	Journal of Electronic Materials volume Volume: 51, Pages: 532–542 Time of Publication: 2022
Abstract	Ceramic composites composed of oxide materials have been synthesized by reaction sintering of Ca3Co4O9 with BiCuSeO nanosheets. In situ x-ray diffraction and thermogravimetric analyses of the compound powders were conducted to understand the phase transformations during heating up to 1173 K. Further thermogravimetric analyses investigated the thermal stability of the composites and the completion of reaction sintering. The microstructure of the formed phases after reaction sintering and the composition of the composites were investigated for varying mixtures. Depending on the amount of BiCuSeO used, the phases present and their composition differed, having a significant impact on the thermoelectric properties. The increase of the electrical conductivity at a simultaneously high Seebeck coefficient resulted in a large power factor of 5.4 μW cm−1 K−2, more than twice that of pristine Ca3Co4O9.
Remark	Link

ID=663

Synthesis, structure and ionic conductivity of nanocrystalline Ce1−xLaxO2−δ as an electrolyte for intermediate temperature solid oxide fuel cells

Authors	Naeemakhtar Momin, J. Manjanna, Lawrence D’Souza, S.T. Aruna, S.Senthil Kumar
Source	Journal of Alloys and Compounds Volume: 896, Pages: 163012 Time of Publication: 2022
Abstract	La-doped CeO2 nanoparticles of composition Ce1−xLaxO2−δ (0 ≤ x ≤ 0.1) have been studied here as prospective electrolytes for intermediate temperature solid oxide fuel cells (IT-SOFCs). They were synthesized by auto-combustion method and the powder samples were calcined at 700 °C to get ultrafine nanocrystalline particles. They were characterized by XRD, Raman, FTIR, XPS, DRS, FESEM/EDX, particle size analyzer and ac-impedance techniques. Ionic conductivity was measured from 350 − 750 °C. The Ce0.90La0.1O2−δ (0.1 LDC) and Ce0.95La0.05O2−δ (0.05 LDC) showed a maximum conductivity of 8.89 × 10−3 and 8.32 × 10−3 S cm−1 at 700 °C, respectively. The σt of 0.1 LDC = 1.01 × 10−2 S cm−1 at 750 °C. The activation energy of 0.1 LDC and 0.05 LDC was found to be 0.70 eV and 0.87 eV, respectively. These values are higher than those reported for La-doped CeO2 in literature. The SOFC performance with 0.05 LDC as electrolyte showed open circuit voltage of 0.81 V and maximum power density of 41 mW cm−2 at 650 °C using hydrogen as fuel.
Remark	Link

ID=662

Unlocking bulk and surface oxygen transport properties of mixed oxide-ion and electron conducting membranes with combined oxygen permeation cell and oxygen probe method

Authors	Yongliang Zhang, Kevin Huang
Source	Journal of Membrane Science Volume: 644, Pages: 120082 Time of Publication: 2022
Abstract	Surface exchange kinetics and bulk diffusion of oxygen are of paramount importance to the activity of oxygen electrocatalysis and performance of electrochemical devices such as fuel cell, metal-air batteries, and oxygen separation membranes. Conventional approaches to obtaining these transport properties are often limited to single property under a specific non-operation related condition. Here we use a combined oxygen permeation cell and oxygen probe methodology to simultaneously attain rates of oxygen surface exchange and bulk conductivity/chemical diffusivity of three representative mixed oxide-ion and electron conductors, namely SrCo0.9Ta0.1O3-δ (SCT), La0.6Sr0.4CoO3-δ (LSC) and La0.6Sr0.4FeO3-δ (LSF), operated under a steady-state oxygen flux. The results explicitly show that SCT exhibit the highest oxide-ion conductivity/chemical diffusivity, fastest rates of surface oxygen exchange kinetics, thus promising to be the best oxygen electrocatalyst. We have also mapped out the distribution of oxygen chemical potential gradient across the membranes and applied B-transport number concept to illustrate the rate-limiting steps in the overall oxygen permeation process.
Remark	Link

ID=659

Electrical properties of yttria-stabilised hafnia ceramics

Authors	Meshari Alotaibi, Linhao Li and Anthony R Wes
Source	Phys. Chem. Chem. Phys. Volume: 23, Pages: 25951 Time of Publication: 2021
Abstract	Cubic, yttria-stabilised hafnia, YSH, ceramics of general formula, YxHf1xO2x/2: x = 0.15, 0.30 and 0.45 were sintered at 1650–1750 1C and characterised by impedance spectroscopy. All three compositions are primarily oxide ion conductors with a small amount of p-type conductivity that depends on atmospheric conditions and appears to increase with x. The electronic conductivity is attributed to hole location on under-bonded oxide ions and the absorption of oxygen molecules by oxygen vacancies, both of which occur on substitution of Hf4+ by Y3+. Composition x = 0.15 has the highest total conductivity and shows curvature in the Arrhenius plot at high temperatures, similar to that of the most conductive yttria-stabilised zirconia.
Remark	Link

ID=658

Electrochemical Performance of SrWO4 Electrolyte for SOFC

Authors	Ahmed Afif, Nikdalila Radenahmad, Juliana Zaini, Abdalla Mohamed Abdalla, Seikh Mohammad Habibur Rahman, Quentin Hoon Nam Cheok, Abul Kalam Azad
Source	The International Journal of Integrated Engineering Volume: 13, Issue: 1, Pages: 74-80 Time of Publication: 2021
Abstract	cheelite structured SrWO4 material was synthesized by the solid-state sintering method and studied with respect to phase stability and ionic conductivity under condition of technological relevance for SOFC applications. The resulting compound was crystallized in the single phase of tetragonal scheelite structure with the space group of I41/a. Room temperature X-ray diffraction and subsequent Rietveld analysis confirms its symmetry, space group and structural parameters. Analysis by SEM illustrated a highly dense structure. SrWO4 sample shows lower conductivity compared to the raditional BCZY perovskite structured materials. SrWO4 sample exhibited an ionic conductivity of 1.93 × 10−6 S cm-¹ at 1000°C in dry Ar condition. Since this scheelite type compound demonstrated significant conductivity and a dense microstructure, it could serve in SOFC as a mixed ion-conducting electrolyte.
Remark	Link

ID=655

Expanded Chemistry and Proton Conductivity in Vanadium-Substituted Variants of γ-Ba4Nb2O9

Authors	Alex J. Brown, Bettina Schwaighofer, Maxim Avdeev, Bernt Johannessen, Ivana Radosavljevic Evans, and Chris D. Ling
Source	Chem. Mater. Volume: 33, Issue: 18, Pages: 7475–7483 Time of Publication: 2021
Abstract	We have substantially expanded the chemical phase space of the hitherto unique γ-Ba4Nb2O9 type structure by designing and synthesizing stoichiometric ordered analogues γ-Ba4V1/3Ta5/3O9 and γ-Ba4V1/3Nb5/3O9 and exploring the solid-solution series γ-Ba4VxTa2–xO9 and γ-Ba4VxNb2–xO9. Undoped Ba4Ta2O9 forms a 6H-perovskite type phase, but with sufficient V doping the γ-type phase is thermodynamically preferred and possibly more stable than γ-Ba4Nb2O9, forming at a 200 °C lower synthesis temperature. This is explained by the fact that Nb5+ ions in γ-Ba4Nb2O9 simultaneously occupy 4-, 5-, and 6-coordinate sites in the oxide sublattice, which is less stable than allowing smaller V5+ to occupy the former two and larger Ta5+ to occupy the latter. The x = 1/3 phase γ-Ba4V1/3Ta5/3O9 shows greatly improved ionic conduction compared to the x = 0 phase 6H-Ba4Ta2O9. We characterized the structures of the new phases using a combination of X-ray and neutron powder diffraction. All compositions hydrate rapidly and extensively (up to 1/3 H2O per formula unit) in ambient conditions, like the parent γ-Ba4Nb2O9 phase. At lower temperatures, the ionic conduction is predominately protonic, while at higher temperatures it is likely other charge carriers make increasing contributions.
Remark	https://doi.org/10.1021/acs.chemmater.1c02340 Link

ID=654

Electrical transport in a molten-solid V2O5–ZrV2O7 composite

Authors	Linn Katinka Emhjellen, Ragnar Strandbakke and Reidar Haugsrud
Source	J. Mater. Chem. A Volume: 9, Pages: 18537-18545 Time of Publication: 2021
Abstract	Molten-solid composite oxides are candidates as oxygen transport membranes (OTMs) at intermediate temperatures (500–700 °C). Effects of the constituent phases and interphases on surface reactions and transport processes in these composites are elusive. Here we contribute fundamental insight to such materials systems, applying electrochemical impedance spectroscopy (EIS) and electromotive force (emf) measurements to investigate the electrical conductivity characteristics of a 30 mol% V2O5–ZrV2O7 composite with a eutectic melting point at ∼670 °C. When V2O5 melts and increases the V2O5 volume percolation, the electrical conductivity increases by a factor of 10 and the activation energy increases from 0.21 to ∼0.7 eV. The oxygen red-ox reaction at the surface changes from being rate limited by charge transfer processes to mass transfer processes as a consequence of fast oxygen exchange in molten V2O5 as compared to the all-solid composite. These effects coincide with the ionic transport number rising from essentially zero to ∼0.4, reflecting a significant increase in the relative oxide ion conductivity. Oxygen permeation across a 30 mol% V2O5–ZrV2O7 membrane was estimated to be in the same order as for several dual-phase membranes, but one magnitude lower than for single-phase mixed conducting membranes at intermediate temperatures.
Remark	DOI: 10.1039/D1TA03750A Link

ID=645

Structural and Electrochemical Properties of Scandia Alumina Stabilized Zirconia Thin Films

Authors	Mantas Sriubas, Darius Virbukas, Nursultan Kainbayev, Kristina Bockute and Giedrius Laukaitis
Source	Coatings Volume: 11, Issue: 7, Pages: 800 Time of Publication: 2021
Abstract	This work presents a systematic investigation of scandia alumina stabilized zirconia (ScAlSZ, composition: ZrO2:Sc2O3:Al2O3 93:6:1 wt.%) thin films (~2 μm). Thin films were formed by the e-beam evaporation method on 450 °C substrates. The influence of Al concentration on thin film microstructure, structure, and electrochemical properties was characterized by EDS, XRD, Raman, and EIS methods. It was found that the aluminum concentration in the deposited thin films decreased with an increase in the deposition rate. The concentration of Al changed from 15.9 to 3.8 at.% when the deposition rates were 0.2 and 1.6 nm/s, respectively. The crystallinity of the thin films depended strongly on the concentration of Al, resulting in an amorphous phase when Al concentration was 22.2 at.% and a crystalline phase when Al concentration was lower. ScAlSZ thin films containing 15.9 at.% of Al had monoclinic and tetragonal phases, while thin films with 1.6 and 3.8 at.% of Al had a mixture of cubic, tetragonal, and monoclinic phases. The phase transition was observed during the thermal annealing process. Cubic and rhombohedral phases formed in addition to monoclinic and tetragonal phases appeared after annealing ScAlSZ thin films containing 15.9 and 22.2 at.% of aluminum. The highest total ionic conductivity (σbulk = 2.89 Sm−1 at 800 °C) was achieved for ScAlSZ thin films containing 3.8 at.% of Al. However, thin films containing a higher concentration of aluminum had more than 10 times lower total conductivity and demonstrated changes in activation energy at high temperatures (>560 °C). Activation energies changed from ~1.10 to ~1.85 eV.
Keywords	electron beam deposition; scandia alumina stabilized zirconia (ScAlSZ); solid oxide fuel cells (SOFC); ionic conductivity
Remark	https://doi.org/10.3390/coatings11070800 Link

ID=643

Preparation of NdBaCo2O5+δ–Ce0.9Gd0.1O1.95 composite cathode by in situ sol-mixing method and its high-temperature electrochemical properties

Authors	Sun Liping, Li Na, Li Qiang, Huo Lihua, Zhao Hui
Source	Journal of Alloys and Compounds Volume: 885, Pages: 160901 Time of Publication: 2021
Abstract	NdBaCo2O5+δ-xCe0.9Gd0.1O1.95 (NBCO-xCGO, x = 0 ~ 8 wt%) composite materials are prepared by novel sol-mixing method and evaluated as cathodes for intermediate-temperature solid oxide fuel cells. The chemical compatibility, thermal expansion behavior and electrochemical performance of NBCO-xCGO composite cathodes are studied. There is no chemical reaction between NBCO and CGO after sintering at 1100 °C for 12 h. Introducing CGO leads to the decrease of both thermal expansion coefficient and conductivity. Among all the composites, NBCO-5CGO shows the lowest polarization resistance of 0.034 Ω cm2 at 700 °C. The anode-supported single-cell with NBCO-5CGO cathode exhibits a maximum power density of 1.0 W cm−2 at 700 °C. The electrochemical impedance spectrum measurement combining with the distribution of relaxation times analysis proves that the addition of CGO nanoparticles significantly improves the surface oxygen dissociation process, and the charge transfer process is identified to be the reaction limiting step to control the oxygen reduction kinetics on NBCO-5CGO composite cathode.
Keywords	Intermediate-temperature solid oxide fuel cell; Composite cathode; Distribution of relaxation times analysis; Oxygen reduction kinetics
Remark	https://doi.org/10.1016/j.jallcom.2021.160901 Link

ID=641

Impedance spectroscopy studies of the chlorophosphate glasses

Authors	L. Ouachouo, L. Bih, E. Haily, M. Jerroudi, I. Saadoune
Source	Materials Today: Proceedings Time of Publication: 2021
Remark	https://doi.org/10.1016/j.matpr.2021.06.041 Link

ID=640

Optical properties and frequency-dependent conductivity of K2O-BaO-TiO2-P2O5 glasses

Authors	E. Haily, L. Biha, M. Jerroudi, A. El bouari
Source	Materials Today: Proceedings Time of Publication: 2021
Abstract	The glass compositions (20-x)K2O-xBaO–30TiO2–50P2O5 with (0ï¿œ¯≤ï¿œ¯xï¿œ¯≤ï¿œ¯20ï¿œ¯mol%) were elaborated using the conventional quenching method. Their related glass-ceramics were developed by controlled crystallization under heat treatments. UV–visible absorption was employed to study the optical properties of the glasses. This technique showed the reduction of Ti4+ to Ti3+ ion content with the substitution of K2O by BaO, and it was found that the BaO addition reduces the structural disorder in the studied glasses. The electrical properties of the glass-ceramics were carried out by impedance spectroscopy in the frequency range from 10ï¿œ¯Hz to 1ï¿œ¯MHz under various temperatures from room temperature to 550ï¿œ¯K. The obtained results showed that the electrical conductivity follows Jonscher’s universal power law and the electrical motion process in the glass-ceramics is provided by the hopping mechanism.
Remark	Link

ID=639

Synthesis and Triple Conductive Properties of Ba and Fe Co-Doped Sr2TiO4 Based Layered Perovskite: (BaxSr2-x) (Ti0.9Fe0.1)O4-δ (X= 0.05, 0.10)

Authors	Yutaro Yagi, Isao Kagomiya, Ken-ichi Kakimoto
Source	Key Engineering Materials Volume: 888, Pages: 37-42 Time of Publication: 2021
Abstract	This study investigated the effects of Ba substitution on protonic conductive properties in the Fe doped Sr2TiO4 layered perovskite. We synthesized sintered samples of (BaxSr2-x)(Ti0.90Fe0.10)O4-δ (x= 0.05, 0.10) (BSTF05, BSTF10). The result of X-ray diffraction suggests that solid solute limitation of Ba is between x= 0.05 and 0.10. BSTF05 at 600 °C shows proton and oxide-ion conductivities as well as elecronic conductivity. It means that BSTF05 is a triple conductor at 600 °C under oxidation atmosphere. The proton conductivities in BSTF05 are lower than that in Ba un-doped Sr2(Ti0.9Fe0.1)O4-δ evaluated in our previous work, suggesting that the effect of the Ba substitution on proton defect generation is small. The redox reaction of Fe ions is more important for creation of proton defects in the layered perovskites.
Remark	https://doi.org/10.4028/www.scientific.net/KEM.888.37 Link

ID=638

Electrochemical, Thermal, and Structural Features of BaF2–SnF2 Fluoride-Ion Electrolytes

Authors	Kazuhiro Mori, Atsushi Mineshige, Takuro Emoto, Maiko Sugiura, Takashi Saito, Kaoru Namba, Toshiya Otomo, Takeshi Abe, and Toshiharu Fukunaga
Source	J. Phys. Chem. C Volume: 125, Issue: 23, Pages: 12568–12577 Time of Publication: 2021
Abstract	Fluoride-ion-conducting compounds are key materials for solid electrolytes in all-solid-state fluoride shuttle batteries (FSBs) and widely regarded as promising rechargeable batteries. However, their ionic conductivities are still insufficient to allow room-temperature operation. Particularly, the transportation of F ions through solid-state ionic devices is yet to be fully understood. We studied the electrochemical, thermal, and structural features of BaF2–SnF2 solid electrolytes by means of AC impedance, differential scanning calorimetry, X-ray diffraction, and neutron diffraction experiments. The substitution of Ba by Sn atoms increased the electrical conductivity of BaF2–SnF2 to 107–109 times that of BaF2; particularly, (BaF2)0.47(SnF2)0.53 exhibited the highest electrical conductivity (σ = 4.1 × 10–3 S/cm at room temperature) with the lowest activation energy (Ea = 17.9 kJ/mol). Structural analysis revealed that (BaF2)0.47(SnF2)0.53 consists of a tetragonal structure (T-phase) and residual amounts of the cubic structure (C-phase). The T-phase could be refined on the basis of a [−SnSnMMSnSn−]-layered structure (M = BaxSn1–x) with three nonequivalent fluorine sites: F1, F2, and F3. The anisotropic displacement of F3 was more pronounced toward F1; thus, the “–F1–F3–F1–” zigzag network between the M and Sn layers plays a key role in two-dimensional fast F-ion diffusion.
Remark	https://doi.org/10.1021/acs.jpcc.1c03326 Link

ID=636

Enhanced activity of catalysts on substrates with surface protonic current in an electrical field – a review

Authors	Yudai Hisai, Quanbao Ma, Thomas Qureishy, Takeshi Watanabe,Takuma Higo, Truls Norby and Yasushi Sekine
Source	Chem. Commun. Volume: 57, Pages: 5737 Time of Publication: 2021
Abstract	It has over the last few years been reported that the application of a DC electric field and resulting current over a bed of certain catalyst-support systems enhances catalytic activity for several reactions involving hydrogen-containing reactants, and the effect has been attributed to surface protonic conductivity on the porous ceramic support (typically ZrO2, CeO2, SrZrO3). Models for the nature of the interaction between the protonic current, the catalyst particle (typically Ru, Ni, Co, Fe), and adsorbed reactants such as NH3 and CH4 have developed as experimental evidence has emerged. Here, we summarize the electrical enhancement and how it enhances yield and lowers reaction temperatures of industrially important chemical processes. We also review the nature of the relevant catalysts, support materials, as well as essentials and recent progress in surface protonics. It is easily suspected that the effect is merely an increase in local vs. nominal set temperature due to the ohmic heating of the electrical field and current. We address this and add data from recent studies of ours that indicate that the heating effect is minor, and that the novel catalytic effect of a surface protonic current must have additional causes.
Remark	Link

ID=632

Microstructure and electrochemical behavior of layered cathodes for molten carbonate fuel cell

Authors	K.Cwieka, A. Lysik, T. Wejrzanowski, T. Norby, W. Xing
Source	Journal of Power Sources Volume: 500, Pages: 229949 Time of Publication: 2021
Abstract	In the present paper, we demonstrate how modifications of the microstructure and the chemical composition can influence the electrochemical behavior of cathodes for molten carbonate fuel cells (MCFCs). Based on our experience, we designed new MCFC cathode microstructures combining layers made of porous silver, nickel oxide or nickel foam to overcome common issues with the internal resistance of the cell. The microstructures of the standard NiO cathode and manufactured cathodes were extensively investigated using scanning electron microscopy (SEM) and porosity measurements. The electrochemical behavior and overall cell performance were examined by means of electrochemical impedance spectroscopy and single-cell tests in operation conditions. The results show that a porous silver layer tape cast onto standard NiO cathode and nickel foam used as a support layer for tape cast NiO porous layer substantially decrease resistance components representing charge transfer and mass transport phenomena, respectively. Therefore, it is beneficial to combine them into a three-layer cathode since it facilitates separation of predominant physio-chemical processes of gas and ions transport in respective layers ensuring high efficiency. The superiority of the three-layer cathode has been proven by low impedance and high power density as compared to standard NiO cathode.
Remark	Link

ID=631

Influence of Doping on the Transport Properties of Y1−xLnxMnO3+δ (Ln: Pr, Nd)

Author	Kacper Cichy and Konrad Swierczek
Source	Crystals Volume: 11, Pages: 510 Time of Publication: 2021
Abstract	It has been documented that the total electrical conductivity of the hexagonal rare-earth manganites Y0.95Pr0.05MnO3+δ and Y0.95Nd0.05MnO3+δ, as well as the undoped YMnO3+δ, is largely dependent on the oxygen excess δ, which increases considerably at temperatures below ca. 300 âŠC in air or O2. Improvement for samples maintaining the same P63cm crystal structure can exceed 3 orders of magnitude below 200 âŠC and is related to the amount of the intercalated oxygen. At the same time, doping with Nd3+ or Pr3+ affects the ability of the materials to incorporate O2, and therefore indirectly influences the conductivity as well. At high temperatures (700–1000 âŠC) and in different atmospheres of Ar, air, and O2, all materials are nearly oxygen-stoichiometric, showing very similar total conduction with the activation energy values of 0.8–0.9 eV. At low temperatures in Ar (δ ≈ 0), the mean ionic radius of Y1−xLnx appears to influence the electrical conductivity, with the highest values observed for the parent YMnO3. For Y0.95Pr0.05MnO3+δ oxide, showing the largest oxygen content changes, the recorded dependence of the Seebeck coefficient on the temperature in different atmospheres exhibits complex behavior, reflecting oxygen content variations, and change of the dominant charge carriers at elevated temperatures in Ar (from electronic holes to electrons). Supplementary cathodic polarization resistance studies of the Y0.95Pr0.05MnO3+δ electrode document different behavior at higher and lower temperatures in air, corresponding to the total conduction characteristics.
Remark	Link

ID=628

Ceramic composites based on Ca3Co4−xO9+δ and La2NiO4+δ with enhanced thermoelectric properties

Authors	R. Hinterding, Z. Zhao, M. Wolf, M. Jakob, O. Oeckler, A. Feldhoff
Source	Open Ceramics Volume: 6, Pages: 100103 Time of Publication: 2021
Abstract	Ceramic composites were produced by combining the oxide materials Ca3Co4−xO9+δ and La2NiO4+δ. Both compounds were characterized by a plate-like crystal shape, but crystal sizes differed by around two orders of magnitude. The composite materials could be successfully prepared by using uniaxial pressing of powder mixtures and pressureless sintering to a porous ceramic. Possible reactions between both materials during sintering were analyzed. The ceramic composites with low amounts of La2NiO4+δ showed enhanced thermoelectric properties, caused by an increasing power factor and simultaneously decreasing thermal conductivity. For the evaluation of the thermoelectric properties, two different types of Ioffe plots were utilized. The maximum figure-of-merit zT at 1073 âK was 0.27 for the pure Ca3Co4−xO9+δ as well as for the sample containing 5 âwt% La2NiO4+δ. However, the average in the temperature range of 373 K to 1073 K could be increased by 20% for the composite material.
Keywords	Calcium cobalt oxide; Composite; Ceramic; Lanthanum nickelate; Reaction sintering; Thermoelectric; Power factor; Figure-of-merit
Remark	Link

ID=627

Amorphous ZnO modified anatase TiO2 thin films templated by tripropylamine and their electrical properties

Authors	Izabella Dascalu, Jose Maria Calderon-Moreno, Petre Osiceanu, Veronica Bratan, Cristian Hornoiu, Simona Somacescu
Source	Thin Solid Films Volume: 729, Pages: 138697 Time of Publication: 2021
Abstract	In the present study we report on a low cost synthesis of amorphous ZnO modified anatase TiO2 (40 and 20 mol% ZnO) thin films deposited via sol-gel spin coating technique on glass substrate. The effects of the composition on the structural, morphological and surface chemistry properties were discussed and correlated with the electrical behavior. Thus, by X-ray diffraction and Raman spectroscopy only TiO2 indexed in the anatase crystalline structure was identified without any ZnO characteristic crystalline phase. The surface chemistry assessed by X-ray Photoelectron spectroscopy highlighted the presence of Ti4+ in TiO2 as well as the presence of Zn2+ coordinated in the amorphous ZnO proved by the Auger ZnLMM transition shifted toward lower binding energies. The films are continuous, homogeneous with grain size below 20 nm and exhibit an intergranular porosity, as it was displayed by Scanning Electron Microscopy. The sensor signal towards CO exposure is strongly related to the amount of the ZnO amorphous phase formation. Thus, we found that a higher content of the ZnO amorphous phase leads to a lower sensitivity. The electrical and sensing measurements were performed in the temperature range (room temperature 400 °C), over the range of CO concentrations (0-2000 ppm). The sensor containing 20 mol.% amorphous ZnO exhibits a good sensitivity at ~300 °C for a low CO concentration .
Keywords	Amorphous zinc oxide; Titanium dioxide; Mixed oxides; Sol-gel spin coating technique; Electrical conductivity; Carbon monoxide detection
Remark	Link

ID=625

Impedance spectroscopy of manganese-doped mixed alkali phosphate glasses

Authors	M. Jerroudi, L. Biha, E. Haily, I. Saadoune
Source	Materials Today: Proceedings Time of Publication: 2021
Abstract	Glassy-compositions in the system 49.95[xNa2O-(1-x)K2O]-0.1MnO2-49.95P2O5 (with x = 0–1 mol%) were elaborated using melt quenching method. The amorphous state of the samples is ensured by the XRD diffraction technique. The electrical properties including dc conductivity, ac conductivity, and electrical modulus were investigated over a large frequency domain at various temperatures. The evolution of the electric conductivity shows a non-linear variation with the composition. It is found that the activation energy is more sensitive to the substitution of the alkali elements and presents a minimum in the intermediate composition (x = 0.5). The non-linearity behavior of the composition dependence of the electrical parameters is a fingerprint of the mixed alkali effect in the glasses under study. The frequency-dependent of the conductivity follows Jonscher’s power law and the correlated barrier hopping mechanism (CBH) was appropriate for the conduction process inside the glasses. In order to avoid the polarization effect due to the electrodes, the electrical modulus formalism is applied to the impedance data. The results obtained show that conduction relaxation is a non-Debye type.
Keywords	Phosphate; Glasses; Mixed alkali effect; Electrical conductivity; Relaxation
Remark	https://doi.org/10.1016/j.matpr.2021.03.467 Link

ID=620

Thermal Conductivity and Thermoelectric Power of Compounds in the Cu–Ge–As–Se System

Authors	O. P. Shchetnikov, N. V. Melnikova, A. N. Babushkin & V. M. Kiseev
Source	Technical Physics volume Volume: 66, Pages: 41–45 Time of Publication: 2021
Abstract	The influence of temperature (in the interval of 300–400 K) and concentrations on the electrical conductivity, thermal conductivity, and thermoelectric power of copper chalcogenide-based crystals with the general formula (GeSe)1 – x(CuAsSe2)x has been considered. Heat transfer mechanisms have been determined. It has been found that the temperature dependence of thermal conductivity is nonmonotonic with a singularity at 358 K. Thermoelectric figure of merit ZT has been calculated.
Remark	Link

ID=618

Mixed ionic-electronic transport in the high-entropy (Co,Cu,Mg,Ni,Zn)1-xLixO oxides

Authors	Maciej Mozdzierz, Juliusz Dabrowa, Anna Stepien, Marek Zajusz, Miroslaw Stygar, Wojciech Zajac, Marek Danielewski, Konrad Swierczek
Source	Acta Materialia Volume: 208, Pages: 116735 Time of Publication: 2021
Abstract	A series of the high-entropy (Co,Cu,Mg,Ni,Zn)1-xLixO oxides with a lithium substitution level of x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30 is evaluated in terms of the crystal structure, morphology and transport properties, with thorough studies aimed at elucidation of the nature of different contributions to the total electrical conductivity. It is found that cubic Fm-3m structure is preserved in the whole investigated series, with (Co,Cu,Mg,Ni,Zn)0.8Li0.2O composition showing a high internal strain, supporting to some degree one of the so-called core effects, anticipated for the high-entropy materials. For samples with Li content x > 0.20 the strain is relaxed by formation of the oxygen vacancies. As unambiguously evidenced by DC polarization experiments and measured impedance spectroscopy data with ionically-blocking Au and reversible Li electrodes used, the previously reported in the literature transition to the lithium superionic conductivity in the Li-rich compounds, up to σi ≈ 1–10⋅10−3 Scm−1, is more complex, with emergence of the electronic conduction as well, reaching similar magnitude for (Co,Cu,Mg,Ni,Zn)0.7Li0.3O. The observed behavior upon increase of lithium concentration (x) can be explained by a qualitative change of the nature of the electronic and ionic defects present in (Co,Cu,Mg,Ni,Zn)1-xLixO series, with initial oxidation of 3d metals (mainly Co), followed by possible formation of the interstitial lithium, and final emergence of the oxygen vacancies. Furthermore, the recorded electrochemical properties of (Co,Cu,Mg,Ni,Zn)0.7Li0.3O lithium cell electrode, suggesting presence of intercalation-like behavior at the initial stages of lithiation, confirm the proposed mixed ionic-electronic conductivity.
Keywords	High-entropy oxides; Crystalline oxides; Lattice defects; Mixed conductor; Li-ion battery
Remark	https://doi.org/10.1016/j.actamat.2021.116735 Link

ID=617

The performance of intermediate temperature solid oxide fuel cells with sputter deposited La1-xSrxCoO3 interlayer

Authors	A. A. Solovyev, A. V. Shipilova, I. V. Ionov, E. A. Smolyanskiy, A. V. Nikonov & N. B. Pavzderin
Source	Journal of Electroceramics Volume: 45, Pages: 156–163 Time of Publication: 2020
Abstract	The paper studies the performance of the intermediate temperature solid oxide fuel cells with the sputter deposited La1-xSrxCoO3 (LSC) interlayer between the cathode and electrolyte. The sputter deposition of the LSC thin films is carried out in argon gas and in a mixture of argon and oxygen gases and then are annealed at 600, 800 and 1000 °C in air for 2 h. The structure and composition of the sputter deposited LSC films are investigated by the X-ray diffraction analysis, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. The polarization resistance of the sputter deposited LSC films (600 nm thick) on the symmetric cells is 0.13, 0.45 and 2.48 Ohm·cm2 measured at 800, 700 and 600 °C, respectively. Measurements are performed by electrochemical impedance spectroscopy. The maximum power density of the anode-supported solid oxide fuel cells with the yttria-stabilized zirconia/gadolinia-doped ceria bilayer electrolyte, LSC interlayer, and LSC cathode is 2.27, 1.58 and 0.68 W/cm2 measured at 800, 700 and 600 °C, respectively. These values of the power density are respectively 1.4, 1.6 and 2.3 times higher than that of the reference cell without the LSC interlayer.
Remark	Link

ID=616

Near-Broken-Gap Alignment between FeWO4 and Fe2WO6 for Ohmic Direct p–n Junction Thermoelectrics

Authors	Raphael Schuler, Federico Bianchini, Truls Norby, and Helmer Fjellvåg
Source	ACS Appl. Mater. Interfaces Volume: 13, Issue: 6, Pages: 7416–7422 Time of Publication: 2021
Abstract	We report a near-broken-gap alignment between p-type FeWO4 and n-type Fe2WO6, a model pair for the realization of Ohmic direct junction thermoelectrics. Both undoped materials have a large Seebeck coefficient and high electrical conductivity at elevated temperatures, due to inherent electronic defects. A band-alignment diagram is proposed based on X-ray photoelectron and ultraviolet–visible light reflectance spectroscopy. Experimentally acquired nonrectifying I–V characteristics and the constructed band-alignment diagram support the proposed formation of a near-broken-gap junction. We have additionally performed computational modeling based on density functional theory (DFT) on bulk models of the individual compounds to rationalize the experimental band-alignment diagram and to provide deeper insight into the relevant band characteristics. The DFT calculations confirm an Fe-3d character of the involved band edges, which we suggest is a decisive feature for the unusual band overlap.
Keywords	thermoelectric oxides, broken-gap junction, Ohmic contact, band alignment, p-n junction, computational first-principles modeling
Remark	https://doi.org/10.1021/acsami.0c19341 Link

ID=615

Effect of the Ba/K ratio on structural, dielectric and energy storage properties of BaO–K2O–TiO2–P2O5 glass-ceramics

Authors	Haily, E.; Bih, L.; El Bouari, A.; Lahmar, A.; El Marssi, M.; Manoun, B.
Source	Physics and Chemistry of Glasses - European Journal of Glass Science and Technology Part B Volume: 61, Issue: 6, Pages: 213-221 Time of Publication: 2020
Abstract	xBaO–(20–x)K2O–30TiO2–50P2O5 with (0≤x≤20 mol%) glasses were successfully elaborated by the melt quenching while their related glass-ceramics were developed by controlled crystallisation. Density and molar volume measurements, differential thermal analysis and Raman spectroscopy were carried out to examine the glassy structure, the results revealed that the addition of BaO increases the reticulation and reinforces the glass network by the creation of strengthened linkages. X-ray diffraction has identified the formation of MTi2(PO4)3 with M=(K, Ba0.5) in all the glass-ceramics (GC) and the precipitation of a secondary BaTiP2O8 phase when x increase beyond 10 mol%. The dielectric properties of the glass-ceramics were studied by impedance spectroscopy, it showed that the addition of BaO induces an enhancement of both thermal and frequency stability of the dielectric parameters (εr and tan δ). The glass-ceramic with 5 mol% of BaO GC-(x=5) presents the highest dielectric constant and the lowest dielectric loss. The P-E hysteresis loops were recorded at room temperature and the energy storage parameters of the glass-ceramics were determined. These parameters were significantly improved by the increase of the BaO content and the optimum parameters were obtained for GC-(x=5). The dielectric and energy storage parameters were discussed according to the structure data.
Remark	DOI: https://doi.org/10.13036/17533562.61.6.015 Link

ID=614

Modification of Ruddlesden-Popper-type Nd2-xNi0.75Cu0.2M0.05O4±δ by the Nd-site cationic deficiency and doping with Sc, Ga or In: Crystal structure, oxygen content, transport properties and oxygen permeability

Authors	Anna Niemczyka, Anna Stepien, Kacper Cichy, Juliusz Dabrowa, Zijia Zhang, Barthomiej Gedziorowski, Kun Zheng, Hailei Zhao, Konrad Swierczek
Source	Journal of Solid State Chemistry Volume: 296, Pages: 121982 Time of Publication: 2021
Abstract	Nd2-xNi0.75Cu0.2M0.05O4±δ (x â= â0 and 0.1; M â= âSc, Ga, and In) Ruddlesden-Popper-type oxides are obtained by a sol-gel route and characterized concerning phase composition and crystal structure. It is found that the largest In3+ cannot be effectively introduced into the structure, while Nd stoichiometric and cation-deficient Nd2-xNi0.75Cu0.2Sc0.05O4±δ and Nd2-xNi0.75Cu0.2Ga0.05O4±δ (x â= â0; 0.1) can be obtained as single-phase materials. Systematic characterization of the crystal structure at high temperatures, oxygen content, as well as transport properties reveals that while the Nd-site deficiency has rather negligible influence on the structure, it causes a substantial decrease of the oxygen content, which at high temperatures leads to a change of the dominant type of defects from the oxygen interstitials to the vacancies for Nd1.9Ni0.75Cu0.2Sc0.05O4±δ and Nd1.9Ni0.75Cu0.2Ga0.05O4±δ. The Nd-site deficiency also causes a decrease of the total conductivity. Importantly, all the examined materials exhibit full chemical stability in CO2 atmosphere, which together with moderate thermal expansion makes them good candidates for the oxygen transport membranes, which can be used e.g. in the air separation technologies. The selected Sc- and Ga-doped compounds evaluated as ceramic membranes show relatively high oxygen fluxes, with the highest value of 0.78 âmL âcm-2 min-1 at ca. 880 â°C registered for 0.9 âmm thick, dense Nd1.9Ni0.75Cu0.2Ga0.05O4±δ membrane.
Keywords	Ruddlesden-Popper oxides; Nonstoichiometric compounds; Crystal structure; Transport properties; Oxygen permeation membranes
Remark	Link

ID=610

Comparative investigation on the functional properties of alkaline earth metal (Ca, Ba, Sr) doped Nd2NiO4+δ oxygen electrode material for SOFC applications

Authors	R. K. Lenka, P.K.Patro, Vivek Patel, L. Muhmood, T. Mahata
Source	Journal of Alloys and Compounds Volume: 860, Pages: 158490 Time of Publication: 2021
Abstract	Functional properties of Nd2NiO4+δ based materials doped with different alkaline earth metal ions for SOFC applications is studied extensively and compared in this article. Phase pure powders of Nd2NiO4 +δ and Nd1.7A0.3NiO4+δ (A=Ca, Sr and Ba) were synthesized by solid state route at 1250 °C from the constituent precursor oxides and carbonates. Good compatibility of these cathode materials with GDC electrolyte is confirmed through XRD analysis of the composite powder heat treated at 1250 °C. Electrical conductivity of undoped Nd2NiO4+δ is found to attain a maximum at ~470 °C and then decreases noticeably with increase in temperature. The decrease in conductivity at higher temperatures is not significant for alkaline earth metal ion doped systems. In the lower temperature range, electrical conductivity decreases with alkaline earth metal ion doping and this decrement is more as the size of the dopant cation increases with an exception for Sr doped samples. However, at the operating temperature of the fuel cell (say 800 °C) electrical conductivity of Ca and Sr doped Nd2NiO4+δ are higher than the undoped material. Polarization resistance of the cathode materials are evaluated from the measured impedance spectra of symmetric cells and activation energy for oxygen reduction reaction is calculated from the Arrhenius plot of polarization resistance. Activation energy decreases with alkaline earth metal ion doping and this decrease is more in case of Ca doping followed by Sr and Ba doping. Electrolyte supported button cells fabricated under identical processing conditions were tested at 800 °C; highest power density of 188 mW cm−2 is obtained for the cell having Ca doped Nd2NiO4+δ as oxygen electrode.
Keywords	SOFC; Air electrode; Nd2NiO4; Area specific resistance; I-V characteristics
Remark	https://doi.org/10.1016/j.jallcom.2020.158490 Link

ID=609

Synthesis and processing of SOFC components for the fabrication and characterization of anode supported cells

Authors	Aritza Wain-Martin, Roberto Campana, Aroa Morán-Ruiz, Aitor Larrañaga, María Isabel Arriortua
Source	Boletín de la Sociedad Española de Cerámica y Vidrio Time of Publication: 2020
Abstract	In this article, it is intended to evaluate the performances of previously synthesized different nanometric compounds as SOFC components under real conditions. For this purpose, anodic supports SOFCs have been manufactured in different configurations. The compounds NiO-(Y2O3)0.08(ZrO2)0.92 (NiO–YSZ), (Y2O3)0.08(ZrO2)0.92 (YSZ), Sm0.2Ce0.8O1.9 (SDC), La0.6Sr0.4FeO3 (LSF) and LaNi0.6Fe0.4O3 (LNF) were used as anode support, electrolyte, barrier, cathode and contact layer, respectively. To obtain the cells, the anode supports were produced by uniaxial pressing and the remaining layers were added using the airbrush technique, assembling them by different sintering processes. The cells developed have been electrochemically tested in a temperature range between 750 and 865 °C. Additionally, degradation tests have been carried out under constant current. Moreover, to characterize the microstructure of the cells, a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectroscopy (EDX) analyzer has been used. The results obtained show that the incorporation of cathode and contact layers increases the power densities and decreases the total resistances of the cells with respect to the cell without cathode, especially with the addition of the LNF contact layer. Despite the improvement obtained, more tests have to be carried out in order to optimize the performance of SOFC devices in degradation tests.
Keywords	Solid oxide fuel cells; Processing; Composite; Degradations; Electrochemical impedance spectra
Remark	Available online 22 December 2020 Link

ID=608

Increasing the thermal expansion of proton conducting Y-doped BaZrO3 by Sr and Ce substitution

Authors	Amir Masoud Dayaghi, Reidar Haugsrud, Marit Stange, Yngve Larring, Ragnar Strandbakke, Truls Norby
Source	Solid State Ionics Volume: 359, Pages: 115534 Time of Publication: 2021
Abstract	Proton conducting oxide electrolytes find potential application in proton ceramic fuel cells and electrolyzers operating at intermediate temperatures, e.g. 400–600 °C. However, state-of-the-art proton conducting ceramics based on Y-doped BaZrO3 (BZY) have lower thermal expansion coefficient (TEC) than most commonly applied or conceived supporting electrode structures, making the assembly vulnerable to degradation due to cracks or spallation. We have increased the TEC of 20 mol% Y-doped BZY (BZY20) by partially substituting Ba and Zr with Sr and Ce, respectively, to levels which still maintain the cubic structure and sufficiently minor n-type conduction; (Ba0.85Sr0.15)(Zr0.7Ce0.1Y0.2)O2.9 (BSZCY151020). High temperature XRD shows that this material has a cubic structure (space group ) in the temperature range of 25–1150 °C and a linear TEC of ~10 × 10−6 K−1, as compared to the ~8 × 10−6 K−1 for BZY. It exhibited a DC conductivity of ~5 mS cm−1 at 600 °C in wet H2. This electrolyte with increased TEC may find application in proton ceramic electrochemical cells in general and metal supported ones in particular.
Keywords	Barium zirconate; BZY; Thermal expansion coefficient; TEC; Conductivity; Proton; Proton ceramic electrochemical cells; Metal-supported
Remark	https://doi.org/10.1016/j.ssi.2020.115534 Link

ID=607

Properties of Barium Cerate Thin Films Formed Using E-Beam Deposition

Authors	Monica Susana Campos Covarrubias, Mantas Sriubas, Kristina Bockute, Piotr Winiarz, Tadeusz Miruszewski, Wojciech Skubida, Daniel Jaworski, MichaÅ Bartmanski, Marek Szkodo, Maria Gazda and Giedrius Laukaitis
Source	Crystals Volume: 10, Pages: 1152 Time of Publication: 2020
Abstract	This article focuses on the properties of the BaCeO3 thin films formed by electron-beam vapor deposition and investigates the formation of barium cerates on supports with different thermal expansion coefficients (Stainless Steel, Invar, Glass Sealing, and Inconel substrates) and the influence of the technological parameters on the properties of the formed thin films with an emphasis on the stability of the films. Morphology and phase composition and mechanical and electrical properties were investigated. It was found that the main factors influencing the phase composition and morphology of the films are the temperature of the support and the deposition rate. However, the mechanical properties of the films are mostly influenced by strains introduced to thin films by using different supports. Two interesting features of the electrical properties of the studied strained films were noticed: the film with the highest in-plane tensile strain showed the lowest activation energy of total conductivity, whereas the film with the lowest strain showed the highest value of total conductivity.
Remark	Link

ID=603

From insulator to oxide-ion conductor by a synergistic effect from defect chemistry and microstructure: acceptor-doped Bi-excess sodium bismuth titanate Na0.5Bi0.51TiO3.015

Authors	Fan Yang, Julian S. Dean, Qiaodan Hu, Patrick Wu, Emilio Pradal-Velázquez, Linhao Li and Derek C. Sinclair
Source	Journal of Materials Chemistry A Issue: 47 Time of Publication: 2020
Abstract	The influence of Ti-site acceptor-doping (Mg2+, Zn2+, Sc3+, Ga3+ and Al3+) on the electrical conductivity and conduction mechanism of a nominally Bi-excess sodium bismuth titanate perovskite, Na0.5Bi0.51TiO3.015 (NB0.51T), is reported. Low levels of acceptor-type dopants can introduce appreciable levels of oxide-ion conductivity into NB0.51T, i.e., 0.5% Mg-doping for Ti4+ can enhance the bulk conductivity of NB0.51T by more than 3 orders of magnitude with the oxide-ion transport number going from <0.1 for NB0.51T to >0.9 at 600 °C. The intriguing electrical behaviour in acceptor-doped NB0.51T dielectrics is a synergistic effect based on the defect chemistry and ceramic microstructure in these materials. NB0.51T ceramics with extremely low levels of doping show an inhomogeneous microstructure with randomly distributed large grains embedded in a small grained matrix. This can be considered as a two-phase composite with large grains as a conductive phase and small grains as an insulating phase based on an empirical conductivity – grain size relationship. Variation in the fraction of the conductive, large grained phase with increasing doping levels agrees with the oxide-ion transport number. This electrical two-phase model is supported by finite element modelling. This study reveals the significance of ceramic microstructure on the electrical conduction behaviour of these materials and can provide a guideline for selecting suitable doping strategies to meet the electrical property requirements of NBT-based ceramics for different applications.
Remark	Link

ID=601

NiO–ZnO based junction interface as high-temperature contact materials

Author	Temesgen D.Desissa
Source	Ceramics International Volume: 47, Issue: 6, Pages: 8053-8059 Time of Publication: 2021
Abstract	Contact materials play a crucial role in an electronic device operating at moderate and elevated temperatures where chemical and thermal stability is of great importance. Oxide materials and their interfaces are potential candidates as high-temperature contact materials due to their high chemical and thermal stabilities. In this work, polycrystalline oxides of Ni0.98Li0.02O and Zn0.98Al0.02O were used to make junction interfaces, where the solid-state synthesis method was used to obtain the individual oxide materials. After assembly of the junction interfaces, properties such as electrical, chemical, and thermal stabilities of the interfaces were investigated. The electrical properties were assessed through current-voltage (I–V) and electrochemical impedance spectroscopy (EIS) measurements, where the interface revealed a transition from electrically rectifying to slightly ohmic contact within a temperature range from 500–1000 °C. After annealing the junction interfaces at these elevated temperatures, no secondary phase was observed at the junction interface, i.e., the interfaces remain chemically stable. Moreover, the effect of isothermal annealing on the I–V characteristics curve of the junction showed an increased reverse current output over long annealing time, attributed mainly to the increased effective contact area at the junction interface and cation inter-diffusion processes. Furthermore, an investigation of the cation inter-diffusion mechanism revealed mainly lattice diffusion of Zn2+ into Ni0.98Li0.02O, while Ni2+ diffusion into Zn0.98Al0.02O exhibited both lattice and grain-boundary diffusion mechanisms.
Keywords	Interfaces; Thermal stability; Electrical properties; Diffusion
Remark	Link

ID=599

Cation-driven electrical conductivity in Ta-doped orthorhombic zirconia ceramics

Authors	Bibi Malmal Moshtaghioun, Miguel A. Laguna-Bercero, Jose I. Peña, Diego Gómez-García, Arturo Domínguez-Rodríguez
Source	Ceramics International Volume: 47, Issue: 5, Pages: 7248-7252 Time of Publication: 2021
Abstract	This paper is devoted to the study of the electrical conductivity of tantalum-doped zirconia ceramics prepared by spark plasma sintering. In this study, the temperature dependence of conductivity in as-prepared specimens and in those previously annealed in air is determined and compared. A semi-empirical model, which is based on the oxidation states of the cations, has been developed and successfully assessed. According to this, the conductivity is basically controlled by the diffusion of tetravalent zirconium cations in both cases, although the concentration of these species varies drastically with the amount of induced oxygen vacancies. This is a quite unexpected fact, since conductivity is normally controlled by anionic diffusion in zirconia ceramics. This option is forbidden here due to the presence of substitutional pentavalent cations. Therefore, conductivity values are much lower than those reported in trivalent or divalent substitutional cation doped zirconia ceramics.
Remark	Link

ID=598

Direct Solid Oxide Electrolysis of Carbon Dioxide:Analysis of Performance and Processes

Authors	Severin Foit, Lucy Dittrich, Tobias Duyster, Izaak Vinke, Rüdiger-A. Eichel and L.G.J. (Bert) de Haart
Source	Processes Volume: 8, Pages: 1390 Time of Publication: 2020
Abstract	Chemical industries rely heavily on fossil resources for the production of carbon-basedchemicals. A possible transformation towards sustainability is the usage of carbon dioxide as asource of carbon. Carbon dioxide is activated for follow-up reactions by its conversion to carbonmonoxide. This can be accomplished by electrochemical reduction in solid oxide cells. In thiswork, we investigate the process performance of the direct high-temperature CO2electrolysis bycurrent-voltage characteristics (iV) and Electrochemical Impedance Spectroscopy (EIS) experiments.Variations of the operation parameters temperature, load, fuel utilization, feed gas ratio and flowrate show the versatility of the procedure with maintaining high current densities of 0.75 up to1.5 A·cm−2, therefore resulting in high conversion rates. The potential of the high-temperature carbondioxide electrolysis as a suitable enabler for the activation of CO2as a chemical feedstock is thereforeappointed and shown.
Remark	Link

ID=597

Structural, optical, and dielectric properties of Bi2O3-K2O-TiO2-P2O5 glasses and related glass-ceramics

Authors	E. Hailya, L. Bih, A. El Bouari, A. Lahmar, M. El Marssi & B. Manoun
Source	Phase Transitions Volume: 93, Issue: 10-11 Time of Publication: 2020
Abstract	The glasses in the Bi2O3-K2O-TiO2-P2O5 system were elaborated by the conventional quenching method. Their structure was studied by Raman spectroscopy, and additional information is determined from density measurements and thermal analysis. The optical absorption of the glasses is investigated and it is found that the optical gap and the Urbach energy decrease and increase, respectively, with increasing Bi2O3 content. The crystallization of the glasses was performed under controlled heat treatments to develop glass-ceramics. Their dielectric constants are carried out by impedance spectroscopy. The variations of the permittivity (Ïµr) and the dielectric loss (tanδ) versus frequency and temperature are determined. It is evidenced that the introduction of Bi2O3 in the glasses diminished the dispersion at low frequencies. The presence of bismuth oxide in the materials is also beneficial since it allowed the formation of glass-ceramics with high dielectric constant and low dielectric loss.
Remark	Link

ID=596

Strategies to Mitigate the Degradation of Stainless-SteelInterconnects Used in Solid Oxide Fuel Cells

Author	Claudia GÐŸbel
Source	Time of Publication: 2020
Abstract	Interconnects are a vital part of solid oxide fuel cells (SOFC), where they electricallyconnect individual cells to form a fuel cell stack. They are a main contributor to theoverall stack cost and the limited life-time of fuel cells, and, therefore, improvementscarried out on the interconnect level could further the commercialization of SOFCs.The limited life-time of the interconnect is related to the material used today, ferriticstainless steels (FSS). FSS interconnects are more cost-effective than previously usedceramics, but they degrade under the conditions prevalent in an SOFC: high temperaturesbetween 600°C and 850°C, and a p(O2) gradient. Certain corrosion phenomena thatoccur, such as Cr evaporation and continuous oxide scale growth, negatively impact cellperformance due to cathode poisoning and increased electrical resistance, respectively.These phenomena have been found to be effectively mitigated by coatings, such as the(Co,Mn)3O4(MCO) coating, or reactive element coatings, such as Ce.The present thesis examines these coatings with regard to three aspects: (i) doesthe semi-conducting spinel coating affect the electrical resistance of the interconnectnegatively, or is its conductivity negligible in comparison to the continuously growingCr2O3scale below it; (ii) does the coating self-heal if it is cracked even at intermediatetemperatures, i.e. 650°C and 750°C, or do the cracks persist and increase Cr evaporation;and (iii) is the long-term stability of the state-of-the-art Ce/Co coating (10 nm Ce/640 nmCo) still effective after 35 000 h, or not. The second aspect is not only important tounderstand corrosion behavior, but it would also allow for large-scale roll-to-roll PVDcoating, which is significantly more cost-effective than batch coating.Another corrosion phenomenon that is elucidated within the scope of this work is thedual atmosphere effect. This effect leads to increased corrosion on the air-facing side ofthe interconnect if the FSS is exposed to a dual atmosphere, i.e. air on one side andhydrogen on the other side, compared to if the FSS is exposed to an air-only atmosphere.A new theory as to why the dual atmosphere effect occurs is proposed, and it is indirectlyverified by means of excluding all other possibilities. Factors that influence the dualatmosphere effect are discussed, and it is shown how the dual atmosphere effect could, inpart, be mitigated.
Keywords	Solid Oxide Fuel Cell; Corrosion; Interconnect; Cr Evaporation; Area SpecificResistance; Deformation; Long-term; Dual Atmosphere; Hydrogen
Remark	THESIS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Link

ID=594

Mitigation of grain boundary resistance inLa2/3-xLi3xTiO3perovskite as an electrolyte forsolid-state Li-ion batteries

Authors	Tomasz Polczyk, Wojciech Zajac, Magdalena Ziabka, and Konrad Swierczek
Source	J Mater Sci Energy materials Pages: 2435–2450 Time of Publication: 2021
Abstract	In this work, we report that modification of the chemical composition of grainboundaries of La2/3-xLi3xTiO3double perovskite, one of the most promising Li-ion conducting solid electrolytes, can be a convenient and versatile way ofcontrolling the space charge potential, leading to a mitigated electrical resistanceof the grain boundaries. Two groups of additives are investigated: lithium-enriching agents (Li3BO3, LiF) and 3dmetal ions (Co2?,Cu2?), both expected toreduce the Schottky barrier. It is observed that Li-containing additives workeffectively at a higher sintering temperature of 1250°C. Regarding copper, itshows a much stronger positive impact at lower temperature, 1150°C, while theaddition of cobalt is always detrimental. Despite overall complex behavior, it isdocumented that the decreased space charge potential plays a more importantrole in the improvement of lithium conduction than the thickness of the grainboundaries. Among the proposed additives, modification of La2/3-xLi3xTiO3by2 mol.% Cu2?results in the space charge potential reduction by 32 mV inrelation to the reference sample, and the grain boundary specific conductivityincrease by 80%, as measured at 30°C. Introduced additive allows to obtain asimilar effect on the conductivity as elevating the sintering temperature, whichcan facilitate manufacturing procedure.
Remark	Link

ID=593

Crystal structures and proton transport properties of Sr2(Ti1-xMx)O4-δ (M = Fe, Al)

Authors	Yutaro Yagi, Isao Kagomiya, Ken-ichi Kakimoto
Source	Solid State Sciences Volume: 108, Pages: 106407 Time of Publication: 2020
Abstract	This study focuses on the effects of acceptor dopants in proton-conductive Sr2TiO4-based layered perovskites. We synthesized Sr2Ti0.9Fe0.1O4-δ (STF10) and Sr2Ti0.95Al0.05O4-δ (STA05) and evaluated the influence of ion substitution on their crystal structures, electrical conductivities, and proton transport properties. Our obtained results suggest that a redox reaction is the more favorable mechanism for the introduction of proton defects to Fe-doped samples compared with water vapor absorption, while the reverse is true for Al-doped samples. STF10 was found to exhibit a larger electrical conductivity at low temperatures than STA05. In addition, STF10 presented a proton transport number of 0.5 at 600 °C, while the corresponding value for STA05 was 0.5–0.6 at 450–600 °C. The higher proton transport number of STA05 at 450–550 °C compared to that of STF10 indicates that the Al-dopant suppressed the electronic conductivity owing to its constant valency. We therefore considered that characterization of the changes in material properties related to ion substitution can serve as a guide for material selection when developing proton-conducting solid oxide fuel cell technologies.
Remark	Link

ID=592

Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li2OHCl

Authors	Fei Wang, Hayden A. Evans, Kwangnam Kim, Liang Yin, Yiliang Li, Ping-Chun Tsai, Jue Liu, Saul H. Lapidus, Craig M. Brown, Donald J. Siegel, and Yet-Ming Chiang
Source	Chem. Mater. Volume: 32, Issue: 19, Pages: 8481–8491 Time of Publication: 2020
Abstract	Li2OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having ∼1/3 of the Li sites vacant, while the presence of the OH– anion introduces the possibility of rotational disorder that may be coupled to cation migration. Here, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li2OHCl, which undergoes an orthorhombic to cubic phase transition near 311 K (≈38 °C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 × 10–5mS/cm at 37 °C to 1.4 × 10–3 mS/cm at 39 °C). X-ray and neutron experiments conducted over the temperature range 20–200 °C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to “paddlewheel” rotation of the dynamic OH– anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility.
Remark	Link

ID=591

Conduction properties of acceptor-doped BaTiO3–Bi(Zn1/2Ti1/2)O3-based ceramics

Authors	Ryan R. McQuade, Pavel Mardilovich, Nitish Kumar & David P. Cann
Source	Journal of Materials Science Volume: 55, Pages: 16290–16299 Time of Publication: 2020
Abstract	A series of acceptor-doped ceramics based on the solid solution, (1-x)BaTiO3–xBi(Zn1/2Ti1/2)O3 (BT-BZT), where x = 0.1, 0.2, 0.3, 0.4, were prepared via solid-state synthesis to investigate the effect of doping and BZT content on conduction properties. Impedance spectroscopy measurements showed an increase in conductivity through acceptor doping with Mg on the Ti-site (Mg′′Ti). Ceramics of the composition, 0.80BaTiO3–0.20Bi(Zn1/2Ti1/2)O3 with 3 mol% Mg′′Ti, showed the highest conductivity in this study at 1.28 mScm−1 (~ 600 °C), an order of magnitude improvement over the stoichiometric composition. Variable pO2 impedance measurements revealed p-type conductivity in the grain while EMF measurements showed that above ~ 550 °C, ions are the dominant charge carriers (transference number, ti = 0.91 at 735 °C). Similarly, all 3 mol% Mg-doped compositions above x = 0.1 were primarily ionic conductors with transference numbers above ti = 0.79 (735 °C). X-ray diffraction data showed a pseudocubic primary phase for all samples with evidence of additional impurity phases accompanying samples with 3 mol% Mg′′Ti or greater.
Remark	Link

ID=589

Ionic conductivity in LixTaOy thin films grown by atomic layer deposition

Authors	Yang Hu, Ville Miikkulainen, Kenichiro Mizohata, Truls Norby, Ola Nilsen, Helmer Fjellvåg
Source	Electrochimica Acta Volume: 361, Pages: 137019 Time of Publication: 2020
Abstract	The material system Li-Ta-O is a promising candidate for thin-film solid-state electrolytes in Li-ion batteries. In the present study, we have varied the Li content x in LixTaOy thin films grown by atomic layer deposition (ALD) with the aim of improving the Li-ion conductivity. The amorphous films were grown at 225 °C on insulating sapphire and on conductive Ti substrates using tantalum ethoxide (Ta(OEt)5), lithium tert-butoxide (LiOtBu) and water as reactants. The film composition was determined by time-of-flight elastic recoil detection analysis (TOF-ERDA), displaying an almost linear relationship between the pulsed and deposited Li content. The ionic conductivities were determined by in-plane and cross-plane AC measurements, exhibiting an Arrhenius-type behaviour and comparatively weak thickness-dependence. Increasing Li content x from 0.32 to 0.98 increases the film conductivity by two orders of magnitude while higher Li content x = 1.73 results in decreased conductivity. A room-temperature conductivity σRT of ~10−8 S cm−1 is obtained for a 169 nm thick Li0.98TaOy film. The evolution of conductivity and activation energy suggests a competing effect between the concentration and the mobility of mobile Li ions when more Li are incorporated. The compositional dependence of Li transport mechanism is discussed.
Keywords	Atomic layer deposition; LixTaOy thin films; Solid-state electrolytes; TOF-ERDA; Ionic conductivity
Remark	Link

ID=587

Structural and Electrochemical Properties of Tysonite Ce0.95A0.05F2.95 (A = Mg, Ca, Sr, and Ba): Fast-Fluoride-Ion-Conducting Solid Electrolytes

Authors	Kazuhiro Mori, Yoshiyuki Morita, Takashi Saito, Takashi Kamiyama, Toshiya Otomo, Takeshi Abe, and Toshiharu Fukunaga
Source	J. Phys. Chem. C Volume: 124, Issue: 34, Pages: 18452–18461 Time of Publication: 2020
Abstract	All-solid-state fluoride shuttle batteries (FSBs) present endless possibilities for next-generation rechargeable batteries. However, no standard choice for solid electrolytes and electrodes in FSBs has been established to date. Additionally, details of how F ions travel through the working device are yet to be fully understood. Here, we studied the electrochemical properties of tysonite Ce0.95A0.05F2.95 (A = Ca, Sr, and Ba) and Ce0.95Mg0.05F2.95 (actually, a composite of CeF3 and MgF2) solid electrolytes, and their crystal structures using neutron diffraction data. In particular, Ce0.95Ca0.05F2.95 exhibited the highest electrical conductivity and the shortest bond between F ions. Furthermore, F-vacancies introduced by the substitution of Ca2+ for Ce3+ were accommodated only at the F1 site. The bond valence sum (BVS) analysis results indicated that there was a significant difference in the BVS values of F ions: BVS(F1) = −0.92 on [F1] layers, and BVS(F2) = −1.13 and BVS(F3) = −1.07 on [M (=Ce0.95Ca0.05), F2, F3] layers, which were stacked alternately along the c-axis of the trigonal cell. The BVS(F2) value was relatively lower than the BVS(F1) and BVS(F3) ones, indicating that F2 is tightly bonded to M compared to that of F1 or F3. The findings suggested that F1–F1 and F1–F3 sublattices play a key role in the high mobility of the conducting F ions.
Remark	Link

ID=585

Structural and Electrochemical Properties of Tysonite Ce0.95A0.05F2.95 (A = Mg, Ca, Sr, and Ba): Fast-Fluoride-Ion-Conducting Solid Electrolytes

Authors	Kazuhiro Mori, Yoshiyuki Morita, Takashi Saito, Takashi Kamiyama, Toshiya Otomo, Takeshi Abe, and Toshiharu Fukunaga
Source	J. Phys. Chem. C Volume: 124, Issue: 34, Pages: 18452–18461 Time of Publication: 2020
Abstract	All-solid-state fluoride shuttle batteries (FSBs) present endless possibilities for next-generation rechargeable batteries. However, no standard choice for solid electrolytes and electrodes in FSBs has been established to date. Additionally, details of how F ions travel through the working device are yet to be fully understood. Here, we studied the electrochemical properties of tysonite Ce0.95A0.05F2.95 (A = Ca, Sr, and Ba) and Ce0.95Mg0.05F2.95 (actually, a composite of CeF3 and MgF2) solid electrolytes, and their crystal structures using neutron diffraction data. In particular, Ce0.95Ca0.05F2.95 exhibited the highest electrical conductivity and the shortest bond between F ions. Furthermore, F-vacancies introduced by the substitution of Ca2+ for Ce3+ were accommodated only at the F1 site. The bond valence sum (BVS) analysis results indicated that there was a significant difference in the BVS values of F ions: BVS(F1) = −0.92 on [F1] layers, and BVS(F2) = −1.13 and BVS(F3) = −1.07 on [M (=Ce0.95Ca0.05), F2, F3] layers, which were stacked alternately along the c-axis of the trigonal cell. The BVS(F2) value was relatively lower than the BVS(F1) and BVS(F3) ones, indicating that F2 is tightly bonded to M compared to that of F1 or F3. The findings suggested that F1–F1 and F1–F3 sublattices play a key role in the high mobility of the conducting F ions.
Remark	Link

ID=584

Structural characterization and electrical/electrochemical studies of Nd1-xBaxCo1-y(Fe, Ti)y O3-δ (0 ≤ x ≤ 0.3, y = 0, 0.2) materials as cathode for SOFCs application

Authors	Paramananda Jena, Dinesh Kumar, Pankaj Kumar Patro, Raja Kishora Lenka, Akhilesh Kumar Singh
Source	Journal of Solid State Chemistry Volume: 292, Pages: 121682 Time of Publication: 2020
Abstract	Perovskite oxide powders of Nd1-xBaxCo1-y (Fe, Ti)y O3-δ (0 ≤ x â≤ â0.3, y â= â0, 0.2) were synthesized by combustion technique and investigated as cathode materials for SOFCs application. The Rietveld refinement of the XRD data confirms the formation of single phase orthorhombic perovskite structure of Pbnm space group within the compositions (0 â≤ âx â≤ â0.1, y â= â0, 0.2). The microstructural studies revealed the grains generated are irregular in shape and non uniform in size in the micrometer range. The X-ray photoelectron spectroscopy (XPS) analysis confirms the presence of mixed valence states of Co3+/Co4+, Fe3+/Fe4+, Ti4+/Ti3+ and O-Lattice/O-Chemisorbed/O-physisorbed species. The measured average CTE values are varies from 18–25 â× â10−6 âK−1 in the temperature range 200–900 â°C for all the synthesized samples. The electrical conductivity values are found to be 252 Scm−1, 308 Scm−1, 157 Scm−1 at 700 â°C for the compositions Nd0.9Ba0·1CoO3-δ (NBC 0.1), Nd0.9Ba0·1Co0·8Fe0·2O3-δ (NBCFO), Nd0.9Ba0·1Co0·8Ti0·2O3-δ (NBCTO), respectively. XRD analysis reveals no chemical reactivity for the compositions NBCFO, NBCTO with 20 âmol% gadolinium doped ceria oxide (Ce0.8Gd0.2O2−δ) electrolyte material after firing at 1200 â°C for 8 âh. The area specific resistances (ASR) were calculated for the symmetrical cells and are found to be 0.67 âΩ âcm2, 1.07 âΩ âcm2 at 850 â°C for the NBCFO, NBCTO compositions, respectively. Among the compositions evaluated Nd0.9Ba0·1Co0·8Fe0·2O3-δ showed highest total electrical conductivity ~308 Scm−1 and lowest ASR value ~0.67 Ωcm2 compared to all other compositions. Hence the result suggests the synthesized Nd0.9Ba0·1Co0·8Fe0·2O3-δ composition could be a promising cathode material for SOFCs application.
Remark	Link

ID=583

Effect of the Complexing Agent in the Pechini Method on the Structural and Electrical Properties of an Ionic Conductor of Formula La1−xSrxAlO3−δ (x = 0, 0.05, 0.1, 0.15)

Authors	F. Hadji, F. Bouremmad, S. ShawutiM. A. Gulgun
Source	Advances in Renewable Hydrogen and Other Sustainable Energy Carriers Pages: 387-393 Time of Publication: 2020
Abstract	The Ion conductors are used as electrolytes in high temperature Solid Oxide Fuel Cells SOFCs. The preparation route has an important role on their structural and electrical properties. In this study, we used a modified Pechini method to prepare an ionic conductor based on lanthanum aluminate doped with strontium La1−xSrxAlO3−δ (x = 0.0.05, 0.1, 0.15). The effect of two complexing agents on structural and electrical properties was studied, we used Ethylene Diamine Tetra Acetic EDTA, and tartaric acid TA as complexing agents. The perovskite phases were obtained at 900 °C and characterized by different techniques; SEM images show that grain size is in the nanometer range, XRD analysis shows that the compounds prepared by use of the two complexing agents crystallize in a perovskite structure with an orthorhombic system and an R3m space group, the doped phases prepared by EDTA have a secondary phase LaSrAl3O7 which is absent in the compounds prepared by tartaric acid. The determination of the ionic conductivity by electrochemical impedance spectroscopy shows clearly the effect of the complexing agent. Indeed we have found that the value of the ionic conductivity is higher for the phases produced by the Pichini method in the presence of tartaric acid as complexing agent.
Remark	Link

ID=582

High Cu content LaNi1-xCuxO3-δ perovskites as candidate air electrode materials for Reversible Solid Oxide Cells

Authors	Anna Niemczyk, Kun Zheng, Kacper Cichy, Katarzyna Berent, Kathrin Küster, Ulrich Starke, Bisham Poudel, Bogdan Dabrowski, Konrad Åšwierczek
Source	International Journal of Hydrogen Energy Volume: 45, Issue: 53, Pages: 29449-29464 Time of Publication: 2020
Abstract	High Cu content perovskite-type LaNi1-xCuxO3-δ oxides are evaluated as alternative air electrode materials for Solid Oxide Cells. Auto-combustion synthesis allowed to obtain fine oxide powders up to a Cu content of x = 0.75 under ambient pressure. Investigations of the crystal structure, oxygen deficiency, chemical and thermal stability, as well as transport properties reveal satisfactory characteristics, with high total electrical conductivity and high concentration of oxygen vacancies at elevated temperatures. LaNi1-xCuxO3-δ-based electrode layers show low polarization resistance values in La0.8Sr0.2Ga0.8Mg0.2O3-δ-based symmetrical cells. The lowest values for Cu-rich compositions at 800 °C are 0.056 Ω cm−2 for LaNi 0.5Cu0.5O3-δ and 0.054 Ω cm−2 for LaNi0.25Cu0.75O3-δ with La0.2Ce0.8O3-δ buffer layer. For the reversible cell with LaNi0.5Cu0.5O3-δ air electrode, approx. 870 mW cm−2 power density output at 900 °C is obtained when fueled with wet H2, as well as over 3 A cm−2 current density at 2 V in the electrolysis mode.
Remark	Link

ID=581

Electrical properties of gadolinia-doped ceria for electrodes for magnetohydrodynamic energy systems

Authors	Michael S. Bowen, Michael Johnson, Ryan McQuade, Bryce Wright, Kyei-Sing Kwong, Peter Y. Hsieh, David P. Cann & C. Rigel Woodside
Source	SN Applied Sciences Volume: 2 Time of Publication: 2020
Abstract	High temperature conducting ceramics are of current interest for use as electrode materials for magnetohydrodynamic (MHD) power generation systems for their high conductivity values and their excellent stability under extreme conditions including operating temperatures above 2000 °C. Ceria doped with Gd (GDC) has been extensively studied for intermediate temperature applications and shows promise as an efficient electrode material. A summary of the current understanding of the electrical properties of GDC is provided with an emphasis on the higher temperature limits. Experiments to further validate the conclusions drawn in the literature review confirm that with electrical conductivities near 10 S/m at 1100 °C make GDC a good candidate electrode material for an MHD power generator.
Remark	Link

ID=580

Domain wall conductivity as the origin of enhanced domain wall dynamics in polycrystalline BiFeO3

Authors	Maja Makarovic, Mustafa ÇaÄri Bayir, Hana Ursic, Andraz Bradesko, and Tadej Rojac
Source	Journal of Applied Physics Volume: 128, Pages: 064104 Time of Publication: 2020
Abstract	Despite their primary importance in modern nanoelectronics, conductive domain walls (DWs) can also have a marking effect on the macroscopic response of polycrystalline ferroelectrics. In particular, a large nonlinear piezoelectric response at sub-Hz driving-field frequencies has been previously observed in BiFeO3, which was linked to the conductive nature of the DWs but whose exact origin has never been explained. In this study, by carefully designing the local conductivity in BiFeO3 using chemical doping, we found that the low-frequency piezoelectric nonlinearity is only observed in the sample with a large fraction of conductive DWs. Supported by nonlinear Maxwell–Wagner modeling, we propose that this large response originates from DW displacements inside a specific set of grains or grain clusters in which the internal electric fields are enhanced due to M-W effects. We thus show that these effects likely arise due to the pronounced local anisotropy in the electrical conductivity, varying from grain to grain, whose origin lies in the conductive DWs themselves. The results demonstrate the possibility of controlling the global nonlinear properties of polycrystalline ferroelectrics by engineering local properties.
Remark	Link

ID=579

Thermal, optical and electrical properties of MnO2-doped mixed sodium potassium phosphate glasses

Authors	M. Jerroudi, L. Bih, S. Yousfi, L. Bejjit, M. Haddad, B. Manoun & P. Lazor
Source	Journal of Thermal Analysis and Calorimetry Time of Publication: 2020
Abstract	Glasses in the system (1 − x)(0.5NaPO3–0.5KPO3)–xMnO2, with 0 ≤ x ≤ 50 mol%, have been prepared using a melt-quench route. The glasses exhibit a yellow to dark color with the increase in manganese content owing to the presence of Mn2+ and Mn3+ ions in the network. The amorphous state of the glasses is evidenced by the X-ray diffraction. In order to get an insight into the physical and structural aspects of these vitreous materials, we have determined some of their parameters such as density, molar volume and glass transition temperature. From differential thermal analysis scan on heating, we evaluated the glass transition temperature (Tg) of each glass, which corresponds to the phase transition temperature from solid to viscous liquid. The density (ρ) as a structural index is found to increase while the corresponding molar volume decreases with MnO2 content. The structural approach of the studied glasses is evaluated by infrared (IR) and electron paramagnetic resonance (EPR) spectroscopies. IR technique allowed us to identify the coexisting bond vibration modes in the glass network, and it has shown that many structural phosphates units coexist, mainly pyrophosphate and metaphosphate structural groups. EPR experiments have shown the presence of Mn2+ centers in the glasses. The UV–Visible absorption is utilized to estimate the values of the optical band gap (Eg) and Urbach energy (ΔE). The optical band gap energy is determined from both the absorption spectrum fitting (ASF) and Tauc’s methods. These optical parameters are composition dependence. The dc conductivity of the glasses is determined in the temperature range from 303 to 473 K. It decreases with increasing manganese content. It is thermally activated and followed an Arrhenius behavior. The crystallization of glasses is realized by submitting them to heat treatments, and the crystallized phases are identified by XRD analysis. The crystallization kinetic was studied under non-isothermal conditions. The activation energy (Ec) and the Avrami parameter (n) were determined.
Remark	Link

ID=577

Support effects on catalysis of low temperature methane steam reforming

Authors	Maki Torimoto, Shuhei Ogo, Yudai Hisai, Naoya Nakano, Ayako Takahashi, Quanbao Ma, Jeong Gil Seo, Hideaki Tsuneki, Truls Norby and Yasushi Sekine
Source	RSC Adv. Volume: 10, Pages: 26418-26424 Time of Publication: 2020
Abstract	Low temperature (<500 K) methane steam reforming in an electric field was investigated over various catalysts. To elucidate the factors governing catalytic activity, activity tests and various characterization methods were conducted over various oxides including CeO2, Nb2O5, and Ta2O5 as supports. Activities of Pd catalysts loaded on these oxides showed the order of CeO2 > Nb2O5 > Ta2O5. Surface proton conductivity has a key role for the activation of methane in an electric field. Proton hopping ability on the oxide surface was estimated using electrochemical impedance measurements. Proton transport ability on the oxide surface at 473 K was in the order of CeO2 > Nb2O5 > Ta2O5. The OH group amounts on the oxide surface were evaluated by measuring pyridine adsorption with and without H2O pretreatment. Results indicate that the surface OH group concentrations on the oxide surface were in the order of CeO2 > Nb2O5 > Ta2O5. These results demonstrate that the surface concentrations of OH groups are related to the proton hopping ability on the oxide surface. The concentrations reflect the catalytic activity of low-temperature methane steam reforming in the electric field.
Remark	Link

ID=576

Defects and polaronic electron transport in Fe2WO6

Authors	Raphael Schuler, Truls Norby, Helmer Fjellvåg
Source	Physical Chemistry Chemical Physics Issue: 27 Time of Publication: 2020
Abstract	We report the synthesis of phase pure Fe2WO6 and its structural characterization by high quality synchrotron X-ray powder diffraction, followed by studies of electric and thermoelectric properties as a function of temperature (200–950 °C) and pO2 (1–10−3 bar). The results are shown to be in accordance with a defect chemical model comprising formation of oxygen vacancies and charge compensating electrons at high temperatures. The standard enthalpy and entropy of formation of an oxygen vacancy and two electrons in Fe2WO6 are found to be 113(5) kJ mol−1 and 41(5) J mol−1 K−1, respectively. Electrons residing as Fe2+ in the Fe3+ host structure act as charge carriers in a small polaron conducting manner. A freezing-in of oxygen vacancies below approximately 650 °C results in a region of constant charge carrier concentration, corresponding to an iron site fraction of XFe2+ ≅ 0.03. By decoupling of mobility from conductivity, we find a polaron hopping activation energy of 0.34(1) eV and a charge mobility pre-exponential u0 = 400(50) cm2 kV−1 s−1. We report thermal conductivity for the first time for Fe2WO6. The relatively high conductivity, large negative Seebeck coefficient and low thermal conductivity make Fe2WO6 an interesting candidate as an n-type thermoelectric in air, for which we report a maximum zT of 0.027 at 900 °C.
Remark	Link

ID=575

Tailoring the electrical conductivity and hardening in BiFeO3 ceramics

Authors	M.MakarovicabcN.KanascA.ZorkodeK.ZibernaaH.UrsicabD.R.Smabraten, S. M. Selbachc, T. Rojac
Source	Volume: 40, Issue: 15, Pages: 5483-5493 Time of Publication: 2020
Abstract	In this report, the influence of cobalt doping and annealing atmosphere on the electrical conductivity and polarization switching of BiFeO3 (BFO) ceramics was studied. Electrical conductivity as well as hardening behavior has been found to increase with introduction of acceptor sites. BFO ceramics doped with Co exhibit p-type conductivity, dominated by Fe4+ defects, which can be successfully reduced during high-temperature annealing in N2. However, indications of local reduction were found, presumably on domain walls and grain boundaries. A mechanism of hardening is proposed, which assumes two types of pinning centers: i) and related and ii) and related, most probably bound into complexes, which are shown to play the key role in the hardening behavior and hysteresis loop pinching and biasing. The results of this study could further promote designing local and bulk conductivity and hardening properties of BFO-based materials.
Keywords	Ceramics; Ferroelectric; Point defects; Conductivity; Hardening
Remark	Link

ID=574

Disagreements between space charge models and grain boundary impedance data in yttrium-substituted barium zirconate

Authors	Tarjei Bondevik, Jonathan M. Polfus, Truls Norby
Source	Solid State Ionics Volume: 353, Pages: 115369 Time of Publication: 2020
Abstract	Although the space charge model is commonly used to explain the high grain boundary resistance in proton conducting yttrium-substituted BaZrO3, it fails in its simplest forms with factors 10–40 to fit experimental data with respect to the characteristic frequency of the grain boundary impedance. We suggest modifications to the model, somewhat improving its fit. Including trapping effects of protons near yttrium substituents reduces the error only by factors less than 1.6. Increasing the width of the grain boundary core reduces the error with factors of 1.5–3. Discretizing the space charge layer, such that protons can only reside on specific, discrete sites, reduces the error with another factor of around 2. Considering reduced proton mobility in the GB by reducing its effective area may give a reduction in the fitting error of a factor of 2. Varying the dielectric constant in the GB does not affect the error considerably. Neither each single modification, nor their combined effect, can, however, account for the majority of the discrepancy between the space charge model and experimental data.
Remark	Link

ID=573

Insights into Crystal Structure and Diffusion of Biphasic Na2Zn2TeO6

Authors	Xinyu Li, Federico Bianchini, Julia Wind, Christine Pettersen, David S. Wragg, Ponniah Vajeeston, and Helmer Fjellvåg
Source	ACS Appl. Mater. Interfaces Volume: 12, Issue: 25, Pages: 27821-28924 Time of Publication: 2020
Abstract	The layered oxide Na2Zn2TeO6 is a fast Na+ ion conductor and a suitable candidate for application as a solid-state electrolyte. We present a detailed study on how synthesis temperature and Na-content affect the crystal structure and thus the Na+ ion conductivity of Na2Zn2TeO6. Furthermore, we report for the first time an O′3-type phase for Na2Zn2TeO6. At a synthesis temperature of 900 °C, we obtain a pure P2-type phase, providing peak performance in Na+ ion conductivity. Synthesis temperatures lower than 900 °C produce a series of mixed P2 and O′3-type phases. The O′3 structure can only be obtained as a pure phase by substituting Li on the Zn-sites to increase the Na-content. Thorough analysis of synchrotron data combined with computational modeling indicates that Li enters the Zn sites and, consequently, the amount of Na in the structure increases to balance the charge according to the formula Na2+xZn2–xLixTeO6 (x = 0.2–0.5). Impedance spectroscopy and computational modeling confirm that reducing the amount of the O′3-type phase enhances the Na+ ion mobility.
Remark	Link

ID=567

High ionic conductivity dysprosium and tantalum Co-doped bismuth oxide electrolyte for low-temperature SOFCs

Authors	P. S. Cardenas-Terrazas, M. T. Ayala-Ayala, J. Muñoz-Saldaña, A. F. Fuentes, D. A. Leal-Chavez, J. E. Ledezma-Sillas, C. Carreño-Gallardo & J. M. Herrera-Ramirez
Source	Ionics Volume: 26, Pages: 4579–4586 Time of Publication: 2020
Abstract	A novel double dysprosium- and tantalum-doped bismuth oxide electrolyte synthesized by solid-state reaction for low-temperature solid oxide fuel cells (LT-SOFCs) is here reported. The phase structures at room temperature were defined by X-ray powder diffraction (XRD). A stable δ-Bi2O3 phase was obtained by co-doping Bi2O3 with Dy2O3 and Ta2O5 in specific contents. The effect of the co-dopant total content (5–15 mol%) on the ionic conductivity was measured as a function of temperature (300 to 700 °C). Results revealed that the (Dy2O3)13(Ta2O5)2(Bi2O3)85 system showed the highest ionic conductivity as 0.08 S cm−1 at 500 °C, which is three times higher than the binary system reported in the literature (E2O3)20(Bi2O3)80 (20ESB) and in the same range as the ternary system with the highest conductivity reported so far (Dy2O3)8(W2O3)4(Bi2O3)88 (8D4WSB). The lowest activation energy for our system was 0.20 eV at temperatures higher than 550 °C.
Remark	Link

ID=566

Ruddlesden-Popper-type Nd2-xNi1-yCuyO4±δ layered oxides as candidate materials for MIEC-type ceramic membranes

Authors	BartÅomiej GÄ™dziorowski, Kacper Cichy, Anna Niemczyk, Anna Olszewska, Zijia Zhang, Szymon KopeÄ, Kun Zheng, Mateusz Marzec, Marta Gajewska, Zhihong Du, Hailei Zhao, Konrad Åšwierczek
Source	Journal of the European Ceramic Society Volume: 40, Issue: 12, Pages: 4056-4066 Time of Publication: 2020
Abstract	Series of Nd2-xNi1-yCuyO4±δ Ruddlesden-Popper-type oxides is obtained by auto-combustion synthesis method and systematically characterized concerning phase composition, formation of solid state solution, crystal structure, oxygen content, as well as regarding transport properties and oxygen permeability when applied as mixed conducting ceramic membranes. The A-site deficiency x is discussed in terms of structural stability and its effect on the oxygen content, with ongoing modification of total electrical conductivity observed. In selected Nd2-xNi0.75Cu0.25O4±δ oxides the dominating oxygen defects at high temperatures can be changed from oxygen interstitials to vacancies by the induced A-site deficiency, which affects bulk- and surface-related transport coefficients, as it is observed in electrical conductivity relaxation studies. The optimized Nd1.9Ni0.75Cu0.25O4±δ sinters having increased ionic conductivity, as well as fine, well-sintered microstructure allow to achieve one of the higher reported oxygen fluxes for CO2-stable Ruddlesden-Popper-based ceramic membranes (e.g. 0.49â¯mLâ¯cm−2â¯min−1 at ca. 880â¯°C for 1.05â¯mm thickness).
Keywords	Ruddlesden-Popper oxides, Nonstoichiometric compounds, Crystal structure, Transport properties, Oxygen permeation membranes
Remark	https://doi.org/10.1016/j.jeurceramsoc.2020.04.054 Link

ID=564

Oxide Ion and Proton Conductivity in Highly Oxygen-Deficient Cubic Perovskite SrSc0.3Zn0.2Ga0.5O2.4

Authors	Chloe A. Fuller, Quentin Berrod, Bernhard Frick, Mark R. Johnson, Maxim Avdeev, John S. O. Evans, and Ivana Radosavljevic Evans
Source	Chem. Mater. Volume: 32, Issue: 10, Pages: 4347–4357 Time of Publication: 2020
Abstract	A series of Zn-substituted compounds, Sr2Sc1–xZnxGaO5–0.5x, based on the brownmillerite-type oxide ion conductor Sr2ScGaO5 have been synthesized, and a single-phase region has been identified at 0.4 ≤ x < 0.6. The structure and dynamics of Sr2Sc0.6Zn0.4GaO4.8 were investigated by X-ray and neutron diffraction, neutron total scattering and pair distribution function (PDF) analysis, impedance spectroscopy, and neutron spectroscopy. The material was found to be a highly disordered cubic perovskite with a remarkable level of oxygen deficiency across a large temperature range. These structural properties lead to an increase of oxide ion conductivity of about two orders of magnitude relative to the parent Sr2ScGaO5. The presence of proton conductivity and some water uptake was suggested by the impedance data and corroborated by thermogravimetric analysis (TGA), solid state nuclear magnetic resonance (NMR), variable temperature X-ray diffraction, and neutron spectroscopy. Both proton and oxide ion conductivity produced a measurable quasi-elastic neutron scattering (QENS) signal, and the onset of each dynamic process could be observed by monitoring the temperature dependence of the elastic and inelastic scattering intensities measured in fixed window scans. Neutron total scattering and PDF studies revealed a local structure that is markedly different from the perovskite average structure, and we propose that Sr2Sc0.6Zn0.4GaO4.8 contains a rare one-coordinate or terminal oxygen site.
Remark	Link

ID=563

High-performing electrolyte-supported symmetrical solid oxide electrolysis cells operating under steam electrolysis and co-electrolysis modes

Authors	Lucile Bernadet, Carlos Moncasi, Marc Torrell, Albert Tarancón
Source	International Journal of Hydrogen Energy Volume: 45, Issue: 28, Pages: 14208-14217 Time of Publication: 2020
Abstract	Symmetrical solid oxide cells (s-SOC) present several advantages compared to typical configuration, as a reduction of sintering steps or a better thermomechanical compatibility between the electrodes and the electrolyte. Different mixed ionic-electronic conductors (MIEC) have been reported as suitable candidates for symmetrical configuration, allowing operations under steam electrolysis (SOEC) or co-electrolysis (co-SOEC) without the use of reducing safe gas (typically employed in SoA nickel based cells). In the present study, Sr2Fe1.5Mo0.5O6−δ (SFM) electrodes are deposited on both sides of YbScSZ tapes previously coated with a Ce1-xGdxO1.9 (GDC) barrier layer grown by PLD. Electrode sintering temperature is optimized and fixed at 1200 °C by means of electrochemical impedance spectroscopy (EIS) measurements in symmetrical atmosphere. The cell is then characterized at 900 °C in SOEC and co-SOEC modes without the use of any safe gas obtaining high current densities of 1.4 and 1.1 A cm−2 at 1.3 V respectively. Short-term reversibility is finally proven by switching the gas atmosphere between the cathode and anode sides while keeping the electrolysis conditions. Similar performances are obtained in both configurations.
Keywords	Solid oxide electrolyser, SOEC, Co-electrolysis, Symmetrical, Energy storage, Safe gas
Remark	https://doi.org/10.1016/j.ijhydene.2020.03.144 Link

ID=561

Mixed-conducting ceramic-carbonate dual-phase membranes: Gas permeation and counter-permeation

Authors	Han-Chun Wu, Gabriel Nile, Jerry Y.S. Lin
Source	Journal of Membrane Science Volume: 605, Pages: 118093 Time of Publication: 2020
Abstract	CO2 and O2 permeable ceramic-carbonate dual-phase membranes can be used in membrane reactors for applications such as selective oxidation of hydrocarbons. Two ceramic-carbonate dual-phase membranes consisting of mixed electronic-ionic conducting perovskite-type ceramics of Pr0.6Sr0.4Co0.2Fe0.8 and SrFe0.9Ta0.1O3-δ are studied for CO2 and O2 permeation and counter-permeation. The geometric factors for the carbonate phase and ceramic phase, obtained from the data of helium permeation and electrical conductivity, are used to calculate the effective carbonate and oxygen ionic conductivity in the carbonate and ceramic phase. Without counter-permeation, O2 permeation through the dual-phase membrane is controlled by oxygen ionic conduction in the ceramic phase and CO2 permeation is determined by the total conductance including effective carbonate and oxygen ionic conductivities in both phases. When the dual-phase membrane is exposed to CO2 on one side and O2 on the other side, counter-permeation of CO2 and O2 occurs in the opposite directions across the membrane. With CO2 counter-permeation, the oxygen ionic flux is higher than that without counter-permeation due to an increase in the driving force for oxygen transport. CO2 permeation consumes oxygen ions transporting through the membrane, resulting in a lower O2 permeation flux compared with the O2-only permeation case. However, O2 counter-permeation has negligible effect on CO2 permeation flux for the dual-phase membranes.
Remark	https://doi.org/10.1016/j.memsci.2020.118093 Link

ID=560

Reaction mechanism of low-temperature catalysis by surface protonics in an electric field

Author	Yasushi Sekine and Ryo Manabe
Source	Faraday Discuss. Time of Publication: 2020
Abstract	The process combining heterogeneous catalysts and DC electric field can achieve high catalytic activities, even under mild conditions (<500 K) with less electrical energy consumption. Hydrogen production by steam reforming of methane, aromatics and alcohol, dehydrogenation of methylcyclohexane, dry reforming of methane, and ammonia synthesis are known to proceed at low temperatures in an electric field. In-situ/operando analyses have been conducted using IR, Raman, XAFS, electrochemical impedance spectroscopy, and isotopic kinetic analyses to elucidate the reaction mechanism for these reactions at low temperatures. Results show that surface proton hopping by a DC electric field, called surface protonics, is important for these reactions at low temperatures because of higher surface adsorbate concentrations at lower temperatures.
Remark	Accepted Manuscript, https://doi.org/10.1039/C9FD00129H Link

ID=559

Peculiar Properties of Electrochemically OxidizedSmBaCo2−xMnxO5+δ(x=0; 0.5 and 1) A-SiteOrdered Perovskites

Authors	Anna Olszewska, Konrad Swierczek and Anna Niemczyk
Source	Crystals Volume: 10, Pages: 205 Time of Publication: 2020
Abstract	Fully-stoichiometric SmBaCo2-xMnxO6oxides (x=0, 0.5, 1) were obtained through theelectrochemical oxidation method performed in 1 M KOH solution from starting materials having closeto equilibrium oxygen content. Cycling voltammetry scans allow us to recognize the voltage range(0.3–0.55 V vs. Hg/HgO electrode) for which electrochemical oxidation occurs with high efficiency.In a similarly performed galvanostatic experiment, the value of the stabilized voltage recorded duringthe oxidation increased with higher Mn content, which seems to relate to the electronic structure ofthe compounds. Results of the iodometric titration and thermogravimetric analysis prove that theproposed technique allows for an increase in the oxygen content in SmBaCo2-xMnxO5+δmaterialsto values close to 6 (δ≈1). While the expected significant enhancement of the total conductivitywas observed for the oxidized samples, surprisingly, their crystal structure only underwent slightmodification. This can be interpreted as due to the unique nature of the oxygen intercalation process at room temperature.
Remark	doi:10.3390/cryst10030205 Link

ID=557

Activation of C−H Bond of Propane by Strong Basic Sites Generated by Bulk Proton Conduction on VâModified Hydroxyapatites for the Formation of Propene

Authors	Sarah Petit, Cyril Thomas, Yannick Millot, JeanâMarc Krafft, Christel LabertyâRobert, Guylène Costentin
Source	ChemCatChem Volume: 12, Issue: 9, Pages: 2506-2521 Time of Publication: 2020
Abstract	Insights into the catalytic transformation of propane to propene on Vâapatite catalysts are provided based on structureâreactivity relationships. Substitution of phosphates by vanadates in the hydroxyapatite structure leads to the formation of Ca10(PO4)6âx(VO4)x(OH)2âyOy Vâoxyâhydroxyâapatite solid solutions (x=0→6). Bulk vanadium incorporation promotes (i) calcium rich terminations (XPS, CO adsorption), (ii) proton deficiency inside the OH− channels (1H NMR) giving rise to O2− native species, (iii) the thermallyâactivated formation of additional O2− species along the OH− channels resulting in Hâbonding interaction (inâsitu DRIFT) and (iv) the proton conduction process that eventually results in the surface exposure of O2− species (inâsitu impedance spectroscopy). The exposure of Ca2+−O2− surface acidâbase pairs allows the dissociation of hydrogen, emphasizing the strong basicity of the related O2− species. Whereas an increasing vanadium content is beneficial to propene selectivity, it scarcely impacts propane conversion. The reaction proceeds mainly upon oxidative dehydrogenation, even if the minor dehydrogenation route is also observed. Surface O2− generated thanks to proton mobility are involved in the C−H bond activation, as shown by the synergistic effect between the oxidative dehydrogenation of propane reaction and the bulk proton conduction measured under operando conditions. This puts emphasis on the key role of strong basic sites for propane activation.
Remark	https://doi.org/10.1002/cctc.201902181 Link

ID=556

First observation of surface protonics on SrZrO3 perovskite under a H2 atmosphere

Authors	Yudai Hisai, Kota Murakami, Yukiko Kamite, Quanbao Ma, Einar Vøllestad, Ryo Manabe, Taku Matsuda, Shuhei Ogo, Truls Norby and Yasushi Sekine
Source	Chem. Commun. Volume: 56, Pages: 2699-2702 Time of Publication: 2020
Abstract	This is the first direct observation that surface proton hopping occurs on SrZrO3 perovskite even under a H2 (i.e. dry) atmosphere. Understanding proton conduction mechanisms on ceramic surfaces under a H2 atmosphere is necessary to investigate the role of proton hopping on the surface of heterogeneous catalysts in an electric field. In this work, surface protonics was investigated using electrochemical impedance spectroscopy (EIS). To extract the surface proton conduction, two pellets of different relative densities were prepared: a porous sample (R.D. = 60%) and a dense sample (R.D. = 90%). Comparison of conductivities with and without H2 revealed that only the porous sample showed a decrease in the apparent activation energy of conductivity by supplying H2. H/D isotope exchange tests revealed that the surface proton is the dominant conductive species over the porous sample with H2 supply. Such identification of a dominant conductive carrier facilitates consideration of the role of surface protonics in chemical reactions.
Remark	Link

ID=554

Indium doping in SrCeO3 proton-conducting perovskites

Authors	Wojciech Skubida, Kun Zheng, Konrad Swierczek, Mateusz Michna, Lukasz Kondracki
Source	Journal of Solid State Chemistry Volume: 248, Pages: 121210 Time of Publication: 2020
Abstract	In this work we present results of studies of In3+ doping in strontium cerate, comprising structural aspects, and oxygen as well as proton conductivity. Crystal structure analysis of single-phase SrCe1-xInxO3-a (x â= â0.1, 0.2 and 0.3) materials in 25–900 â°C temperature range indicates presence of strong orthorhombic distortion of the perovskite-type structure, similar as for the undoped SrCeO3. Limited sinterability of the obtained powders was mitigated by addition of 1 âwt% of NiO, which allowed to manufacture dense sinters at 1400 â°C. Electrochemical impedance spectroscopy measurements done in dry synthetic air show decrease of the ionic (oxygen) conductivity with the increase of In content, as well as associated increase of the activation energy. This indicates that formed oxygen vacancies are trapped in the structure. Overall, electrical conductivity for SrCe1-xInxO3-a in H2O- and D2O-containing atmospheres decreases with In content, but respective H+ and D+ transference numbers are larger for samples with higher indium doping. At 500 â°C the highest proton and deuterium conductivity was recorded for SrCe0.9In0.1O3-a, reaching up to 0.70·10−4 âS âcm−1 and 0.26·10−4 âS âcm−1, respectively. Derived diffusion and surface exchange coefficients are 10−7-10−6 âcm2 âs−1 and 10−6-10−5 âcm âs−1, respectively in 500–700 â°C temperature range.
Keywords	Strontium cerate, In doping, Crystal structure, Hydration, Transport properties, Proton conductivity
Remark	https://doi.org/10.1016/j.jssc.2020.121210

ID=553

A detailed kinetic model for the reduction of oxygen on LSCF-GDC composite cathodes

Authors	Alessandro Donazzi, Giulio Cordaro, Andrea Baricci, Zhao-Bin Ding, Matteo Maestri
Source	Electrochimica Acta Time of Publication: 2020
Abstract	A kinetic investigation of the Oxygen Reduction Reaction (ORR) is performed on LSCF-GDC composite cathodes (La0.4Sr0.6Co0.2Fe0.8O3-δ/Ce0.9Gd0.1O2-δ 50/50) spanning a wide range of operating conditions. EIS tests are carried out on symmetric cells between 700 °C and 560 °C at OCV, with O2/N2 mixtures at varying O2 molar fraction (5–21%). A dynamic, one-dimensional, physic model of the LSCF-GDC electrode is applied to rationalize the experimental results. The model simulates the spectra by solving mass and charge conservation equations, including terms for gas diffusion in the porous electrode and solid state transport in both the LSCF and the GDC lattice. A thermodynamically consistent, detailed kinetic scheme is applied to describe the ORR mechanism, which takes into account elementary steps of adsorption and desorption, first and second electronation at the gas/electrode interface, interfacial and lattice ion transfer. A full set of rate parameters (pre-exponential factors and activation energies) is derived by fitting to inhouse-measured impedance data, and validated against a well-established literature dataset. The sensitivity analysis supports the prevailing role of the TPB route over the 2 PB route, and highlights that the transfer of a single-charged oxygen adatom from the LSCF surface to the GDC lattice governs the ORR. The model clarifies the origin of distortions in measured impedance arcs, and captures the effect of O2 pressure on the observed electrochemical activity.
Remark	https://doi.org/10.1016/j.electacta.2020.135620 Link

ID=551

A CO2-Tolerant Perovskite Oxide with High Oxide Ion and Electronic Conductivity

Authors
Source	Adv. Mater. Time of Publication: 2019
Abstract	Mixed ionic–electronic conductors (MIECs) that display high oxide ion con-ductivity (σo) and electronic conductivity (σe) constitute an important family of electrocatalysts for a variety of applications including fuel cells and oxygen sepa-ration membranes. Often MIECs exhibit sufficient σe but inadequate σo. It has been a long-standing challenge to develop MIECs with both high σo and stability under device operation conditions. For example, the well-known perovskite oxide Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) exhibits exceptional σo and electrocatalytic activity. The reactivity of BSCF with CO2, however, limits its use in practical applications. Here, the perovskite oxide Bi0.15Sr0.85Co0.8Fe0.2O3−δ (BiSCF) is shown to exhibit not only exceptional bulk transport properties, with a σo among the highest for known MIECs, but also high CO2 tolerance. When used as an oxygen separation membrane, BiSCF displays high oxygen permeability comparable to that of BSCF and much higher stability under CO2. The combination of high oxide transport properties and CO2 tolerance in a single-phase MIEC gives BiSCF a significant advantage over existing MIECs for practical applications.
Remark	DOI: 10.1002/adma.201905200 Link

ID=550

Coexistence of three types of sodium motion in double molybdate Na9Sc(MoO4)6: 23Na and 45Sc NMR data and ab initio calculations

Authors	Anton L. Buzlukov, Irina Yu. Arapova, Yana V. Baklanova, Nadezhda I. Medvedeva, Tatiana A. Denisova, Aleksandra A. Savina, Bogdan I. Lazoryak, Elena G. Khaikina and Michel Bardet
Source	Phys. Chem. Chem. Phys. Volume: 22, Pages: 144-154 Time of Publication: 2020
Abstract	The rechargeable Na-ion batteries attract much attention as an alternative to the widely used but expensive Li-ion batteries. The search for materials with high sodium diffusion is important for the development of solid state electrolytes. We present the results of experimental and ab initio studies of the Na-ion diffusion mechanism in Na9Sc(MoO4)6. The ion conductivity reaches the value of 3.6 × 10−2 S cm−1 at T ∼ 850 K. The 23Na and 45Sc NMR data reveal the coexistence of three different types of Na-ion motion in the temperature range from 300 to 750 K. They are activated at different temperatures and are characterized by substantially different dynamics parameters. These features are confirmed by ab initio calculations of activation barriers for sodium diffusion along various paths.
Remark	Link

ID=547

Tuning of Mg content to enhance the thermoelectric properties in binary Mg2+δ Si (δ = 0, 0.1, 0.15, 0.2)

Authors	Priyadarshini Balasubramanian, Manjusha Battabyal, Dhruba Das, Arumugam Chandra Bose and Raghavan Gopalan
Source	Materials Research Express Volume: 6 Time of Publication: 2019
Abstract	We report the enhanced thermoelectric properties of binary Mg2Si by tuning the Mg content. Polycrystalline Mg2+δ Si (where δ is the excess Mg content in the starting composition of the samples and δ = 0, 0.1, 0.15, 0.2) samples were processed by solid-state synthesis route using ball milling followed by rapid spark plasma sintering in order to minimize the Mg loss during processing. Microstructural and x-ray diffraction analysis revealed that, Mg content (δ) of 0.1–0.15 is required to get the binary Mg2Si phase without any elemental Mg/Si phase. Hall effect measurement and Fourier Transform Infrared Spectroscopy analysis show that, the excess Mg content helps to enhance the carrier concentration and charge carrier effective mass due to the occupancy of Mg at the interstitial site in Mg2Si structure. The influence of Mg content on thermoelectric properties, viz., electrical resistivity, Seebeck coefficient and thermal conductivity is investigated from 300 K to 780 K. A marked enhancement in thermoelectric power factor (~1.6 mW m−2K−2) is obtained for Mg2.15Si sample at 780 K. The occupancy of excess Mg at interstitial sites reduces the lattice thermal conductivity by lowering lattice symmetry. A maximum figure of merit (ZT) ~ 0.39 ± 0.03 at 780 K has been achieved in Mg2.15Si sample, the highest among that reported in n-type binary Mg2Si system. This suggests that excess Mg content in the starting composition of Mg2+δ Si helps in stabilizing the phase as well as improves the thermoelectric properties of the Mg2Si.
Remark	https://doi.org/10.1088/2053-1591/ab58fb Link

ID=545

Intriguing electrochemistry in low-temperature single layer ceramic fuel cells based on CuFe2O4

Authors
Source	International Journal of Hydrogen Energy Time of Publication: 2019
Abstract	A composite of CuFe2O4 and Gd-Sm co-doped CeO2 is studied for a single layer ceramic fuel cell application. In order to optimize the cell performance, the effects of sintering temperatures (600 °C, 700 °C, 800 °C, 900 °C and 1000 °C) were investigated for the fabrication of the cells. It was found that the cells sintered at 700 °C outperformed other cells with a maximum peak power density of 344 mW/cm2 at 550 °C. The electrochemical impedance spectroscopy analysis on the best cell revealed significant ohmic losses (0.399 Ω cm2) and polarization losses (0.174 Ω cm2) in the cell. The HR-TEM and SEM gave microstructural information of the cell. The HT-XRD spectra showed the crystal structures in different sintering temperatures. The cell performance was stable and the composite material did not degrade during an 8 h stability test under open-circuit condition. This study opens up new avenues for the exploration of this nanocomposite material for the low temperature single component ceramic fuel cell research.
Keywords	Catalysis; Ceramic; Composite; Fuel cell; Single component
Remark	https://doi.org/10.1016/j.ijhydene.2019.09.175 Link

ID=544

Mn-rich SmBaCo0.5Mn1.5O5+δ double perovskite cathode material for SOFCs

Authors	Anna Olszewska, Yang Zhang, Zhihong Du, Mateusz Marzec, Konrad Świerczek, Hailei Zhao, Bogdan Dabrowski
Source	International Journal of Hydrogen Energy Volume: 44, Issue: 50 Time of Publication: 2019
Abstract	SmBaCo0.5Mn1.5O5+δ oxide with Sm-Ba cation-ordered perovskite-type structure is synthesized and examined in relation to whole RBaCo0.5Mn1.5O5+δ series (R: selected rare earth elements). Presence of Sm and 3:1 ratio of Mn to Co allows to balance physicochemical properties of the composition, with moderate thermal expansion coefficient value of 18.70(1)·10−6 K−1 in 300–900 °C range, high concentration of disordered oxygen vacancies in 600–900 °C range (δ = 0.16 at 900 °C), and good transport properties with electrical conductivity reaching 33 S cm−1 at 900 °C in air. Consequently, the compound enables to manufacture catalytically-active cathode, with good electrochemical performance measured for the electrolyte-supported laboratory-scale solid oxide fuel cell with Ni-Gd1.9Ce0.1O2-δ\|La0.4Ce0.6O2-δ\|La0.8Sr0.2Ga0.8Mg0.2O3-δ\|SmBaCo0.5Mn1.5O5+δ configuration, for which 1060 mW cm−2 power density is observed at 900 °C. Furthermore, the tested symmetrical SmBaCo0.5Mn1.5O5+δ\|La0.8Sr0.2Ga0.8Mg0.2O3-δ\|SmBaCo0.5Mn1.5O5+δ cell delivers 377 mW cm−2 power density at 850 °C, which is a promising result.
Keywords	Mn-rich layered perovskites; Physicochemical properties; Cathode materials; SOFC; Symmetrical SOFC
Remark	https://doi.org/10.1016/j.ijhydene.2019.08.254 Link

ID=541

Thermoelectric properties of A-site deficient La-doped SrTiO3 at 100–900 °C under reducing conditions

Authors	Sathya Prakash Singh, Nikola Kanas, Temesgen D.Desissa, Mats Johnsson, Mari-Ann Einarsrud, Truls Norby, Kjell Wiik
Source	Journal of the European Ceramic Society Volume: 40, Issue: 2, Pages: 401-407 Time of Publication: 2020
Abstract	Lanthanum doped strontium titanate is a potential n-type thermoelectric material at moderate and high temperatures. (La0.12Sr0.88)0.95TiO3 ceramics were prepared by two different routes, conventional sintering at 1500 °C and spark plasma sintering at temperatures between 925 and 1200 °C. Samples with grain size between 40 nm and 1.4 μm were prepared and characterized with respect to their thermoelectric transport properties at temperatures between 100 and 900 °C under reducing conditions (H2/H2O-buffer mixtures). The thermal conductivity was significantly reduced with decreasing grain size reaching a value of 1.3 W m−1. K−1 at 600 °C for grain size of 40 nm and porosity of 19%. Electrical conductivity increased with increasing grain size showing a maximum of 500 S cm−1 at 200 °C for a grain size of 1.4 μm. The highest figure-of-merit (zT) was measured for samples with 1.4 μm average grain size reaching 0.2 at 500 °C.
Remark	https://doi.org/10.1016/j.jeurceramsoc.2019.09.024 Link

ID=538

Conductivity studies on the substituted stannate pyrochlore system Gd2Sn2-x-yMxAyO7 (M= Ti and A = Ru; x = 0.5, 1.0 and 1.5; y = 0.2)

Authors	N. Srinivasan, G.V.M. Kiruthika
Source	Solid State Sciences Volume: 96 Time of Publication: 2019
Abstract	Studies on the Gd2Sn2-x-yMxAyO7 system (M = Ti and A = Ru; x = 0.5, 1.0 and 1.5; y = 0.2) were carried out and the conductivity of the compounds was analyzed in air. All the substituted compounds form ordered pyrochlore structure. Enhanced conductivity properties were observed for the substituted compounds as compared to the Gd2Sn2O7 system. The more polarizable Ti–O and Ru–O bond and the smaller radius of Ti4+ and Ru4+ as compared to Sn4+ has a combined effect on the increased conductivity properties of the compounds. It is interesting to note that a striking enhancement of the total conductivity is observed for Gd2TiSn0.8Ru0.2O7 (~10−3 S/cm at 1000 °C) as compared to Gd2TiSnO7 (10−6 S/cm at 1000 °C). An optimized number of mobile charge carriers and activation energy for the oxide ionic conduction is found to influence the conductivity properties of the compounds.
Keywords	Mixed ionic-electronic conductivity, Stannate pyrochlores, Oxide ion conductors
Remark	https://doi.org/10.1016/j.solidstatesciences.2019.105957 Link

ID=536

Protonic conductivity and thermal properties of cross-linked PVA/TiO2 nanocomposite polymer membranes

Authors	G.M. Aparicio, R.A. Vargas, P.R. Bueno
Source	Journal of Non-Crystalline Solids Volume: 522 Time of Publication: 2019
Abstract	Nanocomposite polymer membranes based on PVA/TiO2 were prepared by a solution casting method. Glutaraldehyde solution (GA) was used as linking agent to improve the chemical, thermal and physical properties of the membranes. The degree of cross-linking was varied by changing the reaction time. The phase behavior of the membranes was examined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). High resolution SEM micrographs show that the TiO2 nanoparticles are homogeneously dispersed, whilst the PVA crosslinks with the inorganic phase and fill in the gap between the nanoparticles. The ionic conductivity measurements were studied by impedance spectroscopy in the radio frequency range between 5 kHz to 5 MHz. Proton conductivity increases by several orders of magnitude with increasing cross-linking reaction time, reaching a maximum of 0.016 Scm−1 at 130 °C for the PVA/TiO2 composition of 1:12%, which was cross-linked for 42 h and then immersed in a 32 wt% KOH solution for 24 h. The ionic activation energy of the prepared membranes ranged from 0.038 KeV to 0.121 KeV. This result was carried out to obtain an estimation of the desorption time of water in the range from room temperature to the decomposition temperature around 500 °C.
Remark	Link

ID=534

Synthesis and Study of (Sr,La)2FeCo0.5Mo0.5O6 − δ Oxides with Double Perovskite Structure

Authors	M. M. Abdullaev, S.Ya. Istomin, A.V. Sobolev, I.A. Presnyakov, E.V. Antipov
Source	Russian Journal of Inorganic Chemistry Volume: 64, Issue: 6, Pages: 696–704 Time of Publication: 2019
Abstract	Complex oxides Sr2 − xLaxFeCo0.5Mo0.5O6 − δ, (x = 0.2, 0.4; δ ≈ 0.03–0.15) have been first synthesized by the sol-gel method. Their crystal structures have been refined by the Rietveld method; the refinement showed that the complex oxides have the structure of cubic double perovskite (a ≈ 2aper, space group Fm3̄m) with partial ordering of Fe(Co) and Mo in the B positions. Based on the 57Fe Mössbauer measurements, the average formal oxidation state of iron has been found to decrease from +3.20 (x = 0.0) to +3.04 (x = 0.4). Our study of the behavior of perovskites in a reducing Ar/H2 atmosphere (8%) revealed a decrease in the reduction resistance with decreasing La content (x = 0.4 → 0). The combination of the properties studied, namely chemical stability with respect to the reaction with Ce1 − xGdxO2 − x/2 and Zr1 − xYxO2 − x/2, high-temperature thermal expansion, and electrical conductivity in air and Ar/H2, shows that Sr1.6La0.4Fe-Co0.5Mo0.5O6 − δ (δ ≈ 0.03) perovskite is more attractive as an electrode material for medium-temperature symmetric solid oxide fuel cells than Sr2FeCo0.5Mo0.5O6 − δ.
Remark	Link

ID=532

Influence of Lanthanum Doping on Structural and Electrical/Electrochemical Properties of Double Perovskite Sr2CoMoO6 as Anode Materials for Intermediate-Temperature Solid Oxide Fuel Cells

Authors	Pravin Kumar, Paramananda Jena, P. K. Patro, R. K. Lenka, A. S. K. Sinha, Prabhakar Singh, Rajendra Kumar Singh
Source	ACS Appl. Mater. Interfaces Volume: 11, Issue: 27, Pages: 24659-24667 Time of Publication: 2019
Abstract	Lanthanum (La3+)-doped double perovskites Sr2CoMoO6 (Sr2–xLaxCoMoO6, 0.00 ≤ x ≤ 0.03) were synthesized via the citrate–nitrate autocombustion route. The Reitveld refinement analysis of X-ray diffraction reveals the tetragonal symmetry as the main phase with space group I4/m and also confirms the presence of some peaks corresponding to extra phase SrMoO4. The SEM micrograph images reflect that grains are in irregular shape and sizes for all samples. Average grain size gradually decreases with the increase of the SrMoO4 phase. The X-ray photoelectron spectroscopy (XPS) analysis confirms the presence of mixed valence states of Mo5+/Mo6+, Co2+/Co3+, and O-lattice/O-chemisorbed/O-physisorbed species. Coefficient of thermal expansion (CTE) analysis shows that the particular composition Sr1.97La0.03CoMoO6 has the lowest CTE value among the compositions studied. The electrical conductivity of Sr2CoMoO6 is enhanced effectively by doping La at Sr sites. The measured area-specific resistance (ASR) for the composition Sr1.97La0.03CoMoO6 (SLCM03) is found to be appreciably low, ∼0.053 Ohm cm–2 at 800 °C. The obtained highest electrical conductivity with the lowest activation energy and low ASR value for the composition Sr1.97La0.03CoMoO6 encompasses it as a promising candidate for anode material in the intermediate-temperature solid oxide fuel cell (IT-SOFC) application.
Remark	Link

ID=531

Scheelite type Sr1−xBaxWO4 (x = 0.1, 0.2, 0.3) for possible application in Solid Oxide Fuel Cell electrolytes

Authors	Ahmed Afif, Juliana Zaini, Seikh Mohammad Habibur Rahman, Sten Eriksson, Md Aminul Islam & Abul Kalam Azad
Source	Scientific Reports Volume: 9 Time of Publication: 2019
Abstract	Polycrystalline scheelite type Sr1−xBaxWO4 (x = 0.1, 0.2 & 0.3) materials were synthesized by the solid state sintering method and studied with respect to phase stability and ionic conductivity under condition of technological relevance for SOFC applications. All compounds crystallized in the single phase of tetragonal scheelite structure with the space group of I41/a. Room temperature X-ray diffraction and subsequent Rietveld analysis confirms its symmetry, space group and structural parameters. SEM illustrates the highly dense compounds. Significant mass change was observed to prove the proton uptake at higher temperature by TG-DSC. All compound shows lower conductivity compared to the traditional BCZY perovskite structured materials. SBW with x = 0.3 exhibit the highest ionic conductivity among all compounds under wet argon condition which is 1.9 × 10−6 S cm−1 at 1000 °C. Since this scheelite type compounds show significant conductivity, the new series of SBW could serve in IT-SOFC as proton conducting electrolyte.
Remark	Article number: 9173 (2019) Link

ID=530

Surface Reconstruction under the Exposure of Electric Fields Enhances the Reactivity of Donor-Doped SrTiO3

Authors	Buğra Kayaalp, Kurt Klauke, Mattia Biesuz, Alessandro Iannaci, Vincenzo M. Sglavo, Massimiliano D’Arienzo, Heshmat Noei, Siwon Lee, WooChul Jung, Simone Mascotto
Source	J. Phys. Chem. C Volume: 123, Issue: 27, Pages: 16883-16892 Time of Publication: 2019
Abstract	In the present work, we show how exposure to electric fields during a high-temperature treatment can be used to manipulate surface properties of donor-doped ceramics and thus improve their reactivity. La0.1Sr0.9TiO3 (LSTO) nanoparticles, prepared by hydrothermal synthesis, were consolidated under air with and without external electric fields. Although neither approaches caused grain growth upon consolidation, the treatment under the influence of the electric field (i.e., flash sintering) remarkably enhanced the segregation of Sr on the material’s surface. In addition, a high concentration of O– defects both in bulk as well as on the material surface was demonstrated by spectroscopic methods. This enhanced defect concentration along with the nanoscopic grain size of the field-consolidated materials is probably one of the triggering factors of their improved charge carrier mobility, as observed by impedance spectroscopy. The effect of such a perturbed defect structure on the reactivity of the materials was evaluated by the total oxidation of methane. For materials treated under the influence of electric fields, the catalytic reaction rate improved by a factor of 3 with respect to that of conventionally treated LSTO, along with a remarkable decrease of the activation energy. Thus, electric-field-assisted processes, usually known for their energy-saving character, can also be deemed as an attractive, forward-looking strategy for improving functional properties of ceramics.
Remark	Link

ID=526

Inkjet Printing Functionalization of SOFC LSCF Cathodes

Authors	Eleonora Venezia, Massimo Viviani, Sabrina Presto, Vasant Kumar and Rumen I. Tomov
Source	Nanomaterials Time of Publication: 2019
Abstract	An important segment of the future renewable energy economy is the implementation of novel energy generation systems. Such electrochemical systems are solid oxide fuel cells, which have the advantage of direct conversion of the chemical energy stored in the fuel to electrical energy with high effciency. Improving the performance and lowering the cost of solid oxide fuel cells (SOFCs) are strongly dependent on finding commercially viable methods for nano-functionalization of their electrodes via infiltration. Inkjet printing technology was proven to be a feasible method providing scalability and high-resolution ink delivery. LaxSr1-xCoyFe1-yO3 cathodes were modified using inkjet printing for infiltration with two different materials: Gd-doped ceria (CGO) commonly used as ion-conductor and La0.6Sr0.4CoO3 (LCO) commonly used as a mixed ionic electronic conductor. As-modified surface structures promoted the extension of the three-phase boundary (TPB) and enhanced the mechanisms of the oxygen reduction reaction. Electrochemical impedance measurements revealed significantly lowered polarization resistances (between 2.7 and 3.7 times) and maximum power output enhancement of 24% for CGO infiltrated electrodes and 40% for LCO infiltrated electrodes.
Remark	Link

ID=525

AlTiN based thin films for degradation protection of tetrahedrite thermoelectric material

Authors	S. Battiston, F. Montagner, S. Fiameni, A. Famengo, S. Boldrini, A. Ferrario, C. Fanciulli, F. Agresti, M. Fabrizio
Source	Journal of Alloys and Compounds Volume: 792, Pages: 953-959 Time of Publication: 2019
Abstract	Efficient protection against degradation process of tetrahedrite-based thermoelectric materials was obtained employing AlTiN based thin films. The coatings were deposited via reactive direct current physical vapour deposition magnetron sputtering. The composition, thermal and electrical behaviour of thin films were investigated by X-ray diffraction, energy dispersive spectroscopy associated to field emission scanning electron microscopy, thermogravimetric analyses and electrical conductivity measurements. The barrier features for oxygen protection during thermal treatment in air at 500 °C were qualitatively evaluated, studying the coating behaviour over the higher operating temperature of tetrahedrite based thermoelectric devices.
Remark	https://doi.org/10.1016/j.jallcom.2019.04.116 Link

ID=523

Comparative Study of Electrical Conduction and Oxygen Diffusion in the Rhombohedral and Bixbyite Ln6MoO12 (Ln = Er, Tm, Yb) Polymorphs

Authors	Anna V. Shlyakhtina, Nikolay V. Lyskov, Maxim Avdeev, Vladimir G. Goffman, Nikolay V. Gorshkov, Alexander V. Knotko, Igor V. Kolbanev, Olga K. Karyagina, Konstantin I. Maslakov, Lidia G. Shcherbakova, Ekaterina M. Sadovskaya, Vladislav A. Sadykov, Nikita
Source	Inorg. Chem. Volume: 58, Issue: 7, Pages: 4275-4288 Time of Publication: 2019
Abstract	Electrical conduction and oxygen diffusion mobility in the bixbyite (Ia3̅) and rhombohedral (R3̅) polymorphs of the Ln6MoO12−Δ (Ln = Er, Tm, Yb; Δ = δ, δ1, δ2; δ1 > δ2) heavy lanthanide molybdates, belonging to new, previously unexplored classes of potential mixed (ionic–electronic) conductors, have been studied in the range of 200–900 °C. The oxygen self-diffusion coefficient in bixbyite (Ia3̅) Yb6MoO12−δ phase estimated by the temperature-programmed heteroexchange with C18O2 was shown to be much higher than that for rhombohedral (R3̅) RI (with large oxygen deficiency) and (R3̅) RII (with small oxygen deficiency) Ln6MoO12−Δ (Ln = Tm, Yb; Δ = δ1; δ1 > δ2) oxides. According to the activation energy for total conduction in ambient air, 0.99, 0.93, and 1.01 eV in Er6MoO12−δ, Tm6MoO12−δ, and Yb6MoO12−δ bixbyites, respectively, oxygen ion conductivity prevails in the range ∼200–500 °C. Oxygen mobility data for the rhombohedral Ln6MoO12−Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) phases RI and RII indicate that the oxygen in these phases exhibits mobility at much higher temperatures, such as those above 600–700 °C. Accordingly, below 600–700 °C they have predominantly electronic conductivity. As shown by total conductivity study of Ln6MoO12−δ (Ln = Er, Tm, Yb) bixbyites (Ia3̅) and rhombohedral phases Ln6MoO12−Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) (R3̅) in dry and wet air, the proton conductivity contribution exists only in Ln6MoO12−δ (Ln = Er, Tm, Yb) bixbyites up to 450–600 °C and decreases with a decreasing of the lanthanide ionic radius. The obtained data on the mobility of oxygen and the presence of proton contribution in bixbyites in the 300–600 °C temperature range make it possible to confirm unequivocally that Ln6MoO12−δ (Ln = Er, Tm, Yb) bixbyites are mixed electron–proton conductors at these temperatures.
Remark	Link

ID=522

Processing of high performance composite cathodes for protonic ceramic fuel cells by exsolution

Authors	Laura Rioja-Monllor, Carlos Bernuy-Lopez, Marie-Laure Fontaine, Tor Grandea and Mari-Ann Einarsrud
Source	J. Mater. Chem. A Volume: 7, Pages: 8609-8619 Time of Publication: 2019
Abstract	La0.5Ba0.5CoO3−δ–BaZrO3 (LB–BZ)-based composite materials were prepared by a modified Pechini sol–gel method combined with exsolution. Two different LB–BZ composites were prepared through two alternative thermal treatments of the precursor gel. A metastable single phase with a perovskite crystal structure was first obtained upon annealing the precursor in an inert atmosphere, and it was further transformed into a two-phase composite by in situ exsolution in air. Comparatively, direct calcination of the LB–BZ gel in air resulted in a two-phase composite with different microstructures and compositions of the two phases. The composite cathode formed by exsolution consisted of a matrix of BZ-phase with ∼45 nm grain size embedding ∼20 nm grains of LB-phase, while the composite cathode obtained by direct calcination consisted of a mixture of both phases with 50–60 nm grain size. Electrodes of symmetric half-cells were spray-coated on the BaZr0.9Y0.1O2.95 electrolyte to examine the electrochemical performance by impedance spectroscopy. The lowest area specific resistance (ASR) was obtained for the composite cathode produced by exsolution with an excellent ASR of 1.54 Ω cm2 at 600 °C and 18 Ω cm2 at 400 °C and an activation energy (Ea) of 0.60 eV in 3% moist synthetic air. This work demonstrates the potential of fabricating high performance nanocomposite cathodes with tailored chemical composition by a novel exsolution method.
Remark	DOI: 10.1039/C8TA10950H Link

ID=520

The effect of Fe‐acceptor doping on the electrical properties of Na1/2Bi1/2TiO3 and 0.94 (Na1/2Bi1/2)TiO3–0.06 BaTiO3

Authors
Source	J. of American Ceramic Society Volume: 102, Issue: 9, Pages: 5295-5304 Time of Publication: 2019
Abstract	Na1/2Bi1/2TiO3 (NBT) based ceramics are amongst the most promising lead‐free ferroelectric materials. It was expected that the defect chemistry and the effect of doping of NBT would be similar to that observed for lead based materials, however, acceptor doping does not lead to ferroelectric hardening. Instead, high oxygen ionic conductivity is induced. Nevertheless, for solid solutions with BaTiO3 (BT), which are more relevant with respect to ferroelectric applications, such a drastic change of electrical properties has not been observed so far. To rationalize the difference in defect chemistry between NBT and its solid solution 94(Na1/2Bi1/2TiO3)–0.06 BaTiO3 (NBT–6BT) compositions with different concentrations of Fe‐dopant were investigated. The study illustrates that the materials exhibit very similar behavior to NBT, and extraordinarily high oxygen ionic conductivity could also be induced in NBT–6BT. The key difference between NBT–6BT and NBT is the range of the dependence of ionic conductivity with dopant concentration. Previous studies of NBT–6BT have not reached sufficiently high dopant concentrations to observe high conductivity. In consequence, the same defect chemical model can be applied to both NBT and its solid solutions. This will help to rationalize the effect of doping on ferroelectric properties of NBT‐ceramics and defect chemistry related degradation and fatigue.
Remark	https://doi.org/10.1111/jace.16401 Link

ID=516

Superprotonic CsH2PO4 in dry air

Authors	C.E. Botez, I. Martinez, A. Price, H. Martinez, J.H. Leal
Source	Journal of Physics and Chemistry of Solids Volume: 129, Pages: 324-328 Time of Publication: 2019
Abstract	The first observation of a stable superprotonic CsH2PO4 (CDP) phase in the absence of high humidity and high pressure is reported. Temperature- and time-resolved impedance spectroscopy data show that the superprotonic conductivity of a CDP pellet measured in dry air (22%rh) in a hermetically sealed chamber holds at σ∼1.5 × 10−2 S cm−1 over a timespan t = 50 h at a temperature T = 260 °C. Nyquist plots confirm the superprotonic nature of the conduction and x-ray diffraction data reveal that no dehydration of the CDP superprotonic phase occurs under the above-mentioned conditions.
Remark	Link

ID=514

Tuning the optical and thermoelectric properties of SrTi0.8−x Sn0.2FexO3

Authors	Keerthana Muthamilselvam, M Mayarani, G Mohan Muralikrishna, Manjusha Battabyal, and Raghavan Gopalan
Source	Materials Research Express Volume: 6, Issue: 4 Time of Publication: 2019
Abstract	Effect of Fe doping on the structure, optical and thermoelectric properties of SrTi0.8Sn0.2O3 sample has been investigated. The SrTi0.8−xSn0.2FexO3 (x = 0, 0.1, 0.3) samples are fabricated using solid-state synthesis route. It is observed that Fe doping helps in reducing the densification temperature of SrTi0.8Sn0.2O3 during spark plasma sintering. Precipitation of Sn has been observed in SrTi0.8−xSn0.2FexO3 (x = 0, 0.1) samples while the SrTi0.8−xSn0.2FexO3 (x = 0.3) sample is of purely single cubic perovskite phase. All the samples consist of nanocrystalline grains and the grain size varies between 150 to 200 nm. Fourier transform infrared spectroscopy (FTIR) analysis reveals the distortion of TiO6 octahedra due to the increase in Fe content. Raman spectroscopy analysis has shown that perovskite cubic structure is stable from room temperature to 873 K. From thermophysical measurements, it is shown that the Fermi band gap reduces from 2.87 to 0.66 eV with increase in Fe in the investigated samples. The Seebeck co-efficient is found to change the sign from n –type to p-type with the increase of Fe concentration in SrTi0.8Sn0.2O3, which is an interesting observation to obtain p-type SrTiO3 based thermoelectric materials. The optical and thermoelectric properties show that Fe doping improves the thermoelectric properties of SrTi0.8Sn0.2O3 ceramics by altering the Seebeck co-efficient and thermal conductivity.
Remark	Link

ID=512

Versatile Application of Redox Processes for REBaCoMnO5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

Authors	Anna Olszewska, Konrad Świerczek, Wojciech Skubida, Zhihong Du, Hailei Zhao, Bogdan Dabrowski
Source	J. Phys. Chem. C Volume: 123, Issue: 1, Pages: 48-61 Time of Publication: 2019
Abstract	Belonging to the not fully explored REBaCo2-xMnxO5+δ system, a series of REBaCoMnO5+δ (RE: selected rare earth elements) oxides having perovskite-type structure is synthesized and studied in terms of their structural properties, oxygen content, stability, thermal expansion, and transport properties. Impact of RE3+ on physicochemical properties of the compounds is derived, with smaller cations causing a decrease of the unit cell volume, lowering of the total oxygen content and thermal expansion, but also suppressing electrical conductivity. It is shown that a proper chemical modification enables to successfully utilize REBaCoMnO5+δ in applications, in which redox processes associated with oxygen reduction/oxidation and transport determine the effectiveness of the working material. In particular, NdBaCoMnO5+δ (with larger Nd3+) shows good chemical stability in relation to Ce0.8Gd0.2O2−δ and La0.8Sr0.2Ga0.8Mg0.2O3-δ solid electrolytes and moderate thermal expansion, 20.04(4)·10–6 K–1 in 300–900 °C. In symmetrical configuration with La0.8Sr0.2Ga0.8Mg0.2O3-δ electrolyte its cathodic polarization resistance is found to be only 0.036 Ω cm2 at 900 °C, making it an excellent candidate cathode for solid oxide fuel cells. At the same time, YBaCoMnO5+δ (with small and cheap Y3+) delivers reversible oxygen storage capacity surpassing 3.4 wt % during the oxygen partial pressure swing process between air and 5 vol % H2 in Ar at 500 °C.
Remark	Link

ID=508

Improved CO2 flux by dissolution of oxide ions into the molten carbonate phase of dual-phase CO2 separation membranes

Authors	Wen Xing, Zuoan Li, Thijs Peters, Marie-Laure Fontaine, Michael McCann, Anna Evans, Truls Norby, Rune Bredesen
Source	Separation and Purification Technology Volume: 212, Pages: 723-727 Time of Publication: 2019
Abstract	In a solid-liquid dual-phase CO2 separation membrane, the native ions in the molten alkali carbonate, including carbonate anions and metal cations can transport CO2 in a process that is charge-compensated by electronic species (electrons or holes), oxide ions, or hydroxide ions, depending on materials and conditions. This strongly affects the design of experiments for assessing the performance of these membranes, and further determines the routes for integration of these membranes in industrial applications. Here we report how dissolved oxides in the liquid carbonate improve the CO2 flux of the membrane due to an enhanced charge-compensating oxygen ion transport. A qualitative understanding of the magnitude and role of oxide ion conductivity in the molten phase and in the solid support as a function of the temperature is provided. Employing a solid matrix of ceria, and dissolving CsVO3 and MoO3 oxides in the molten carbonate phase led to an almost doubled CO2 flux at 550 °C under dry ambient conditions. When the sweep gas contained 2.5% H2O, the CO2 flux was increased further due to formation of hydroxide ions in the molten carbonate acting as charge compensating species. Also, as a consequence of permeation controlled by ions in the liquid phase, the CO2 flux increased with the pore volume of the solid matrix.
Remark	Link

ID=506

Synthesis, Structure, and Conductivity of Alluaudite‐Related Phases in the Na2MoO4–Cs2MoO4–CoMoO4 System

Authors	Vasiliy N. Yudin, Evgeniya S. Zolotova, Sergey F. Solodovnikov, Zoya A. Solodovnikova, Iliya V. Korolkov, Sergey Yu. Stefanovich, Boris M. Kuchumov
Source	Europian Journal of Inorganic Chemistry Volume: 2019, Pages: 277-286 Time of Publication: 2018
Abstract	Phase formation study of the Na2MoO4–Cs2MoO4–CoMoO4 system resulted in new cesium‐containing alluaudite‐related phases. The solid solution Na4–2x‐yCsyCo1+x(MoO4)3 (0 ≤ x, y ≤ 0.30), based on the alluaudite‐type Na4–2xCo1+x(MoO4)3, and triple molybdate Na10(Cs4‐xNax)Co5(MoO4)12 (0 ≤ x ≤ 0.30) were found, and their structures were solved. In the structure of Na3.21Cs0.37Co1.21(MoO4)3 (a = 13.0917(8) Å, b = 13.5443(8) Å, c = 7.1217(4) Å, space group C2/c, β = 112.331(2), Z = 4), the cesium ions partially substitute the Na+ in the channels running along the c‐axis. The structure of Na10(Cs3.77Na0.23)Co5(MoO4)12 (a = 13.6572(3) Å, b = 11.5063(3) Å, c = 27.9898(5) Å, space group Pbca, Z = 4) was proved to be the aristotype for the pseudo orthorhombic Na25Cs8R5(MoO4)24 (R = Fe, Sc, In). The compounds contain alluaudite‐like layers of MoO4 tetrahedra and pairs of edge‐shared (Co, Na)O6 or (R, Na)O6 and NaO6 octahedra, which are connected by bridging MoO4 tetrahedra to form 3D frameworks differing from the alluaudite type. The frameworks contain channels along the c‐axis filled by Cs+ and Na+ ions. Bond valence sum (BVS) maps show that the alluaudite‐related molybdates can have a 2D sodium‐ion conductivity at elevated temperatures in contrast to the alluaudite‐type cathode material Na2+2xFe2‐x(SO4)3 with a 1D conductivity. The measured ionic conductivity of Na4–2xCo1+x(MoO4)3, Na4–2x‐yCsyCo1+x(MoO4)3, and Na10Cs4Co5(MoO4)12 reaches 10–3–10–2 S cm–1 at 500 °C. Abstract The phase relations, structures, ionic conductivity, and Na‐ion migration pathways for alluaudite‐related Na4–2x‐yCsyCo1+x(MoO4)3 and Na10(Cs4‐xNax)Co5(MoO4)12 (new type) were determined. Introducing Cs+ blocks 1D Na‐conductivity in the former phase, but it leads to possible 2D conductivity for the latter and the highest Na+ mobility among known alluaudite‐related molybdates at elevated temperatures.
Remark	https://doi.org/10.1002/ejic.201801307 Link

ID=504

A comprehensive study on improved power materials for high-temperature thermoelectric generators

Authors
Source	Journal of Power Sources Volume: 410-411, Pages: 143-151 Time of Publication: 2019
Abstract	Dense Ca3Co4O9-NaxCoO2-Bi2Ca2Co2O9 (CCO-NCO-BCCO) nanocomposites were produced from sol-gel derived Ca2.25Na0.3Bi0.35Tb0.1Co4O9 powder by four methods: Hot-pressing (HP), spark plasma sintering (SPS) and pressureless sintering in air or O2 atmosphere. Nanocomposites from HP and SPS revealed nanosized grains and showed a thermoelectric power factor of 4.8 and 6.6 μW cm−1 K−2, respectively, at 1073 K in air. A dense 2D nanocomposite with structures on multiple length scales and enhanced thermoelectric properties was obtained from pressureless sintering in O2 atmosphere. The resulting 2D nanocomposite enabled the simultaneous increase in isothermal electrical conductivity σ and Seebeck coefficient α, and showed a thermoelectric power factor of 8.2 μW cm−1 K−2 at 1073 K in air. The impact of materials with enhanced electrical conductivity and power factor on the electrical power output of thermoelectric generators was verified in prototypes. A high electrical power output and power density of 22.7 mW and 113.5 mW cm−2, respectively, were obtained, when a hot-side temperature of 1073 K and a temperature difference of 251 K were applied. Different p- and n-type materials were used to verify the effect of the thermoelectric figure-of-merit and power factor on the performance of thermoelectric generators.
Remark	Link

ID=503

Triple-phase ceramic 2D nanocomposite with enhanced thermoelectric properties

Authors	Michael Bittner, Nikola Kanas, Richard Hinterding, Frank Steinbach, Dennis Groeneveld, Piotr Wemhoff, Kjell Wiik, Mari-Ann Einarsrud, Armin Feldhoff
Source	Journal of the European Ceramic Society Volume: 39, Issue: 4, Pages: 1237-1244 Time of Publication: 2019
Abstract	A thermoelectric triple-phase p-type Ca3Co4O9-NaxCoO2-Bi2Ca2Co2O9 (CCO–NCO–BCCO) 2D nanocomposite was obtained from pressureless sintering in air. The anisotropic thermoelectric properties of the nanocomposite exhibit a high electrical conductivity of 116 S cm−1 and a power factor of 6.5 μW cm−1 K−2 perpendicular to the pressing direction at 1073 K in air. A corresponding zT value of 0.35 was obtained. Three co-doped, thermoelectrically active misfit-layered materials were stacked to form a triple-phase nanocomposite, which combines the advantages of all three materials. The resulting nanocomposite enables simultaneous increases of the isothermal electrical conductivity σ and the Seebeck coefficient α by charge carrier concentration engineering and synergistic effects. The Bi2Ca2Co2O9 and NaxCoO2 phases were stabilized in a Ca3Co4O9 matrix at high temperatures. To evaluate the application of the nanocomposite in high-temperature thermoelectric generators, the representation of the electrical conductivity and power factor in a Ioffe plot was more appropriate than the zT value.
Remark	Link

ID=502

Effects of calcium doping to oxygen reduction activity on Pr2-xCaxNiMnO6 cathode

Authors	Liping Sun, Huan Li, Jiaqi Zhao, Guiling Wang, Lihua Huo, Hui Zhao
Source	Journal of Alloys and Compounds Volume: 777, Pages: 1319-1326 Time of Publication: 2019
Abstract	Pr2-xCaxNiMnO6-δ (PCNMOx, x = 0.0–0.3) are prepared successfully by glycine-nitrate method. The effects of calcium doping to the crystal structure, the oxygen non-stoichiometry, and the cathode properties are evaluated by XRD, SEM, XPS and EIS. The double perovskite PCNMOx crystallize into a monoclinic structure with space group P21/n. The unit cell volumes and thermal expansion coefficients increase systematically with Ca2+ doping, due to the gradual generation of oxygen vacancies in the lattice. Pr2-xCaxNiMnO6-δ exhibits promising chemical compatibility with the electrolyte material Ce0.9Gd0.1O1.95 (GDC) at 1200 °C. The electrochemical characterization results indicate that both oxygen vacancy concentration and electrical conductivity play important roles to cathode properties. The optimum composition Pr1.8Ca0.2NiMnO6-δ shows the lowest polarization resistance of 0.18 Ω cm2 and highest peak power density of 0.3 W cm2 at 700 °C on GDC electrolyte supported fuel cell. The electrochemical impedance measurements under oxygen partial pressures, together with distribution of relaxation times analysis, identify three conjunctive elementary processes involved in the cathode reaction, and prove that the charge transfer process is the major rate-determining step of oxygen reduction reaction.
Remark	Link

ID=501

Metal-Doping of La5.4MoO11.1 Proton Conductors: Impact on the Structure and Electrical Properties

Authors
Source	Inorg. Chem. Volume: 57, Issue: 20, Pages: 12811-12819 Time of Publication: 2018
Abstract	La5.4MoO11.1 proton conductors with different metal doping (Ca2+, Sr2+, Ba2+, Ti4+, Zr4+, and Nb5+) have been prepared and structurally and electrically characterized. Different polymorphs are stabilized depending on the doping and cooling rate used during the synthesis process. The most interesting results are obtained for Nb-doping, La5.4Mo1–xNbxO11.1–x/2, where single compounds are obtained in the compositional range 0 ≤ x ≤ 0.2. These materials are fully characterized by structural techniques such as X-ray and neutron powder diffraction and transmission electron microscopy, which independently confirm the changes of polymorphism. Scanning electron microscopy and impedance spectroscopy measurements in dry/wet gases (N2, O2, and 5% H2–Ar) showed an enhancement of the sinterability and electrical properties of the materials after Nb-doping. Conductivity measurements under very reducing conditions revealed that these materials are mixed ionic-electronic conductors, making them potential candidates for hydrogen separation membranes.
Remark	Link

ID=500

Effect of B-site doping on electrical conductivity of YAlO3 based electrolytes for solid oxide fuel cells

Authors	Ramya Hariharan, Prakash Gopalan
Source	Journal of Electroceramics Volume: 42, Issue: 1-2, Pages: 79–86 Time of Publication: 2019
Abstract	Solid oxide fuel cells (SOFCs) have emerged as high temperature fuel cell technology operating at temperatures around 1000 °C. Lowering the operating temperature enables the use of cheaper materials while maintaining high power outputs. Electrolytes with ABO3-type perovskite structure are good ionic conductors and are promising materials for SOFCs. In this study, a systematic investigation on the synthesis and characterization of Mg- substituted YAlO3 system has been performed. The samples have been synthesized by wet chemical citrate gel route and the electrical conductivity measurements have been conducted in air between 300 and 800 °C. Effect of composition of the phases on total conductivity has been analyzed employing X-ray diffraction. The influence of microstructure on total conductivity has been studied using scanning electron microscopy and orientation imaging microscopy.
Keywords	Intermediate temperature SOFCs, Perovskites, Total conductivity, Citrate gel route, Doping
Remark	Link

ID=496

Dy doped SrTiO3: A promising anodic material in solid oxide fuel cells

Authors	Saurabh Singh, Prabhakar Singh, Massimo Viviani, Sabrina Presto
Source	International Journal of Hydrogen Energy Volume: 43, Issue: 41, Pages: 19242-19249 Time of Publication: 2018
Abstract	The perovskite-type oxides, having a general formula ABO3, are promising candidates for anode materials in solid oxide fuel cells. In particular, doped SrTiO3 based perovskites are potential mixed ionic-electronic conductors and they are known to have excellent thermal and chemical stability along with carbon and sulfur tolerance. In this work, DyxSr1-xTiO3-δ system with x = 0.03, 0.05, 0.08 and 0.10 is studied to understand the influence of Dy content on its structural and electrical behavior. Electrochemical properties are measured, both in air and hydrogen atmosphere, and structural characterizations are performed before and after electrochemical tests and compared each other to study the stability. Results show that DyxSr1-xTiO3-δ powders with x ≤ 0.05, are single phase, while for x ≥ 0.08 a small amount of secondary phases is formed. In air, the conductivity is predominantly mixed ionic-electronic type for x ≤ 0.05, becoming ionic for x ≥ 0.08. It is observed that conductivity, for each composition, increases passing from air to hydrogen and activation energy decreases. Dy0.05Sr0.95TiO3-δ shows the highest conductivity in air whereas Dy0.08Sr0.92TiO3-δ in H2 atmosphere. Degradation observed by XRD is negligible for x ≤ 0.05 but increases with higher Dy content.
Remark	https://doi.org/10.1016/j.ijhydene.2018.08.160 Link

ID=494

Computational Prediction and Experimental Realization of p-Type Carriers in the Wide-Band-Gap Oxide SrZn1–xLixO2

Authors	Christos A. Tzitzeklis, Jyoti K. Gupta, Matthew S. Dyer, Troy D. Manning, Michael J. Pitcher, Hongjun J. Niu, Stanislav Savvin, Jonathan Alaria, George R. Darling, John B. Claridge, and Matthew J. Rosseinsky
Source	Inorg. Chem. Volume: 57, Issue: 19, Pages: 11874-11883 Time of Publication: 2018
Abstract	It is challenging to achieve p-type doping of zinc oxides (ZnO), which are of interest as transparent conductors in optoelectronics. A ZnO-related ternary compound, SrZnO2, was investigated as a potential host for p-type conductivity. First-principles investigations were used to select from a range of candidate dopants the substitution of Li+ for Zn2+ as a stable, potentially p-type, doping mechanism in SrZnO2. Subsequently, single-phase bulk samples of a new p-type-doped oxide, SrZn1–xLixO2 (0 < x < 0.06), were prepared. The structural, compositional, and physical properties of both the parent SrZnO2 and SrZn1–xLixO2 were experimentally verified. The band gap of SrZnO2 was calculated using HSE06 at 3.80 eV and experimentally measured at 4.27 eV, which confirmed the optical transparency of the material. Powder X-ray diffraction and inductively coupled plasma analysis were combined to show that single-phase ceramic samples can be accessed in the compositional range x < 0.06. A positive Seebeck coefficient of 353(4) μV K–1 for SrZn1–xLixO2, where x = 0.021, confirmed that the compound is a p-type conductor, which is consistent with the pO2 dependence of the electrical conductivity observed in all SrZn1–xLixO2 samples. The conductivity of SrZn1–xLixO2 is up to 15 times greater than that of undoped SrZnO2 (for x = 0.028 σ = 2.53 μS cm–1 at 600 °C and 1 atm of O2).
Remark	Link

ID=493

Microstructure and doping effect on the enhancement of the thermoelectric properties of Ni doped Dy filled CoSb3 skutterudites

Authors	Vikrant Trivedi, Manjusha Battabyal, Priyadarshini Balasubramanian, G. Mohan Muralikrishna, Pawan Kumar Jain and Raghavan Gopalan
Source	Sustainable Energy Fuels Volume: 2, Pages: 2687-2697 Time of Publication: 2018
Abstract	The thermoelectric properties of nanostructured Ni doped Dy filled CoSb3 skutterudites (Dy0.4Co4−xNixSb12 (x = 0, 0.4, and 0.8)) have been reported. The samples are processed using a solid-state synthesis route. The structural analysis of the samples using X-ray diffraction reveals the existence of a single skutterudite phase in Ni doped samples irrespective of the Ni concentration. Microstructure studies using transmission electron microscopy and scanning electron microscopy show the existence of nanometer (∼60 nm) size equiaxed grains in the investigated samples. A few recrystallized elongated grains (∼200 nm) are observed in the Dy0.4Co3.2Ni0.8Sb12 sample. The power factor of the Dy0.4Co3.2Ni0.8Sb12 sample is enhanced to 5.2 mW mK−2, which is the highest power factor for the doped ternary skutterudites reported so far. The enhancement of the power factor is due to the substantial reduction in electrical resistivity with an increase in Ni concentration at higher temperature. The lattice thermal conductivity is drastically reduced to 0.3 W mK−1 at 773 K in the Dy0.4Co3.2Ni0.8Sb12 sample due to the enhanced phonon scattering from Ni induced point defects and grain boundaries. As a result, a huge increase in the figure of merit (ZT ∼ 1.4 ± 0.14) at 773 K is observed in the Dy0.4Co3.2Ni0.8Sb12 sample, the highest among those of the single element filled CoSb3 skutterudites reported so far at this temperature. Hence, Ni doping could enhance the thermoelectric efficiency of Dy filled CoSb3 skutterudites. This can be taken as a reference to synthesize CoSb3 skutterudite thermoelectric materials having a higher figure of merit.
Remark	DOI: 10.1039/C8SE00395E Link

ID=492

Computational Prediction and Experimental Realization of p-Type Carriers in the Wide-Band-Gap Oxide SrZn1–xLixO2

Authors	Christos A. Tzitzeklis, Jyoti K. Gupta, Matthew S. Dyer, Troy D. Manning, Michael J. Pitcher, Hongjun J. Niu, Stanislav Savvin, Jonathan Alaria, George R. Darling, John B. Claridge, and Matthew J. Rosseinsky
Source	Inorg. Chem. Time of Publication: 2018
Abstract	It is challenging to achieve p-type doping of zinc oxides (ZnO), which are of interest as transparent conductors in optoelectronics. A ZnO-related ternary compound, SrZnO2, was investigated as a potential host for p-type conductivity. First-principles investigations were used to select from a range of candidate dopants the substitution of Li+ for Zn2+ as a stable, potentially p-type, doping mechanism in SrZnO2. Subsequently, single-phase bulk samples of a new p-type-doped oxide, SrZn1–xLixO2 (0 < x < 0.06), were prepared. The structural, compositional, and physical properties of both the parent SrZnO2 and SrZn1–xLixO2 were experimentally verified. The band gap of SrZnO2 was calculated using HSE06 at 3.80 eV and experimentally measured at 4.27 eV, which confirmed the optical transparency of the material. Powder X-ray diffraction and inductively coupled plasma analysis were combined to show that single-phase ceramic samples can be accessed in the compositional range x < 0.06. A positive Seebeck coefficient of 353(4) μV K–1 for SrZn1–xLixO2, where x = 0.021, confirmed that the compound is a p-type conductor, which is consistent with the pO2 dependence of the electrical conductivity observed in all SrZn1–xLixO2 samples. The conductivity of SrZn1–xLixO2 is up to 15 times greater than that of undoped SrZnO2 (for x = 0.028 σ = 2.53 μS cm–1 at 600 °C and 1 atm of O2).
Remark	DOI: 10.1021/acs.inorgchem.8b00697 Link

ID=491

Thermoelectric Properties of (1-x)LaCoO₃.(x)La_0.95Sr_0.05CoO₃ composite

Authors	Ashutosh Kumar, Karuna Kumari, B Jayachandran, D Sivaprahasam and Ajay D Thakur
Source	Materials Research Express Time of Publication: 2018
Abstract	Thermopower in cobalt oxides has been a rich area of interest due to the existence of the different charge states along-with different spin states. In this report, we have systematically studied the structural and thermal transport properties of ($1-x$)LaCoO$_3$.($x$)La$_{0.95}$Sr$_{0.05}$CoO$_3$ composite. The Seebeck coefficient ($alpha$) values for the composite increases at high temperatures compared to the LaCoO$_3$ (LCO) and La$_{0.95}$Sr$_{0.05}$CoO$_3$ (LSCO) systems. The electrical conductivity ($sigma$) decreases with the increase in the LSCO fraction which may be attributed to the localization of charge carriers due to intersite diffusion. All the samples show increase in the value of $sigma$ with increase in temperature. The thermal conductivity ($kappa$) values decrease with the increase of LSCO content in the composite and the phonon thermal conductivity dominates over the total thermal conductivity. We observe a maximum value of figure of merit (ZT)$sim$0.06 at 640,K for $x=$0.05.
Remark	Link

ID=490

Wide bandgap oxides for low-temperature single-layered nanocomposite fuel cell

Authors
Source	Nano Energy Volume: 53, Pages: 391-397 Time of Publication: 2018
Abstract	A composite of wide bandgap lithium-nickel-zinc-oxide (LNZ) and gadolinium-doped-cerium-oxide (GDC) was systematically analyzed for a low-temperature nanocomposite fuel cell in a so-called single-component configuration in which the electrodes and electrolyte form a homogenous mixture. We found that the operational principle of a single-layer fuel cell can be explained by electronic blocking by the oxide mixture with almost insulator-like properties in the operating voltage regime of the fuel cell, which will prevent short-circuiting, and by its catalytic properties that drive the fuel cell HOR and ORR reactions. The resistance to charge transport and leakage currents are dominant performance limiting factors of the single-component fuel cell. A test cell with Au as current collector reached a power density of 357 mWcm−2 at 550 °C. Changing the current collector to a Ni0.8Co0.15Al0.05LiO2 (NCAL) coated Ni foam produced 801 mWcm−2, explained by better catalytic properties. However, utilizing NCAL coated Ni foam may actually turn the 1-layer fuel cell device into a traditional 3-layer (anode-electrolyte-cathode) structure. This work will help in improving the understanding of the underlying mechanisms of a single-layer fuel cell device important to further develop this potential energy technology.
Keywords	Bandgap; Ceramic; Fuel cell; Ionic conductivity; Nanocomposite; Single-component
Remark	https://doi.org/10.1016/j.nanoen.2018.08.070 Link

ID=489

Crystal Structure and Coordination of B-Cations in the Ruddlesden–Popper Phases Sr3−xPrx(Fe1.25Ni0.75)O7−δ (0 ≤ x ≤ 0.4)

Authors
Source	Inorganics Volume: 6, Issue: 3 Time of Publication: 2018
Abstract	Compounds Sr3−xPrxFe1.25Ni0.75O7−δ with 0 ≤ x ≤ 0.4 and Ruddlesden–Popper n = 2 type structures were synthesized and investigated by X-ray and neutron powder diffraction, thermogravimetry, and Mössbauer spectroscopy. Both samples, prepared at 1300 °C under N2(g) flow and samples subsequently air-annealed at 900 °C, were studied. The structures contained oxygen vacancies in the perovskite layers, and the Fe/Ni cations had an average coordination number less than six. The oxygen content was considerably higher for air-annealed samples than for samples prepared under N2, 7 − δ = ~6.6 and ~5.6 per formula unit, respectively. Mössbauer data collected at 7 K, below magnetic ordering temperatures, were consistent with X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) results. The electrical conductivity was considerably higher for the air-annealed samples and was for x = 0.1~30 S·cm−1 at 500 °C. The thermal expansion coefficients were measured in air between room temperature and 900 °C and was found to be 20–24 ppm·K−1 overall.
Keywords
Remark	Link

ID=484

Assessment of layered La2-x(Sr,Ba)xCuO4-δ oxides as potential cathode materials for SOFCs

Authors	Anna Niemczyk, Anna Olszewska, Zhihong Du, Zijia Zhang, Konrad Świerczeka, Hailei Zhao
Source	International Journal of Hydrogen Energy Volume: 43, Issue: 32, Pages: 15492-15504 Time of Publication: 2018
Abstract	In this paper, selected layered cuprates with La2-x(Sr,Ba)xCuO4-δ formula are evaluated as candidate cathode materials for Solid Oxide Fuel Cells. Two synthesis routes, a typical solid state reaction and a sol-gel method yield well-crystallized La1.5Sr0.5CuO4-δ, La1.6Ba0.4CuO4-δ and La1.5Sr0.3Ba0.2CuO4-δ materials having tetragonal I4/mmm space group, but differing in morphology of the powder. Fine powders obtained using sol-gel route seem to be more suitable for preparation of the porous cathode layers having good adhesion on the solid electrolyte, but powders obtained after the solid state route can be also successfully utilized. Investigations of structural and transport properties, the oxygen nonstoichiometry and its change with temperature, thermal expansion, as well as chemical and thermal stability are systematically performed, to evaluate and compare basic physicochemical properties of the oxides. At room temperature the average valence state of copper is found to be in 2.2–2.35 range, indicating oxygen deficiency in all of the compounds, which further increases with temperature. The conducted high-temperature X-ray diffraction tests reveal moderate, but anisotropic thermal expansion of La2-x(Sr,Ba)xCuO4-δ, with higher expansion at temperatures above 400 °C occurring along a-axis, due to the oxygen release. However, the corresponding chemical expansion effect is small and the materials possess moderate thermal expansion in the whole studied temperature range. All compounds show relatively high electrical conductivity at the elevated temperatures, related to the Cu2+/Cu3+ charge transfer, with the highest values recorded for La1.5Sr0.5CuO4-δ. Comprehensive studies of chemical stability of the selected La1.5Sr0.5CuO4-δ material with La0.8Sr0.2Ga0.8Mg0.2O3-δ solid electrolyte revealed complex behavior, with stability being dependent apart from temperature, also on morphology of the powders. A model describing such behavior is presented. While it is possible to minimize reactivity and characterize electrochemical properties of the La1.5Sr0.5CuO4-δ-based cathode layer, usage of the buffer layer is indispensable to maintain full stability. It is shown that mutual chemical compatibility of La1.5Sr0.5CuO4-δ and commonly used La0.4Ce0.6O2-δ buffer layer material is excellent, with no reactivity even at 1000 °C for prolonged time. Laboratory-scale fuel cell with the La1.5Sr0.5CuO4-δ cathode sintered at the optimized temperature is able to deliver 0.16 W cm−2 at 800 °C while fueled with wet hydrogen.
Keywords	Layered cuprates, Cathodic polarization, Chemical stability, LSGM, Buffer layer, SOFC
Remark	https://doi.org/10.1016/j.ijhydene.2018.06.119 Link

ID=481

Electrochemical and degradation study of Sr0.6Na0.4SiO3-δ

Authors	Kapil Sood, Jyoti Kaswan, Surinder P. Singh, Truls Norby, Suddhasatwa Basu
Source	Journal of Solid State Electrochemistry Volume: 22, Issue: 10, Pages: 3009–3013 Time of Publication: 2018
Abstract	The high ionic conductivity of Na-doped SrSiO3 (SNS) is a topic of interest due to contradictory reports on its conductivity and stability by various groups. From a recent NMR study, it is proposed that Na+ is mainly responsible for ionic conductivity in an amorphous Na2Si2O5 phase present in SNS. The present study further extends to determine experimentally the ion transport number as well as material characteristics after long time annealing at 600 °C. The conductivity behavior of as-sintered and annealed nominally Sr0.6Na0.4SiO3-δ is investigated and a sharp fall (~ 2 order magnitude) of the same at 800 °C is found. An XPS study is included for comprehensive understanding of conductivity and degradation behavior of SNS material. On basis of the collective results, we propose a rational description of the conduction and material degradation of SNS.
Keywords	SrSiO3, Transport number, SOFC, Ionic conductivity, Protonic conductivity
Remark	Link

ID=480

Novel ReBaCo1.5Mn0.5O5+δ (Re: La, Pr, Nd, Sm, Gd and Y) perovskite oxide: influence of manganese doping on the crystal structure, oxygen nonstoichiometry, thermal expansion, transport properties, and application as a cathode material in solid oxide f

Authors	Anna Olszewska, Zhihong Du, Konrad Świerczek, Hailei Zhao and Bogdan Dabrowski
Source	Journal of Materials Chemistry A Issue: 6, Pages: 13271-13285 Time of Publication: 2018
Abstract	In this work, a novel series of Mn-containing ReBaCo1.5Mn0.5O5+δ (Re: selected rare earth elements) perovskite-type oxides is studied, with systematic measurements of physicochemical properties being reported. Comparison with the very well-studied, parent ReBaCo2O5+δ allows determination of the role of the introduced manganese concerning modification of the crystal structure at room temperature and its evolution at high temperatures, variation of the oxygen content, thermal stability of the materials, and total electrical conductivity, as well as thermal and chemical expansion. Generally, the presence of Mn cations does not affect the tendency for A-site cation ordering, resulting in an increased unit cell volume of the compounds, as well as causing an increase of the oxygen content. Reduced thermal expansion, together with high values of electrical conductivity and suitable thermal stability, makes the compounds containing larger Re3+ cations attractive from the point of view of application as cathode materials in solid oxide fuel cells. Chemical compatibility studies reveal the sufficient stability of the considered perovskites in relation to Ce0.8Gd0.2O2−δ solid electrolyte, while unexpected, somewhat increased reactivity towards La0.8Sr0.2Ga0.8Mg0.2O3−δ and La0.4Ce0.6O2−δ is also reported. Furthermore, the electrochemical tests of the symmetric cells show strong dependence of the polarization resistance of the electrode on the synthesis and sintering temperatures. For the selected and optimized NdBaCo1.5Mn0.5O5+δ layer employed in the electrolyte-supported (LSGM) symmetric cell with a CGO buffer layer, the cathodic polarization resistance is 0.043 Ω cm2 at 900 °C. A wet hydrogen-fuelled button-type cell with the NdBaCo1.5Mn0.5O5+δ-based cathode is also prepared, delivering the maximum power density exceeding 1.3 W cm−2 at 850 °C.
Remark	DOI: 10.1039/C8TA03479F Link

ID=479

High performance ceramic nanocomposite fuel cells utilizing LiNiCuZn-oxide anode based on slurry method

Authors
Source	International Journal of Hydrogen Energy Time of Publication: 2018
Abstract	A multi-oxide material LiNiCuZn-oxide was prepared through a slurry method as an anode for ceramic nanocomposite fuel cell (CNFC). The CNFCs using this anode material, LSCF as cathode material and a composite electrolyte consisting of CaSm co-doped CeO2 and (NaLiK)2CO3 produced ∼1.03 W/cm2 at 550 °C due to efficient reaction kinetics at the electrodes and high ionic transport in the nanocomposite electrolyte. The electrochemical impedance spectroscopy revealed low ionic transport losses (0.238 Ω cm2) and low polarization losses (0.124 Ω cm2) at the electrodes. The SEM measurements revealed the porous microstructures of the composite materials at electrode and the dense mixture of CaSm co-doped CeO2 and (NaLiK)2CO3. The Brunauer-Emmett-Teller (BET) analysis revealed high surface areas, 4.1 m2/g and 3.8 m2/g, of the anode and cathode respectively. This study provides a promising material for high performance CNFCs.
Keywords	Ceramic, Conductivity, Fuel cell, Multi-oxide, Nanocomposite, Synthesis
Remark	https://doi.org/10.1016/j.ijhydene.2018.03.232 Link

ID=476

Influence of annealing at intermediate temperature on oxygen transport kinetics of Pr2NiO4+δ

Authors
Source	J. Mater. Chem. A Volume: 6, Pages: 8331-8339 Time of Publication: 2018
Abstract	Electrical conductivity relaxation (ECR) and oxygen permeation measurements were conducted, at 750 °C, to assess the long-term oxygen transport characteristics of the mixed ionic–electronic conducting Pr2NiO4+δ with a K2NiF4 structure. The results show that the apparent values for the oxygen diffusion and surface exchange coefficients extracted from the data and the associated oxygen flux increase over 120 h by 1–2 orders of magnitude. The results of post-mortem X-ray diffraction analysis of the samples show partial to virtually complete decomposition of Pr2NiO4+δ under the conditions of the experiments to Pr4Ni3O10+δ, PrNiO3−δ, Pr6O11, and traces of NiO. Pulse 18O–16O isotopic exchange (PIE) measurements confirmed fast surface exchange kinetics of the higher-order Ruddlesden–Popper phase Pr4Ni3O10+δ and Pr6O11 formed upon decomposition. Additional factors related to the microstructure, however, need to be considered to explain the observations.
Remark	Link

ID=475

Thermoelectric properties of (1-x)LaCoO3.xLa0.7Sr0.3MnO3 composite

Authors	Ashutosh Kumar, Karuna Kumari, B. Jayachandran, D. Sivaprahasam, Ajay D.Thakur
Source	Journal of Alloys and Compounds Volume: 749, Pages: 1092-1097 Time of Publication: 2018
Abstract	We report the thermoelectric (TE) properties of (1-x)LaCoO3.xLa0.7Sr0.3MnO3 (0 < x < 0.50) composite in a temperature range 320–800 K. Addition of La0.7Sr0.3MnO3 to LaCoO3 in small amount (5 weight %) improves the overall Seebeck coefficient (α) at higher temperatures. The electrical conductivity however decreases due to a decrease in carrier concentration of the composite. The decrease in electrical conductivity of the composite at high temperature may be attributed to the insulating nature of the LSMO above room temperature. Thermal conductivity (κ) of all the samples increases with an increase in the temperature, but decreases with increasing LSMO content. We also report the local variation of Seebeck coefficient across the composite samples measured using a precision Seebeck measurement system. A maximum value of 0.09 for the figure of merit (ZT) is obtained for 0.95LaCoO3.0.05La0.7Sr0.3MnO3 at 620 K which is significantly higher than the ZT of either of LaCoO3 or La0.7Sr0.3MnO3 at 620 K. This suggests the potential for enhancement of operating temperatures of hitherto well known low temperature thermoelectric materials through suitable compositing approach.
Keywords	Thermal conductivity, Electrical conductivity, Perovskites, Manganites, Cobaltate, Composite
Remark	https://doi.org/10.1016/j.jallcom.2018.03.347 Link

ID=474

Lanthanum doped strontium titanate - ceria anodes: deconvolution of impedance spectra and relationship with composition and microstructure

Authors	Dariusz Burnat, Gunnar Nurk, Lorenz Holzer, Michal Kopecki, Andre Heel
Source	Journal of Power Sources Volume: 385, Pages: 62-75 Time of Publication: 2018
Abstract	Electrochemical performance of ceramic (Ni-free) SOFC anodes based on La0.2Sr0.7TiO3-δ (LST) and Gd0.1Ce0.9O1.95-δ (CGO) is thoroughly investigated. Microstructures and compositions are systematically varied around the percolation thresholds of both phases by modification of phase volume fractions, particle size distributions and firing temperature. Differential impedance spectroscopy was performed while varying gas composition, electrical potential and operating temperature, which allows determining four distinct electrode processes. Significant anode impedances are measured at low frequencies, which in contrast to the literature cannot be linked with gas concentration impedance. The dominant low frequency process (∼1 Hz) is attributed to the chemical capacitance. Combined EIS and microstructure investigations show that the chemical capacitance correlates inversely with the available surface area of CGO, indicating CGO surface reactions as the kinetic limitation for the dominant anode process and for the associated chemical capacitance. In anodes with a fine-grained microstructure this limitation is significantly smaller, which results in an impressive power output as high as 0.34 Wcm−2. The anodes show high redox stability by not only withstanding 30 isothermal redox cycles, but even improving the performance. Hence, compared to conventional Ni-cermet anodes the new LST-CGO material represents an interesting alternative with much improved redox-stability.
Keywords	SOFC, LST, Microstructure analysis, Electrochemical impedance, Spectroscopy, Redox Anodes
Remark	https://doi.org/10.1016/j.jpowsour.2018.03.024 Link

ID=473

Influence of texture and grain misorientation on the ionic conduction in multilayered solid electrolytes – interface strain effects in competition with blocking grain boundaries

Authors	J. Keppner, J. Schubert, M. Ziegner, B. Mogwitz, J. Janek and C. Korte
Source	Physical Chemistry Chemical Physics Issue: 14 Time of Publication: 2018
Abstract	Interface strain and its influence on the ionic transport along hetero-interfaces has gained a lot of attention over the last decade and is controversially discussed. We investigate the relaxation of mismatch induced interfacial strain as a function of the degree of orientation/texture of the columnar crystallites and assess the impact on the oxygen ion conductivity in Er2O3/YSZ multilayer systems. Results from X-ray diffraction clearly show, that the width of the strained hetero-interface region increases with an increasing degree of orientation of the crystallites. The combined impact of film texture and strain at the hetero-interfaces of the film on the ionic conductivity however is not easily deduced from these measurements. The samples with the highest degree of orientation, i.e. with only one azimuthal variant, show strong anisotropic electrical properties. In samples with a lower degree of orientation, i.e. samples with a fiber texture, anisotropic properties cannot be detected, possibly due to a geometrical averaging of the electrical properties. The expected strain induced monotonic increase of the ionic conductivity with decreasing layer thickness and thus increasing interfacial influence could only be detected for samples with a fiber texture and a considerable degree of crystallite misorientation. This leads to the important conclusion that the texture and therefore the nature of the grain boundaries and their network influence the ionic conductivity of the multilayer thin films in the same order of magnitude as the misfit induced interface strain. Thus, the potential design of strain-controlled ionic conductors requires additionally the control of the microstructure in terms of grain orientation.
Remark	Link

ID=472

Crystal Structure, Hydration, and Two-Fold/Single-Fold Diffusion Kinetics in Proton-Conducting Ba0.9La0.1Zr0.25Sn0.25In0.5O3−a Oxide

Authors	Wojciech Skubida, Anna Niemczyk, Kun Zheng, Xin Liu and Konrad Świeczek
Source	Crystals Volume: 8, Issue: 3, Pages: 136 Time of Publication: 2018
Abstract	In this work, hydration kinetics related to the incorporation of water into proton-conducting Ba0.9La0.1Zr0.25Sn0.25In0.5O3−a perovskite-type oxide are presented, with a recorded transition on temperature from a single-fold to a two-fold behavior. This can be correlated with an appearance of the electronic hole component of the conductivity at high temperatures. The collected electrical conductivity relaxation data allowed to calculate chemical diffusion coefficient D and surface exchange reaction coefficient k, as well as respective activation energies of their changes on temperature. Presented results are supplemented with a systematic characterization of the structural properties of materials synthesized at different temperatures, amount of incorporated water after hydration in different conditions, influence of water content on the crystal structure, as well as electrical conductivity in dry, H2O- and D2O-containing air, which enabled to evaluate proton (deuterium) conductivity.
Keywords	Perovskite oxides; substituted barium indate; hydration; proton conductivity; relaxation experiments; coupled/decoupled ionic transport.
Remark	doi:10.3390/cryst8030136 Link

ID=471

Sol-gel synthesis of ZnO/Zn2-xFexTiO4 powders: structural properties, electrical conductivity and dielectric behavior

Authors	Izabella Dascalu, Cristian Hornoiu, Jose Maria Calderon-Moreno, Madalin Enache, Daniela Culita, Simona Somacescu
Source	Journal of Sol-Gel Science and Technology Volume: 86, Issue: 1, Pages: 151–161 Time of Publication: 2018
Abstract	The aim of this work was an investigation of structural and electrical properties of ZnO/Zn2-xFexTiO4 (x = 0.7, 1, 1.4) powders. The compounds obtained by sol-gel method are characterized by several techniques: X-ray diffraction (XRD), N2 adsorption–desorption isotherms, scanning and transmission electron microscopy (SEM and TEM), X-ray photoelectron spectroscopy (XPS), electrical and dielectrical measurements. The XRD, SEM and XPS analysis confirmed the formation of ZnFeTiO4 inverse spinel structure. The electrical and dielectrical properties of ZnO/Zn2-xFexTiO4 (x = 0.7, 1, 1.4) were measured by impedance spectroscopy, revealing a decrease in the electrical conductivity and the dielectric constant with Fe content.
Keywords	Sol-gel, ZnO/ZnFeTiO4, dielectric constant, AC conductivity
Remark	Link

ID=470

p-Type/n-type behaviour and functional properties of KxNa(1-x)NbO3 (0.49 ≤ x ≤ 0.51) sintered in air and N2

Authors	Fayaz Hussain, Iasmi Sterianou, Amir Khesro, Derek C. Sinclair, Ian M. Reaney
Source	Journal of the European Ceramic Society Volume: 38, Issue: 9, Pages: 3118-3126 Time of Publication: 2018
Abstract	Potassium sodium niobate (KNN) is a potential candidate to replace lead zirconate titanate in sensor and actuator applications but there are many fundamental science and materials processing issues to be understood before it can be used commercially, including the influence of composition and processing atmosphere on the conduction mechanisms and functional properties. Consequently, KNN pellets with different K/Na ratios were sintered to 95% relative density in air and N2 using a conventional mixed oxide route. Oxygen vacancies (VO••) played a major role in the semi-conduction mechanism in low p(O2) for all compositions. Impedance spectroscopy and thermo-power data confirmed KNN to be n-type in low p(O2) in contradiction to previous reports of p-type behaviour. The best piezoelectric properties were observed for air- rather than N2-sintered samples with d33 = 125 pC/N and kp = 0.38 obtained for K0.51Na0.49NbO3.
Keywords	p-Type, n-Type, Low p(O2), Oxygen vacancies, Seebeck coefficient
Remark	https://doi.org/10.1016/j.jeurceramsoc.2018.03.013 Link

ID=469

La1.8Sr0.2Ni0.8M0.2O4 (M = Fe, Co, or Cu) Complex Oxides: Synthesis, Structural Characterization, and Dielectric Properties

Authors	T.I. Chupakhina, N.V. Mel’nikova, E.A. Yakovleva, Yu. A. Nikitina
Source	Russian Journal of Inorganic Chemistry Volume: 63, Issue: 2, Pages: 141–148 Time of Publication: 2018
Abstract	New solid solutions La1.8Sr0.2Ni0.8M0.2O4 (M = Fe, Co, or Cu) have been prepared, and their crystal- chemical characteristics and electric properties studied. The studied materials have been shown to have activation-time conductivity. Structural distortions have been found to affect the dielectric properties of ceramic samples. La1.8Sr0.2Ni0.8M0.2O4 is observed to have the greatest distortion of АО9 coordination polyhedra and a higher dielectric constant.
Remark	Link

ID=466

Structural transformations, water incorporation and transport properties of tin-substituted barium indate

Authors	Kacper Cichy, Wojciech Skubid, Konrad Świerczek
Source	Journal of Solid State Chemistry Volume: 262, Pages: 58-67 Time of Publication: 2018
Abstract	Incorporation of water into tin-substituted BaIn1-xSnxO3-δ (x = 0.1–0.3) is shown to influence crystal structure at room temperature, structural transformations at high temperatures and ionic transport properties of the materials. Increasing tin content stabilizes oxygen vacancy-disordered perovskite-type phase, which together with large changes of the unit cell volume occurring during hydration and dehydration processes, result in a complex structural behavior, as documented by high-temperature X-ray diffraction and thermogravimetric studies. Impedance spectroscopy measurements at elevated temperatures (350–800 °C) revealed very high proton conductivity in BaIn.8Sn.2O3-δ, exceeding 1.1·10−3 S cm−1 at 500 °C, with high values of the transference number in wet air. At the same time, relaxation kinetics of the electrical conductivity showed a monotonous nature, which indicates negligible component of the electronic hole conductivity in the hydrated material. The oxides are extremely moisture-sensitive, which results in a significant mechanical stability problems, affecting possibility to prepare electrolyte membranes.
Keywords	Barium indate, Hydration, Structural transformations, Proton conductivity, Relaxation experiments
Remark	https://doi.org/10.1016/j.jssc.2018.03.004 Link

ID=465

Single-crystal x-ray diffraction and impedance spectroscopy investigations of the RbxCs1-xH2PO4 (0≤x≤1) proton conductor series

Authors	A.G. Goos, A.J. Encerrado Manriquez, H. Martinez, A.D. Price, C.E. Botez
Source	Journal of Physics and Chemistry of Solids Volume: 118, Pages: 200-210 Time of Publication: 2018
Abstract	We have used single-crystal x-ray diffraction to investigate the structural modifications induced by Rb-doping of the superprotonic conductor CsH2PO4. We found that the monoclinic P21/m CsH2PO4 modification persists within the RbxCs1-xH2PO4 (0 ≤ x ≤ 1) series upon Rb-doping from x = 0.1 to x = 0.7. Rb0.8Cs0.2H2PO4 (x = 0.8), however, exhibits a previously unreported P21/c monoclinic phase, where the mirror plane is lost and disorder is present in the PO4 tetrahedra even at room temperature. Higher levels of x display a tetragonal I-42d unit cell isomorphic with the known structure of RbH2PO4. The temperature dependence of the proton conductivity determined from impedance spectroscopy data collected within the 160⁰C-250 °C range is also markedly different at high Rb-doping levels, x ≥ 0.8. Finally, we found that Rb0.9Cs0.1H2PO4 undergoes a transition from its room-temperature tetragonal I-42d phase to an intermediate-temperature monoclinic P21/m modification at a significantly lower temperature (∼80 °C) than its RbH2PO4 counterpart (∼120 °C).
Remark	https://doi.org/10.1016/j.jpcs.2018.03.011 Link

ID=464

Performance evaluation of Mn and Fe doped SrCo 0.9 Nb 0.1 O 3-δ cathode for IT-SOFC application

Authors	Lokesh Bele, R.K. Lenka, P.K. Patro, L.M. uhmood, T. Mahata and P.K. Sinha
Source	IOP Conference Series: Materials Science and Engineering Volume: 310
Abstract	Cathode materials of Mn and Fe doped SrCo0.9Nb0.1O3-δ, are synthesized by solid state route for intermediate temperature fuel cell applications. Phase pure material is obtained after calcining the precursors at 1100oC. Phase compatibility is observed between this novel cathode material with gadolinia doped ceria (GDC)electrolyte material as reflected in the diffraction pattern. The state of art YSZ electrolyte is not compatible with this cathode material. Average thermal expansion coefficient of the material varies between 17 to 22 X 10-6 K-1 on doping, from room temperature to 800 oC. Increase in thermal expansion coefficient is observed with Mn and Fe doping associated with the loss of oxygen from the crystal. The electrical conductivity of the cathode material decreases with Fe and Mn doping. Mn doped samples show lowest conductivity. From the symmetric cell measurement lower area specific resistance (0.16 Ω-cm2) is obtained for un-doped samples, at 850 oC. From the initial results it can be inferred that Mn/Fe doping improves neither the thermal expansion coefficient nor the electrochemical activity.
Remark	Link

ID=463

Does the conductivity of interconnect coatings matter for solid oxide fuel cell applications?

Authors	Claudia Goebel, Alexander G. Fefekos, Jan-Erik Svensson, Jan Froitzheim
Source	Journal of Power Sources Volume: 383, Pages: 110-114 Time of Publication: 2018
Abstract	The present work aims to quantify the influence of typical interconnect coatings used for solid oxide fuel cells (SOFC) on area specific resistance (ASR). To quantify the effect of the coating, the dependency of coating thickness on the ASR is examined on Crofer 22 APU at 600 °C. Three different Co coating thicknesses are investigated, 600 nm, 1500 nm, and 3000 nm. Except for the reference samples, the material is pre-oxidized prior to coating to mitigate the outward diffusion of iron and consequent formation of poorly conducting (Co,Fe)3O4 spinel. Exposures are carried out at 600 °C in stagnant laboratory air for 500 h and subsequent ASR measurements are performed. Additionally the microstructure is investigated with scanning electron microscopy (SEM). On all pre-oxidized samples, a homogenous dense Co3O4 top layer is observed beneath which a thin layer of Cr2O3 is present. As the ASR values range between 7 and 12 mΩcm2 for all pre-oxidized samples, even though different Co3O4 thicknesses are observed, the results strongly suggest that for most applicable cases the impact of the coating on ASR is negligible and the main contributor is Cr2O3.
Keywords	Solid oxide fuel cell, Interconnect, Corrosion, Coating, Area specific resistance, Cr2O3
Remark	https://doi.org/10.1016/j.jpowsour.2018.02.060 Link

ID=462

Amorphous-cathode-route towards low temperature SOFC

Authors	Andrea Cavallaro, Stevin S. Pramana, Enrique Ruiz-Trejo, Peter C. Sherrell, Ecaterina Ware, John A. Kilner and Stephen J. Skinner
Source	Volume: 2, Pages: 862-875 Time of Publication: 2018
Abstract	Lowering the operating temperature of solid oxide fuel cell (SOFC) devices is one of the major challenges limiting the industrial breakthrough of this technology. In this study we explore a novel approach to electrode preparation employing amorphous cathode materials. La0.8Sr0.2CoO3−δ dense films have been deposited at different temperatures using pulsed laser deposition on silicon substrates. Depending on the deposition temperature, textured polycrystalline or amorphous films have been obtained. Isotope exchange depth profiling experiments reveal that the oxygen diffusion coefficient of the amorphous film increased more than four times with respect to the crystalline materials and was accompanied by an increase of the surface exchange coefficient. No differences in the surface chemical composition between amorphous and crystalline samples were observed. Remarkably, even if the electronic conductivities measured by the Van Der Pauw method indicate that the conductivity of the amorphous material was reduced, the overall catalytic properties of the cathode itself were not affected. This finding suggests that the rate limiting step is the oxygen mobility and that the local electronic conductivity in the amorphous cathode surface is enough to preserve its catalytic properties. Different cathode materials have also been tested to prove the more general applicability of the amorphous-cathode route.
Remark	DOI: 10.1039/C7SE00606C Link

ID=461

Stability of the superprotonic conduction of (1-x)CsH2PO4/xSiO2 (0 ≤ x ≤ 0.3) composites under dry and humid environments

Authors	J.H.Leal, H.Martinez, I.Martinez, A.D.Price, A.G.Goos, C.E.Botez
Source	Materials Today Communications Volume: 15, Pages: 11-17 Time of Publication: 2018
Abstract	We have used temperature- and time-resolved electrochemical impedance spectroscopy, x-ray diffraction, and thermal analysis methods to investigate the effect of mixing CsH2PO4 with nano-silica on the superprotonic conduction of this solid acid. We collected data on (1-x)CsH2PO4/xSiO2 (0 ≤ x ≤ 0.3) composites in dry (air) and humid (PH2O ∼ 0.38 atm) environments at temperatures below and above the superprotonic transition of CsH2PO4 (TSP ∼ 234 °C). We first observed that a three-order-of-magnitude proton conductivity jump occurred in the unmixed sample (x = 0) at TSP, even under dry conditions and despite chemical changes (dehydration). We also found that the proton conductivity of the x = 0.1, 0.2 and 0.3 composites measured at T = 260 °C in air is nearly one order of magnitude greater than that of the unmixed phosphate (x = 0). Even more significantly, we found that humid sample environments have no effect on the stability of the proton conductivity of the x = 0.2 composite measured over a 10 h timespan at temperatures above TSP. This is contrary to the behavior of the x = 0 sample, which is known [31] to be stable under humid conditions, but undergoes a three-order-of-magnitude proton conductivity drop in air.
Keywords	Superprotonic phase, Composite materials, X-ray diffraction, Impedance spectroscopy
Remark	https://doi.org/10.1016/j.mtcomm.2018.02.021 Link

ID=460

Co-deficient PrBaCo2−xO6−δ perovskites as cathode materials for intermediate-temperature solid oxide fuel cells: Enhanced electrochemical performance and oxygen reduction kinetics

Authors	Likun Zhang, Shuli Li, Tian Xia, Liping Sun, Lihua Huo, Hui Zhao
Source	International Journal of Hydrogen Energy Volume: 43, Issue: 7, Pages: 3761-3775 Time of Publication: 2018
Abstract	Co-deficient PrBaCo2−xO6−δ perovskites (x = 0, 0.02, 0.06 and 0.1) are synthesized by a solid-state reaction, and the effects of Co-deficiency on the crystal structure, oxygen nonstoichiometry and electrochemical properties are investigated. The PrBaCo2−xO6−δ samples have an orthorhombic layered perovskite structure with double c axis. The degree of oxygen nonstoichiometry increases with decreasing Co content (0 ≤ x ≤ 0.06) and then slightly decreases at x = 0.1. All the samples exhibit the electrical conductivity values of >300 S cm−1 in the temperature range of 100–800 °C in air, which match well the requirement of cathode. With significantly enhanced electrochemical performance and good chemical compatibility between PrBaCo2−xO6−δ and CGO, this system of Co-deficient perovskite is promising cathode material for IT-SOFCs. Among all these components, PrBaCo1.94O6−δ gives lowest polarization resistance of 0.059 Ω cm2 at 700 °C in air. When tested as cathode in fuel cell, the anode-supported Ni-YSZ\|YSZ\|CGO\|PrBaCo1.94O6−δ cell delivers a maximum peak power density of 889 mW cm−2 at 650 °C, which is higher than that of PrBaCoO6−δ cathode-based cell (764 mW cm−2). The oxygen reduction kinetics at the PrBaCo1.94O6−δ cathode interface is also explored, and the rate-limiting steps for oxygen reduction reaction are determined.
Keywords	Intermediate-temperature solid oxide fuel cells, Cathode material, Layered perovskite, Electrochemical performance, Oxygen reduction kinetics
Remark	https://doi.org/10.1016/j.ijhydene.2018.01.018 Link

ID=457

Electrical conductivity of NiMo–based double perovskites under SOFC anodic conditions

Authors	Sabrina Presto, Pravin Kumar, Salil Varma, Massimo Viviani, Prabhakar Singh
Source	International Journal of Hydrogen Energy Volume: 43, Issue: 9, Pages: 4528-4533 Time of Publication: 2018
Abstract	Three different materials are prepared by chemical reaction route, Sr2NiMoO6 (SNM00), Sr1.96La004NiMoO6 (SLNM04) and Sr1.99Ce0.01NiMoO6 (SCNM01) and conductivity is measured under reducing atmosphere, in order to study their suitability as anode materials in SOFC application. Selected materials correspond to compositions reported with highest conductivity in air at operative temperatures of a SOFC among the systems SLNM (Sr2−xLaxNiMoO6, 0.02 ≤ x ≤ 0.10) and SCNM (Sr2−xCexNiMoO6, 0.01 ≤ x ≤ 0.05). The end member Sr2NiMoO6 (SNM) is also considered as reference. Their conductivities considerably increase in wet hydrogen and follow Arrhenius behavior with lower activation energy. Effects of reduction on microstructure and phase stability are also studied by scanning electron microscopy and X–ray diffraction. The enhancement in conductivity is discussed in terms of defects chemistry. Amongst all measured samples, SLNM04 shows the highest conductivity in reducing atmosphere without phase degradation, which makes it a promising anode material for Solid Oxide Fuel Cells (SOFC).
Keywords	Double perovskite Reduction Electrical conductivity Anodic materials SOFC
Remark	https://doi.org/10.1016/j.ijhydene.2018.01.066 Link

ID=455

Proton and oxygen ion conductivity in the pyrochlore/fluorite family of Ln2−xCaxScMO7−δ (Ln = La, Sm, Ho, Yb; M = Nb, Ta; x = 0, 0.05, 0.1) niobates and tantalates

Authors	A. V. Shlyakhtina, K. S. Pigalskiy, D. A. Belov, N. V. Lyskov, E. P. Kharitonova, I. V. Kolbanev, A. B. Borunova, O. K. Karyagina, E. M. Sadovskaya, V. A. Sadykov and N. F. Eremeev
Source	Dalton Transaction Volume: 47, Pages: 2376-2392 Time of Publication: 2018
Abstract	The tolerance factor is a good criterion to understand the structural transitions in Ln2−xCaxScMO7−δ (Ln = La, Sm, Ho, Yb; M = Nb, Ta; x = 0, 0.05, 0.1). Decreasing the Ln ionic radius in Ln2ScNb(Ta)O7 leads to a morphotropic transition from a pyrochlore to a fluorite-like structure. Ca2+-doping leads to a pyrochlore-to-fluorite transition in Ln2−xCaxScMO7−δ (Ln = La, Sm) and a fluorite-to-pyrochlore transition in Ho2−xCaxScNbO7−δ. Proton contribution to the total conductivity was observed for Ln2−xCaxScNb(Ta)O7−δ (Ln = La, Sm; x = 0, 0.05, 0.1) 3+/5+ pyrochlores and the maximum proton contribution was shown by Sm1.9Ca0.1ScMO6.95 (M = Nb, Ta), which are located at the boundary between pyrochlores and fluorites (comparative study of electrical conduction and oxygen diffusion). Proton conduction of Sm1.9Ca0.1ScNbO6.95 and Sm1.9Ca0.1ScTaO6.95 pyrochlores persists up to 800 and 850 °C, respectively. The conductivity of fluorite-like Ho2−xCaxScNbO7−δ (x = 0, 0.05) and Yb2ScNbO7 is dominated by the oxygen ion transport, in accordance with their energy activation values 1.09–1.19 eV. The dielectric permittivity and TG studies were used for the investigation of oxygen vacancy dynamics and water incorporation into the Ln2−xCaxScNb(Ta)O7−δ (Ln = La, Sm, Ho, Yb; x = 0, 0.05, 0.1) lattice. It is shown that oxygen vacancy-related dielectric relaxation in the range of 550–650 °C (ambient air), typical of pyrochlores and fluorites with pure oxygen ion conductivity, decreases and disappears for proton-conducting oxides.
Keywords	Proton and oxygen ion conductivity, Pyrochlore/fluorite family
Remark	DOI: 10.1039/C7DT03912C Link

ID=453

Structural and electrochemical characterization of BaCe0.7Zr0.2Y0.05Zn0.05O3 as an electrolyte for SOFC-H

Authors	Ahmed Afif, Nikdalila Radenahmad, Chee Ming Lim, Quintin Cheok, Md. Aminul Islam, Seikh Mohammad Habibur Rahman, Abul Kalam Azad
Source	IOP Conf. Series: Materials Science and Engineering Volume: 121 Time of Publication: 2016
Abstract	As a potential electrolyte for proton-conducting solid oxide fuel cells (SOFC-Hs)and to get better protonic conductivity and stability, zinc doped BCZY material has been found to be promising. In this study, we report a new composition of proton conductors BaCe0.7Zr0.2Y0.05Zn0.05O3 (BCZYZn5) which was investigated using XRD, SEM and conductivity measurements. Rietveld refinement of the XRD data revel a cubic perovskite structure with Pm-3m space group. BaCe0.7Zr0.2Y0.05Zn0.05O3 shows cell parameter a = 4.3452(9) Å. Scanning electron microscopy images shows that the grain sizes are large and compact which gives the sample high density and good protonic conductivity. The total conductivity in wet atmosphere is significantly higher than that of dry condition and the conductivity was found to be 0.276 x 10-3 Scm-1 and 0.204 x 10-3 Scm-1 at 600°C in wet and dry Ar, respectively. This study indicated that perovskite electrolyte BCZYZn5 is a promising material for the next generation intermediate temperature solid oxide fuel cells (IT-SOFCs).
Remark	Link

ID=452

Enhanced O2 Flux of CaTi0.85Fe0.15O3−δ Based Membranes by Mn Doping

Authors	Polfus, J. M., Xing, W., Riktor, M., Sunding, M. F., Dahl, P. I., Hanetho, S. M., Mokkelbost, T., Larring, Y., Fontaine, M.-L. and Bredesen, R.
Source	Journal of the American Ceramic Society Volume: 99, Issue: 3, Pages: 1071–1078 Time of Publication: 2016
Abstract	Dense symmetric membranes of CaTi0.85−xFe0.15MnxO3−δ (x = 0.1, 0.15, 0.25, 0.4) are investigated in order to determine the optimal Mn dopant content with respect to highest O2 flux. O2 permeation measurements are performed as function of temperature between 700°C–1000°C and as function of the feed side math formula ranging between 0.01 and 1 bar. X-ray photoelectron spectroscopy is utilized to elucidate the charge state of Mn, and synchrotron radiation X-ray powder diffraction (SR-XPD) is employed to investigate the structure symmetry and cell volume of the perovskite phase at temperatures up to 800°C. The highest O2 permeability is found for x = 0.25 over the whole temperature and math formula ranges, followed by x = 0.4 above 850°C. The O2 permeability for x = 0.25 reaches 0.01 mL(STP) min−1 cm−1 at 925°C with 0.21 bar feed side math formula and Ar sweep gas. X-ray photoelectron spectroscopy indicates that the charge state of Mn changes from approx. +3 to +4 when x > 0.1, which implies that Mn mainly improves electronic conductivity for x > 0.1. The cell volume is found to decrease linearly with Mn content, which coincides with an increase in the activation energy of O2 permeability. These results are consistent with the interpretation of the temperature and math formula dependency of O2 permeation. The sintering behavior and thermal expansion properties are investigated by dilatometry, which show improved sinterability with increasing Mn content and that the thermal expansion coefficient decreases from 12.4 to 11.9 × 10−6 K−1 for x = 0 and x = 0.25, respectively.

ID=451

Fabrication and characterization of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF)-Ce0.9Gd0.1O1.95 (GDC) composite thick film for anode supported solid oxide fuel cells

Authors	Atul P. Jamale, C. H. Bhosale, L. D. Jadhav
Source	Journal of Materials Science: Materials in Electronics Volume: 27, Issue: 1, Pages: 795–799 Time of Publication: 2016
Abstract	Nowadays, the commercialization of solid oxide fuel cell (SOFC) is impeded by the chemical compatibility and polarization losses in association with electrode/electrolyte interface. Thus, to minimize these difficulties, the thick film of LSCF-GDC (50:50 wt%) composite was deposited onto GDC electrolyte to form perfect LSCF-GDC/GDC structure. The chemically compatibility of LSCF-GDC upon sintering of 1000 °C was confirmed from the X-ray diffraction studies. Typically, the film with 15 μm thickness possesses the porous structure, availing the free path for oxygen diffusion. The electrochemical impedance analysis of symmetric cell with LSCF-GDC as an electrode implies the relaxation of charge transfer and electrochemical reduction reaction with temperature. The NiO-GDC (30:70 wt%) supported SOFC with GDC and LSCF-GDC as an electrolyte and cathode, respectively was tested for their performance. The cell generates the maximum powder density of 315 μWcm−2 at 500 °C.
Remark	Link

ID=449

The Band Gap of BaPrO3 Studied by Optical and Electrical Methods

Authors
Source	Journal of the American Ceramic Society Volume: 99, Issue: 2, Pages: 492–498 Time of Publication: 2016
Abstract	We report on measurements of the electrical and optical properties of BaPrO3. The temperature dependences of the electrical conductivity σ and the Seebeck coefficient α of polycrystalline samples were studied over a wide temperature range (300°C–1050°C). At lower temperatures, the observed charge transport can be described as thermally activated hopping of electron-based small polarons with an activation energy of 0.37 eV. An observed change in temperature dependence of both σ and α around 700°C was observed and interpreted as a transition from extrinsic to intrinsic carrier transport. The intrinsic conduction can be modeled with an apparent electrical band gap of ~2 eV. Optical absorption and emission spectroscopy in the UV–VIS–NIR range revealed a series of characteristic absorption thresholds and the type of optical transitions was identified by combining transmittance and diffuse-reflectance spectroscopy methods. An absorption edge of indirect type with onset at 0.6 eV is attributed to small polaron effects. The higher lying absorption thresholds of direct origin positioned at around 1.8 and 3.8 eV are correlated with thermal activation parameters from electrical measurements and discussed in terms of the band gap of BaPrO3.
Remark	DOI: 10.1111/jace.13961 Link

ID=447

New alluaudite-related triple molybdates Na25Cs8R5(MoO4)24 (R = Sc, In): synthesis, crystal structures and properties

Authors	Aleksandra A. Savina, Sergey F. Solodovnikov, Dmitry A. Belov, Zoya A. Solodovnikova, Sergey Yu. Stefanovich, Bogdan I. Lazoryak and Elena G. Khaikina
Source	New Journal of Chemistry Volume: 41, Pages: 5450 Time of Publication: 2017
Abstract	New triple molybdates Na25Cs8R5(MoO4)24 (R = Sc, In) were prepared as powders and ceramics by solid state reactions, and their single crystals were also obtained from melts by spontaneous сrystallization. The structures were determined by single crystal XRD analysis. The electrical conductivity of ceramics was measured by impedance spectroscopy. The crystal structures were determined in monoclinic sp. gr. P21/c, a = 14.0069(3) Å,b = 12.6498(3) Å, c = 28.6491(6) Å, b = 90.007(1)1 (Sc) and a = 14.0062(2) Å, b = 12.6032(2) Å, c = 28.7138(4) Å,b = 90.001(1)1 (In). Together with triclinic Na25Cs8Fe5(MoO4)24, the titled compounds form a distinctive family of pseudo-orthorhombic alluaudite-related structures with the parent sp. gr. Pbca. Its structural features are alluaudite-like polyhedral layers composed of pairs of edge-shared (R, Na)O6 and NaO6 octahedra connected by bridging MoO4 tetrahedra. The layers are joined together by means of interlayer MoO4 tetrahedra, thus forming open 3D frameworks with cavities filled with Cs+ and Na+ ions. The manner of stacking layers is somewhat different from the alluaudite type. The compounds undergo phase transitions at 668 (Sc) and 725 (In) K accompanied by an abrupt increase of electrical conductivity presumably Na+-ionic in nature. Above these transitions, the conductivity is as high as 10(3) Scm(-1), which makes Na25Cs8R5(MoO4)24 (R = Sc, In) promising solid state electrolytes.
Remark	DOI: 10.1039/c7nj00202e Link

ID=446

Enhanced Flexible Thermoelectric Generators Based on Oxide–Metal Composite Materials

Authors	Benjamin Geppert, Artur Brittner, Lailah Helmich, Michael Bittner, Armin Feldhoff
Source	Journal of Electronic Materials Volume: 46, Issue: 4, Pages: 2356–2365 Time of Publication: 2017
Abstract	The thermoelectric performance of flexible thermoelectric generator stripes was investigated in terms of different material combinations. The thermoelectric generators were constructed using Cu-Ni-Mn alloy as n-type legs while varying the p-type leg material by including a metallic silver phase and an oxidic copper phase. For the synthesis of Ca3Co4O9/CuO/Ag ceramic-based composite materials, silver and the copper were added to the sol–gel batches in the form of nitrates. For both additional elements, the isothermal specific electronic conductivity increases with increasing amounts of Ag and CuO in the samples. The amounts for Ag and Cu were 0 mol.%, 2 mol.%, 5 mol.%, 10 mol.%, and 20 mol.%. The phases were confirmed by x-ray diffraction. Furthermore, secondary electron microscopy including energy dispersive x-ray spectroscopy were processed in the scanning electron microscope and the transmission electron microscope. For each p-type material, the data for the thermoelectric parameters, isothermal specific electronic conductivity σ and the Seebeck coefficient α, were determined. The p-type material with a content of 5 mol.% Ag and Cu exhibited a local maximum of the power factor and led to the generator with the highest electric power output Pel.
Remark	Link

ID=444

Crystal structure and proton conductivity of BaSn 0.6 Sc 0.4 O 3 d : insights from neutron powder di ff raction and solid-state NMR spectroscopy

Authors	Francis G. Kinyanjui, Stefan T. Norberg, Christopher S. Knee, Istaq Ahmed, Stephen Hull, Lucienne Buannic, Ivan Hung, Zhehong Gan, Fr ́ed ́eric Blanc, Clare P. Grey and Sten G. Eriksson
Source	J.Mater.Chem.A Volume: 4, Issue: 14, Pages: 5088-5101 Time of Publication: 2016
Abstract	The solid-state synthesis and structural characterisation of perovskite BaSn1−xScxO3−δ (x = 0.0, 0.1, 0.2, 0.3, 0.4) and its corresponding hydrated ceramics are reported. Powder and neutron X-ray diffractions reveal the presence of cubic perovskites (space group Pm[3 with combining macron]m) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. 119Sn and 45Sc solid-state NMR spectroscopy data highlight the existence of oxygen vacancies in the dry materials, and their filling upon hydrothermal treatment with D2O. It also indicates that the Sn4+ and Sc3+ local distribution at the B-site of the perovskite is inhomogeneous and suggests that the oxygen vacancies are located in the scandium dopant coordination shell at low concentrations (x ≤ 0.2) and in the tin coordination shell at high concentrations (x ≥ 0.3). 17O NMR spectra on 17O enriched BaSn1−xScxO3−δ materials show the existence of Sn–O–Sn, Sn–O–Sc and Sc–O–Sc bridging oxygen environments. A further room temperature neutron powder diffraction study on deuterated BaSn0.6Sc0.4O3−δ refines the deuteron position at the 24k crystallographic site (x, y, 0) with x = 0.579(3) and y = 0.217(3) which leads to an O–D bond distance of 0.96(1) Å and suggests tilting of the proton towards the next nearest oxygen. Proton conduction was found to dominate in wet argon below 700 °C with total conductivity values in the range 1.8 × 10−4 to 1.1 × 10−3 S cm−1 between 300 and 600 °C. Electron holes govern the conduction process in dry oxidizing conditions, whilst in wet oxygen they compete with protonic defects leading to a wide mixed conduction region in the 200 to 600 °C temperature region, and a suppression of the conductivity at higher temperature.
Remark	DOI: 10.1039/c5ta09744d Link

ID=441

DC-bias dependent impedance spectroscopy of BaTiO3–Bi(Zn1/2Ti1/2)O3 ceramics

Authors
Source	J. Mater. Chem. C Volume: 4, Pages: 1782-1786 Time of Publication: 2016
Remark	DOI: 10.1039/C5TC04247J Link

ID=437

Defect mechanisms in BaTiO3-BiMO3 ceramics

Authors
Source	Journal of the American Ceramic Society Time of Publication: 2018
Abstract	Often, addition of BiMO3 to BaTiO3 (BT) leads to improvement in resistivity with a simultaneous shift to n-type conduction from p-type for BT. In considering one specific BiMO3 composition, that is, Bi(Zn1/2Ti1/2)O3 (BZT), several prospective candidates for the origin of this n-type behavior in BT-BZT were studied—loss of volatile cations, oxygen vacancies, bismuth present in multiple valence states and precipitation of secondary phases. Combined x-ray and neutron diffraction, prompt gamma neutron activation analysis and electron energy loss spectroscopy suggested much higher oxygen vacancy concentration in BT-BZT ceramics (>4%) as compared to BT alone. X-ray photoelectron spectroscopy and x-ray absorption spectroscopy did not suggest the presence of bismuth in multiple valence states. At the same time, using transmission electron microscopy, some minor secondary phases were observed, whose compositions were such that they could result in effective donor doping in BT-BZT ceramics. Using experimentally determined thermodynamic parameters for BT and slopes of Kröger-Vink plots, it has been suggested that an ionic compensation mechanism is prevalent in these ceramics instead of electronic compensation. These ionic defects have an effect of shifting the conductivity minimum in the Kröger-Vink plots to higher oxygen partial pressure values in BT-BZT ceramics as compared to BT, resulting in a significantly higher resistivity values in air atmosphere and n-type behavior. This provides an important tool to tailor transport properties and defects in BT-BiMO3 ceramics, to make them better suited for dielectric or other applications.
Remark	DOI: 10.1111/jace.15403, Version of Record online: 8 JAN 2018 Link

ID=436

The Effect of Ni Doping on the Performance and Electronic Structure of LSCF Cathodes Used for IT-SOFCs

Authors	Alessandro Longo, Leonarda F. Liotta, Dipanjan Banerjee, Valeria La Parola, Fabrizio Puleo, Chiara Cavallari, Christoph J. Sahle, Marco Moretti Sala, and Antonino Martorana
Source	J. Phys. Chem.: C Time of Publication: 2017
Abstract	We investigated the effect of nickel doping on the electronic structure and performance of nanostructured La0.6Sr0.4Co0.2Fe0.8–0.03Ni0.03O3−δ prepared by the one-pot sol–gel method. The commercial undoped La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF0.8) was used as reference. Moreover, for comparison, Ni (3 mol %) was deposited by wetness impregnation over the La0.6Sr0.4Co0.2Fe0.8O3−δ. We show by in situ X-ray absorption spectroscopy at 900 °C under air flow that nickel enters the B perovskite site of the material and favors the stabilization of the cobalt oxidation state, as evidenced by the delay in the decrease of the average Co valence with respect to undoped samples. Our results are further supported by in situ X-ray Raman spectroscopy (XRS) that allowed us to monitor the temperature evolution of the O K-edge. XRS evidences that nickel-doped LSCF shows unmodified O2p-TM3d density of states, which proves that the Co oxidation state is preserved. Electrochemical impedance spectroscopy measurements were carried out over half-cell systems consisting of LSCF-based materials deposited onto a Ce0.8Gd0.2O2−δ electrolyte. The improvement of the electrochemical performances of the Ni-doped La0.6Sr0.4Co0.2Fe0.8–0.03Ni0.03O3−δ sample with respect to a reference Ni-impregnated LSCF is attributed to the stabilization of the TM-O6 structural units, which were recently proposed as the functional units for oxygen reduction.
Remark	DOI: 10.1021/acs.jpcc.7b07626 Link

ID=434

Optimisation of growth parameters to obtain epitaxial Y-doped BaZrO3 proton conducting thin films

Authors
Source	Volume: 314, Pages: 9–16 Time of Publication: 2018
Abstract	We hereby report developments on the fabrication and characterization of epitaxial thin films of proton conducting Y-doped BaZrO3 (BZY) by pulsed laser deposition (PLD) on different single crystal substrates (MgO, GdScO3, SrTiO3, NdGaO3, LaAlO3 and sapphire) using Ni-free and 1% Ni-containing targets. Pure, high crystal quality epitaxial films of BZY are obtained on MgO and on perovskite-type substrates, despite the large lattice mismatch. The deposition conditions influence the morphology, cell parameters and chemical composition of the film, the oxygen partial pressure during film growth being the most determining. Film characterization was carried out using X-ray diffraction, transmission electron and atomic force microscopies, wavelength dispersive X-ray spectroscopy and angle-resolved X-ray photoelectron spectroscopy. All films show a slight tetragonal distortion that is not directly related to the substrate-induced strain. The proton conductivity of the films depends on deposition conditions and film thickness, and for the optimised conditions its total conductivity is slightly higher than the bulk conductivity of the target material (3 mS/cm at 600 °C, in wet 5% H2/Ar). The conductivities are, however, more than one order of magnitude lower than the highest reported in literature and possible reasoning is elucidated in terms of local and extended defects in the films.
Keywords	BaZrO3; Thin film; Electrolyte; Proton conductivity; SOFC; PC-SOFC
Remark	https://doi.org/10.1016/j.ssi.2017.11.002 Link

ID=433

Improvement of thermoelectric properties of lanthanum cobaltate by Sr and Mn co-substitution

Authors	Ashutosh Kumar, D. Sivaprahsam, Ajay D. Thakur
Source	Journal of Alloys and Compounds Volume: 735, Pages: 1787–1791 Time of Publication: 2018
Abstract	We report thermoelectric (TE) properties of Sr and Mn co-substituted LaCoO3 system from room temperature to 700 K. Sr-substitutions at La and Mn at Co site in LaCoO3 improves the electrical conductivity (σ). Thermal conductivity (κ) of all the samples increases with the increase in temperature but decreases with the substitution in LaCoO3. An estimation of the electronic thermal conductivity (κe) suggests a dominant phonon contribution to thermal conductivity in this system. A maximum value of the figure of merit is 0.14 at 480 K for La0.95Sr0.05Co0.95Mn0.05O3.
Keywords	Powders: solid-state reaction; Thermal conductivity; Electrical conductivity; Perovskites
Remark	https://doi.org/10.1016/j.jallcom.2017.11.334 Link

ID=428

Characteristics of LaCo0.4Ni0.6-xCuxO3-δ ceramics as a cathode material for intermediate-temperature solid oxide fuel cells

Authors	Yi-XinLiu, Sea-Fue Wang,Yung-Fu Hsu, Hung-Wei Kai, Piotr Jasinski
Source	Journal of the European Ceramic Society Time of Publication: 2017
Abstract	In this study, the effects of Cu-ion substitution on the densification, microstructure, and physical properties of LaCo0.4Ni0.6-xCuxO3-δ ceramics were investigated. The results indicate that doping with Cu ions not only enhances the densification but also promotes the grain growth of LaCo0.4Ni0.6-xCuxO3-δ ceramics. The Cu substitution at x ≤ 0.2 can suppress the formation of La4Ni3O10, while the excess Cu triggers the formation of La2CuO4.032 phase. The p-type conduction of LaCo0.4Ni0.6O3-δ ceramic was significantly raised by Cu substitution because the acceptor doping () triggered the formation of hole carriers; this effect was maximized in the case of LaCo0.4Ni0.4Cu0.2O3-δ composition (1480 S cm−1 at 500 °C). Thermogravimetric data revealed a slight weight increase of 0.29% for LaCo0.4Ni0.4Cu0.2O3-δ compact up to 871 °C; this is due to the incorporation of oxygen that creates metal vacancies and additional carriers, partially compensating the conductivity loss due to the spin-disorder scattering. As the temperature of the LaCo0.4Ni0.4Cu0.2O3-δ compacts rose above 871 °C, significant weight loss with temperature was observed because of the release of lattice oxygen to the ambient air as a result of Co (IV) thermal reduction accompanied by the formation of oxygen vacancies. A solid oxide fuel cell (SOFC) single cell with Sm0.2Ce0.8O2-δ (electrolyte) and LaCo0.4Ni0.4Cu0.2O3-δ (cathode) was built and characterized. The Ohmic (0.256 Ω cm2) and polarization (0.434 Ω cm2) resistances of the single cell at 700 °C were determined; and the maximum power density was 0.535 W cm−2. These results show that LaCo0.4Ni0.4Cu0.2O3-δ is a very promising cathode material for SOFC applications.
Keywords	Solid oxide fuel cells, Cell performance, Impedance Cathode
Remark	Available online 8 November 2017, https://doi.org/10.1016/j.jeurceramsoc.2017.11.019 Link

ID=424

High-temperature properties of (La,Ca)(Fe,Mg,Mo)O3-δ perovskites as prospective electrode materials for symmetrical SOFC

Authors	S.Ya.Istomin, A.V.Morozov, M.M.Abdullayev, M.BatukbJ.Hadermann, S.M.Kazakov, A.V.Sobolev, I.A.Presniakov, E.V.Antipov
Source	Journal of Solid State Chemistry Volume: 258, Pages: 1-10 Time of Publication: 2018
Abstract	La1−yCayFe0.5+x(Mg,Mo)0.5−xO3-δ oxides with the orthorhombic GdFeO3-type perovskite structure have been synthesized at 1573 K. Transmission electron microscopy study for selected samples shows the coexistence of domains of perovskite phases with ordered and disordered B-cations. Mössbauer spectroscopy studies performed at 300 K and 573 K show that while compositions with low Ca-content (La0.55Ca0.45Fe0.5Mg0.2625Mo0.2375O3-δ and La0.5Ca0.5Fe0.6Mg0.175Mo0.225O3-δ) are nearly oxygen stoichiometric, La0.2Ca0.8Fe0.5Mg0.2625Mo0.2375O3-δ is oxygen deficient with δ ≈ 0.15. Oxides are stable in reducing atmosphere (Ar/H2, 8%) at 1173 K for 12 h. No additional phases have been observed at XRPD patterns of all studied perovskites and Ce1−xGdxO2−x/2 electrolyte mixtures treated at 1173–1373K, while Fe-rich compositions (x≥0.1) react with Zr1−xYxO2−x/2 electrolyte above 1273 K. Dilatometry studies reveal that all samples show rather low thermal expansion coefficients (TECs) in air of 11.4–12.7 ppm K−1. In reducing atmosphere their TECs were found to increase up to 12.1–15.4 ppm K−1 due to chemical expansion effect. High-temperature electrical conductivity measurements in air and Ar/H2 atmosphere show that the highest conductivity is observed for Fe- and Ca-rich compositions. Moderate values of electrical conductivity and TEC together with stability towards chemical interaction with typical SOFC electrolytes make novel Fe-containing perovskites promising electrode materials for symmetrical solid oxide fuel cell.
Keywords	Symmetrical solid oxide fuel cell, Perovskites, Crystal structure, High-temperature electrical conductivity
Remark	https://doi.org/10.1016/j.jssc.2017.10.005 Link

ID=423

New Solid Electrolyte Na9Al(MoO4)6: Structure and Na+ Ion Conductivity

Authors	Aleksandra A. Savina, Vladimir A. Morozov, Anton L. Buzlukov, Irina Yu. Arapova, Sergey Yu. Stefanovich, Yana V. Baklanova, Tatiana A. Denisova, Nadezhda I. Medvedeva, Michel Bardet, Joke Hadermann, Bogdan I. Lazoryak, and
Source	Chem. Mater. Volume: 29, Issue: 20, Pages: 8901–8913 Time of Publication: 2017
Abstract	Solid electrolytes are important materials with a wide range of technological applications. This work reports the crystal structure and electrical properties of a new solid electrolyte Na9Al(MoO4)6. The monoclinic Na9Al(MoO4)6 consists of isolated polyhedral [Al(MoO4)6]9– clusters composed of a central AlO6 octahedron sharing vertices with six MoO4 tetrahedra to form a three-dimensional framework. The AlO6 octahedron also shares edges with one Na1O6 octahedron and two Na2O6 octahedra. Na3–Na5 atoms are located in the framework cavities. The structure is related to that of sodium ion conductor II-Na3Fe2(AsO4)3. High-temperature conductivity measurements revealed that the conductivity (σ) of Na9Al(MoO4)6 at 803 K equals 1.63 × 10–2 S cm–1. The temperature behavior of the 23Na and 27Al nuclear magnetic resonance spectra and the spin-lattice relaxation rates of the 23Na nuclei indicate the presence of fast Na+ ion diffusion in the studied compound. At T<490 K, diffusion occurs by means of Na+ ion jumps exclusively through the sublattice of Na3–Na5 positions, whereas Na1 and Na2 become involved in the diffusion processes (through chemical exchange with the Na3–Na5 sublattice) only at higher temperatures.
Remark	DOI: 10.1021/acs.chemmater.7b03989 Link

ID=422

Alkali and Alkaline Earth Oxoacid Salts; Synthesis, Hydration, Stability, and Electrical Conductivity

Author	AA Elstad
Source	Time of Publication: 2017
Abstract	Proton-conducting electrolytes are sough after for use in various applications within the field of electrochemistry. Pure and high proton conductivity has been found in many perovskite-type oxides like BaZrO3 (BZY) and BaCeO3, with BaCeO3-based materials being among the best proton-conducting oxides. In the intermediate temperature range of 400 to 800 C, BZY has been established as one of the most promising materials, exhibiting a protonic conductivity higher than 1 10􀀀2 S cm􀀀1 over the whole temperature range. However, it is difficult to process, and the resulting materials are usually grainy and possess highly resistive grain-boundaries [1]. For low-temperature regions, compounds like CsHSO4 and CsH2PO4 show great potential with respect to protonic conductivity, even displaying superprotonic transitions that immensely increase their conductivity, however their stability is lacking with respect to temperature and solubility in water [2]. With this project, the aim is to broaden the horizon and investigate compounds that fall outside the common perovskite-definition. In this work, various solid acids (E.g. KBaPO4, NaCaHSiO4 and BaH2SiO4), in which the cations are alkali and alkaline earth metals and the anionic groups are separated XO4 tetrahedra, are synthesized and subsequently characterized by X-Ray Diffraction (XRD), Thermogravimetric Analysis (TG), as well as electrical characterization by Impedance Spectroscopy (IS). The work on KBaPO4 culminated in a submitted paper [3]. KBaPO4 has been proposed to transform into a great protonic conductor upon hydration at low temperatures. Effectively, hydration through steam at 80 C is said to give the compound a protonic conductivity of 1 10􀀀2 S cm􀀀1 just below 100 C [4]. This is a remarkable result and, if it can be reproduced, it can become a viable rival to BZY. For this reason, KBaPO4 was chosen as a topic for this work. Here, we synthesize KBaPO4 through a high-temperature solid state reaction, and subsequently characterize the system with respect to thermal stability and its inherent electrical conductivity. Through electrical measurements, we found that the conductivity of pure KBaPO4 was very low, around 2 10􀀀6 S cm􀀀1 at 600 C, with an activation energy exceeding 1 eV. The compound is indifferent to the presence of humidity, and results indicate that the charge carrier in the compound is not protonic, but rather it is theorized to be potassium ions, with potassium Frenkel defects being the predominating defect, however this has not been explicitly confirmed. All in all, we propose a defect model for KBaPO4 with Frenkel defects as the predominating defects. Through attempts at hydrating KBaPO4 in accordance to the method proposed by Goodenough, we found that it does not transform into a high-conductivity phase, but rather decomposes into potassium doped Ba3(PO4)2, and that the resulting system shows similar properties, such as thermal stability (Decomposing at 300 C) and protonic conductivity (1:6 10􀀀6 S cm􀀀1 at 250 C), to the system Ba3-xKxHx(PO4)2 previously investigated by Haile et al. [5], albeit with a significantly lower potassium content than the systems they have characterized, possibly indicating that a saturation of K in Ba3(PO4)2 has been reached. By subsequently heating Ba3-xKxHx(PO4)2 to high temperatures, the system is found to expel potassium and form a two-phase system of Ba3(PO4)2 and a secondary phase of KBaPO4, showing similarities to the system Ba3(1-x)K3x(PO4)2-x previously investigated by Iwahara et al. [6]. Through impedance spectroscopy of said system, we found evidence that points toward the system being a protonic conductor, with a bulk conductivity slightly higher than 1 10􀀀3 S cm􀀀1 at 600 C, and an activation energy of around 0:67 eV. This is one order of magnitude higher than the one previously reported by Iwahara et al., and only one order of magnitude lower than that of BaZrO3. Parallelly, NaCaHSiO4 and related compounds ABHXO4 (A􀀀􀀀 Li, Na or K. B􀀀􀀀 Ca, Sr or Ba. X􀀀􀀀 Si, Ge or Sn) were synthesized hydrothermally and subsequently characterized. Electrical characterization of NaCaHSiO4 gave low conductivities, although protonic, of 1:8 10􀀀8 S cm􀀀1 at 250 C, with an activation energy of 0:9 eV. Based on the results, we propose a defect model in which interstitial hydroxide ions and interstitial protons str significant defects in the compound. However, although NaCaHSiO4 could be successfully synthesized and subsequently characterized, the other syntheses did not yield the desired results. In fact, the only synthesis that yielded a pure product was that which gave Sr2SiO4, possibly providing a hydrothermal approach to synthesizing a compound previously produced by a hightemperature solid state reaction. Lastly, the compound BaH2SiO4 was synthesized, according to a hydrothermal route, and characterized with respect to thermal stability and electrical conductivity. It was found to exhibit a conductivity of 2:5 10􀀀8 S cm􀀀1 at 200 C with an activation energy of 0:88 eV, comparable to that of NaCaHSiO4. Due to BaH2SiO4 showing similar response to various atmospheres as NaCaHSiO4, a defect model containing hydroxide and hydrogen interstitials is proposed for BaH2SiO4 as well. Compared to earlier reports, a discrepancy was found in that the BaH2SiO4 decomposes prior to temperature regions in which data on electrical conductivity has been previously reported. Another, separate investigation into BaH2SiO4 is therefore recommended.
Remark	Thesis for the degree of ’Master of Science’, Depertment of Chemistry, University of Oslo Link

ID=421

Defect chemistry and electrical properties of BiFeO3

Authors
Source	Journal of Materials Chemistry C Issue: 38 Time of Publication: 2017
Abstract	BiFeO3 attracts considerable attention for its rich functional properties, including room temperature coexistence of magnetic order and ferroelectricity and more recently, the discovery of conduction pathways along ferroelectric domain walls. Here, insights into the defect chemistry and electrical properties of BiFeO3 are obtained by in situ measurements of electrical conductivity, σ, and Seebeck coefficient, α, of undoped, cation-stoichiometric BiFeO3 and acceptor-doped Bi1−xCaxFeO3−δ ceramics as a function of temperature and oxygen partial pressure pO2. Bi1−xCaxFeO3−δ exhibits p-type conduction; the dependencies of σ and α on pO2 show that Ca dopants are compensated mainly by oxygen vacancies. By contrast, undoped BiFeO3 shows a simultaneous increase of σ and α with increasing pO2, indicating intrinsic behavior with electrons and holes as the main defect species in almost equal concentrations. The pO2-dependency of σ and α cannot be described by a single point defect model but instead, is quantitatively described by a combination of intrinsic and acceptor-doped characteristics attributable to parallel conduction pathways through undoped grains and defect-containing domain walls; both contribute to the total charge transport in BiFeO3. Based on this model, we discuss the charge transport mechanism and carrier mobilities of BiFeO3 and show that several previous experimental findings can readily be explained within the proposed model.
Remark	Link

ID=420

Performance and stability in H2S of SrFe0.75Mo0.25O3-δ as electrode in proton ceramic fuel cells

Authors	S.Wachowski, M.Polfus, T.Norby
Source	Journal of the European Ceramic Society Volume: 38, Issue: 1, Pages: 163-171 Time of Publication: 2018
Abstract	The H2S-tolerance of SrFe0.75Mo0.25O3-δ (SFM) electrodes has been investigated in symmetric proton ceramic fuel cells (PCFC) with BaZr0.8Ce0.1Y0.1O3-δ (BZCY81) electrolyte. The ionic conductivity of the electrolyte under wet reducing conditions was found to be insignificantly affected in the presence of up to 5000 ppm H2S. The fuel cell exhibited an OCV of about 0.9 V at 700 °C, which dropped to about 0.6 V and 0.4 V upon exposure to 500 and 5000 ppm H2S, respectively, on the fuel side. Post characterization of the fuel cell revealed significant degradation of the anode in terms of microstructure and chemical composition due to formation of sulfides such as SrS, MoS2 and Fe3S4. Nevertheless, the fuel cell was still functional due to the sufficient electronic conductivity of some of these sulfides.
Keywords	Proton ceramic fuel cells (PCFC), Sulfur tolerance, H2S, Strontium ferrite, Barium zirconate
Remark	https://doi.org/10.1016/j.jeurceramsoc.2017.08.020 Link

ID=419

Improvement of thermoelectric properties of lanthanum cobaltate by Sr and Mn co-substitution

Authors	Ashutosh Kumar, D. Sivaprahsam, Ajay D. Thakur
Source	Journal of Alloys and Compounds Volume: 735, Pages: 1787–1791 Time of Publication: 2017-12
Abstract	We report thermoelectric (TE) properties of Sr and Mn co-substituted LaCoO3 system from room temperature to 700 K. Sr-substitutions at La and Mn at Co site in LaCoO3 improves the electrical conductivity (σ). Thermal conductivity (κ) of all the samples increases with the increase in temperature but decreases with the substitution in LaCoO3. An estimation of the electronic thermal conductivity (κe) suggests a dominant phonon contribution to thermal conductivity in this system. A maximum value of the figure of merit is 0.14 at 480 K for La0.95Sr0.05Co0.95Mn0.05O3.
Keywords	Seebsys, Powders: solid-state reaction, Thermal conductivity, Electrical conductivity, Perovskites
Remark	Link

ID=417

On the formation of phases and their influence on the thermal stability and thermoelectric properties of nanostructured zinc antimonide

Authors	Priyadarshini Balasubramanian, Manjusha Battabyal, Duraiswamy Sivaprahasam and Raghavan Gopalan
Source	Journal of Physics D: Applied Physics Volume: 50, Issue: 1 Time of Publication: 2016-11
Abstract	To investigate the thermal reliability of the structure and thermoelectric properties of the zinc antimony compounds, undoped (Zn4Sb3) and doped (Zn4Sb2.95Sn0.05 and Co0.05Zn3.95Sb3) zinc antimonide samples were processed using the powder metallurgy route. It was observed that the as-prepared undoped sample contains a pure β-Zn4Sb3 phase, whereas the doped samples consist of Ω-ZnSb as the major phase and β-Zn4Sb3 as the minor phase. Differential scanning calorimetry analysis confirms the stability of the β-Zn4Sb3 phase up to 600 K. X-ray diffraction data of the undoped and doped samples show that the nanocrystallinity of the as-prepared samples is retained after one thermal cycle. The thermal bandgap, thermopower and thermal conductivity are not affected by the thermal cycle for the doped samples. A maximum power factor of 0.6 mW m−1 K−2 was achieved in the Sn-doped sample (Zn4Sb2.95Sn0.05). This is enhanced to 0.72 mW m−1 K−2 after one thermal cycle at 650 K under Ar atmosphere and slightly decreases after the third thermal cycle. In the case of the Co-doped sample (Co0.05Zn3.95Sb3), the power factor increases from 0.4 mW m−1 K−2 to 0.7 mW m−1 K−2 after the third thermal cycle. A figure of merit of ~0.3 is achieved at 573 K in the Zn4Sb2.95Sn0.05 sample. The results from the nanoindentation experiment show that Youngs modulus of the Sn-doped sample (Zn4Sb2.95Sn0.05) after the thermal cycle is enhanced (96 GPa) compared to the as-prepared sample (~76 GPa). These important findings on the thermal stability of the thermoelectric and mechanical properties of Sn-doped samples (Zn4Sb2.95Sn0.05) confirm that Sn-doped zinc antimonide samples can be used as efficient thermoelectric materials for device applications.
Keywords	Seebsys
Remark	Link

ID=416

The effect of Cu2O nanoparticle dispersion on the thermoelectric properties of n-type skutterudites

Authors	M Battabyal, B Priyadarshini, D Sivaprahasam, N S Karthiselva, R Gopalan
Source	Journal of Physics D: Applied Physics Volume: 48, Issue: 45 Publisher: IOP Publishing Ltd, Time of Publication: 2015-11
Abstract	We report the thermoelectric properties of Ba0.4Co4Sb12 and Sn0.4Ba0.4Co4Sb12 skutterudites dispersed with Cu2O nanoparticles. The samples were synthesized by ball milling and consolidated by spark plasma sintering. Dispersion of Cu2O is found to significantly influence the electrical resistivity and thermopower at high temperatures with a more pronounced effect on the electrical resistivity due to the energy filtering effect at the interface between Cu2O nanoparticles and a Ba0.4Co4Sb12 and Sn0.4Ba0.4Co4Sb12 matrix. At 573 K, the electrical resistivity of Ba0.4Co4Sb12 decreases from 5.01 × 10−5 Ohmm to 2.98 × 10−5 Ohmm upon dispersion of Cu2O. The dispersion of Cu2O reduces the thermal conductivity of the samples from 300 K and above by increasing the phonon scattering. The lowest observed thermal conductivity at 573 K is found to be 2.001 W mK−1 in Cu2O dispersed Ba0.4Co4Sb12 while it is 2.91 W mK−1 in the Ba0.4Co4Sb12 sample without Cu2O dispersion. Hence Cu2O dispersion plays a significant role in the thermoelectric properties and a maximum figure of merit (ZT ) ~ 0.92 is achieved in Cu2O dispersed Ba0.4Co4Sb12 at 573 K which is more than 200% compared to the pure Ba0.4Co4Sb12 sample. The results from nanoindentation experiments show that the Cu2O dispersed sample (Cu2O + Sn0.4Ba0.4Co4Sb11.6) has a higher reduced Youngs modulus (~139 GPa) than the pure Sn0.4Ba0.4Co4Sb11.6 sample (~128 GPa).
Keywords	Seebsys
Remark	Link

ID=415

Phase stability and thermoelectric properties of Cu10.5Zn1.5Sb4S13 tetrahedrite

Authors	Subramaniam Harisha, Duraisamy Sivaprahasam, Manjusha Battabyal, Raghavan Gopalan
Source	Journal of Alloys and Compounds Volume: 667, Pages: 323-328 Time of Publication: 2016-05
Abstract	Cu10.5Zn1.5Sb4S13 tetrahedrite compound was prepared by mechanical milling of Cu2S, ZnS and Sb2S3 powders and spark plasma sintered (SPS) to dense samples. The phase formation, chemical homogeneity, thermal stability of the compound and the thermoelectric properties of the sintered samples were evaluated. Single phase tetrahedrite with the crystallite size of 40 nm was obtained after 30 h of milling followed by annealing at 573 K for 6 h in an argon atmosphere. In-situ high-temperature X-ray diffraction studies revealed that the phase is stable up to 773 K. The Seebeck coefficient of the sintered samples of density >98% shows p-type behavior with maximum thermopower of 170 μV/K at 573 K. The electrical resistivity (ρ) decreases with temperature up to 475 K and then increases. A low thermal conductivity of 0.5 W/(m⋅K), in combination with moderate power factor gave a maximum ZT of ∼0.038 at 573 K in Cu10.5Zn1.5Sb4S13 sample having a grain size of ∼200 nm.
Keywords	Seebsys, Thermoelectric, Tetrahedrite, Solid state reactions, Spark plasma sintering, Figure of merit
Remark	Cu10.5Zn1.5Sb4S13 Link

ID=414

Study of novel proton conductors for high temperature Solid Oxide Cells

Author	Anastasia Iakovleva
Source	Time of Publication: 2015
Abstract	The main objective of the present work was the systematic study of several groups of materials: Gd3-xMexGaO6-δ (Me = Ca2+, Sr2+), Ba2Y1+xNb1-xO6-δ , and BaZr0.85Y0.15O3-δ (BZY15) as proton conductors. We developed a synthesis route for each group of materials such as microwave- assisted citric acid combustion method, freezedrying synthesis and modified citrate-EDTA complexing method. Pure nanopowders and dense ceramics were obtained after these syntheses plus a classical sintering process. The structure and composition of the obtained products were characterized by X-Ray diffraction (XRD) and scanning electron microscopy (SEM). The temperature dependences of the conductivity were investigated by impedance spectroscopy as a function of pO2 and pH2O. For the family of Gd3-xMexGaO6-δ (Me = Ca2+, Sr2+), we studied the influence of dopant nature and content on the structural and electrical properties. Results indicate that the substitution possible till 10 % of doping content. According to the SEM observations, the grain size is increased with increasing dopant content. Concerning electrical properties, we found an increase of conduction with increasing dopant content. All compounds present a good stability in humid, hydrogen and CO2 containing atmosphere. In case of Ba2Y1+xNb1-xO6-δ materials, the physico-chemical properties of synthesized materials have been characterized by the XRD and SEM techniques. The average grain size increased significantly with increasing amount of Y3+. Conduction properties were slightly improved with the partial substitution of niobium by yttrium. The stability of Ba2Y1+xNb1-xO6-δ compounds was investigated under different atmospheres and conditions. The ionic conduction in this case is quite low, which has been explained by futher molecular dynamics simulations. Finally, we studied the influence of an ZnO and NiO additives on the sintering of BZY15, being these sintering aids used to lower the sintering temperature. Zinc oxide as a sintering aid lowers the sintering temperature by 300 °C and slightly increases the bulk and total conductivity of BZY15.
Remark	THESE DE DOCTORAT

ID=413

Advanced low-temperature ceramic nanocomposite fuel cells using ultra high ionic conductivity electrolytes synthesized through freeze-dried method and solid-route

Authors
Source	Materials Today Energy Volume: 5, Pages: 338-346 Time of Publication: 2017
Abstract	Low ionic conductivity and slow reaction kinetics often limit the performance of a ceramic nanocomposite fuel cell (CNFC). Here, we report a novel synthesis method, freeze-dried method, to achieve a record high ionic conductivity for nanocomposite electrolytes (>0.5 S/cm) based on Ce0.85Sm0.15O2 (SDC) and a eutectic mixture of Na2CO3, Li2CO3, K2CO3 (NLK). The highest ionic conductivity (0.55 S/cm) was reached by increasing the carbonate content of the electrolyte to 35 wt%. For the sake of comparison, the nanocomposite electrolytes were also prepared through solid-route. Composite anodes and cathodes for complete fuels were prepared from NiO and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF), respectively using both solid-route and freeze-dried nanocomposite electrolytes. Complete fuel cells manufactured from these nanocomposite materials produced ∼1.1 W/cm2 at 550 °C. The EIS measurements revealed low ohmic losses (0.18 Ω cm2) and even lower charge transfer resistance (0.05 Ω cm2). In addition, it was found that the open-circuit-voltage (OCV) of the CNFCs improved from 1.1 V to 1.2 V when a mixture of air and CO2 was supplied as compared to the case when only air was supplied at the cathode. Finally, high temperature X-ray diffraction (HT-XRD) revealed stable structures of SDC, NiO and LSCF up to 600 °C, which shows the thermal stability of these fuel cell materials.
Keywords	Fuel cells, Ceramic, Nanocomposite, Carbonate, Ionic conductivity, Perovskite
Remark	https://doi.org/10.1016/j.mtener.2017.07.017 Link

ID=412

Stability and range of the type II Bi1 − xWxO1.5 + 1.5x solid solution

Authors	Julia Wind, Paula Kayser, Zhaoming Zhang, Ivana Radosavljevic Evansc, Chris D.Ling
Source	Solid State Ionics Volume: 308, Pages: 173-180 Time of Publication: 2017
Abstract	We have established the stability and range of the cubic type II phase of Bi1 − xWxO1.5 + 1.5x using a combination of X-ray diffraction, neutron diffraction and X-ray absorption spectroscopy. Type II is a high temperature modification that can be obtained by quenching/rapid cooling of samples with compositions between x = 0.148 to x = 0.185. Slower cooling rates yield the stable low temperature polymorph, the tetragonal type Ib phase (Bi rich samples), and mixtures of type Ib and Aurivillius phase (W-rich samples). Throughout the entire solid solution range, type II exhibits a (3 + 3) dimensional incommensurate modulation with modulation vectors slightly smaller than 1/3 based on a cubic fluorite type subcell (δ-Bi2O3). The main structural motifs are well-defined tetrahedra of WO6 octahedra in a δ-Bi2O3-matrix, with additional W being incorporated on corners and face centers of the approximate commensurate 3 × 3 × 3 supercell in octahedral coordination, confirmed by XANES analysis of the W L3-edge. Impedance measurements reveal oxide ionic conductivities comparable to those of yttria-stabilised zirconia even after a decrease in ionic conductivity of about half an order of magnitude on thermal cycling due to transition to the tetragonal type Ib phase.
Keywords	Oxide ionic conductors, Solid solution, Bismuth oxide, Incommensurately modulated structures, Neutron diffraction, XANES
Remark	https://doi.org/10.1016/j.ssi.2017.07.015 Link

ID=408

Tailoring the electrode-electrolyte interface of Solid Oxide Fuel Cells (SOFC) by laser micro-patterning to improve their electrochemical performance

Authors	J.A.Cebollero, R.Lahoz, M.A.Laguna-Bercero, A.Larrea
Source	Journal of Power Sources Volume: 360, Pages: 336-344 Time of Publication: 2017
Abstract	Cathode activation polarisation is one of the main contributions to the losses of a Solid Oxide Fuel Cell. To reduce this loss we use a pulsed laser to modify the surface of yttria stabilized zirconia (YSZ) electrolytes to make a corrugated micro-patterning in the mesoscale. The beam of the laser source, 5 ns pulse width and emitting at λ = 532 nm (green region), is computer-controlled to engrave the selected micro-pattern on the electrolyte surface. Several laser scanning procedures and geometries have been tested. Finally, we engrave a square array with 28 μm of lattice parameter and 7 μm in depth on YSZ plates. With these plates we prepare LSM-YSZ/YSZ/LSM-YSZ symmetrical cells (LSM: La1-xSrxMnO3) and determine their activation polarisation by Electrochemical Impedance Spectroscopy (EIS). To get good electrode-electrolyte contact after sintering it is necessary to use pressure-assisted sintering with low loads (about 5 kPa), which do not modify the electrode microstructure. The decrease in polarisation with respect to an unprocessed cell is about 30%. EIS analysis confirms that the reason for this decrease is an improvement in the activation processes at the electrode-electrolyte interface.
Keywords	SOFC, Laser machining, Corrugated surface, Electrode polarisation, Cathode activation, Electrode/electrolyte interface
Remark	https://doi.org/10.1016/j.jpowsour.2017.05.106 Link

ID=407

Suppression of electrical conductivity and switching of conduction mechanisms in ‘stoichiometric’ (Na0.5Bi0.5TiO3)1−x(BiAlO3)x (0 ≤ x ≤ 0.08) solid solutions

Authors	Fan Yang, Patrick Wu and Derek C. Sinclair
Source	Journal of Materials Chemistry C Volume: 5, Pages: 7243-7252 Time of Publication: 2017
Abstract	(Na0.5Bi0.5TiO3)1−x(BiAlO3)x (0 ≤ x ≤ 0.08) solid solutions were prepared by a solid state reaction and their electrical properties were established by ac impedance spectroscopy and electromotive force transport number measurements. Incorporation of BiAlO3 (BA) decreases the electrical conductivity of Na0.5Bi0.5TiO3 (NBT) and sequentially changes the conduction mechanism with increasing x from predominant oxide-ion conduction to mixed ionic–electronic conduction and finally to predominant electronic conduction. The suppressed oxide-ion conduction by BA incorporation significantly reduces the dielectric loss at elevated temperatures and produces excellent high-temperature dielectric materials for high BA contents. The possible reasons for the suppressed oxide-ion conduction in the NBT–BA solid solutions have been discussed and we propose that the local structure, especially trapping of oxygen vacancies by Al3+ on the B-site, plays a key role in oxide-ion conduction in these apparently ‘stoichiometric’ NBT-based solid-solution perovskite materials.
Remark	DOI: 10.1039/C7TC02519J Link

ID=406

High conductive (LiNaK)2CO3Ce0.85Sm0.15O2 electrolyte compositions for IT-SOFC applications

Authors	Ieeba Khan, Muhammad Imran Asghar, Peter D.Lund, Suddhasatwa Basu
Source	International Journal of Hydrogen Energy Volume: 42, Issue: 32, Pages: 20904-20909 Time of Publication: 2017
Abstract	Composite electrolytes of lithium, sodium, and potassium carbonate ((LiNaK)2CO3), and samarium doped ceria (SDC) have been synthesized and the carbonate content optimized to study conductivity and its performance in intermediate-temperature solid oxide fuel cell (IT-SOFC). Electrolyte compositions of 20, 25, 30, 35, 45 wt% (LiNaK)2CO3–SDC are fabricated and the physical and electrochemical characterization is carried out using X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscope, and current–voltage measurements. The ionic conductivity of (LiNaK)2CO3–SDC electrolytes increases with increasing carbonate content. The best ionic conductivity is obtained for 45 wt% (LiNaK)2CO3–SDC composite electrolyte (0.72 S cm−1 at 600 °C) followed by the 35 wt% (LiNaK)2CO3–SDC composite electrolyte (0.55 S cm−1 at 600 °C). The symmetrical cell of the 35 wt% (LiNaK)2CO3–SDC composite electrolyte with lanthanum strontium cobalt ferrite (LSCF) electrode in air gives an area specific resistance of 0.155 Ω cm2 at 500 °C. The maximum power density of the fuel cell using 35 wt% (LiNaK)2CO3–SDC composite electrolyte, composite NiO anode and composite LSCF cathode is found to be 801 mW cm−2 at 550 °C.
Keywords	IT-SOFC, Ternary carbonate–SDC electrolyte, Carbonate loading, Composite electrolytes
Remark	https://doi.org/10.1016/j.ijhydene.2017.05.152 Link

ID=405

Mixed ionic–electronic conduction in K1/2Bi1/2TiO3

Authors	Linhao Li, Ming Li, Ian M. Reaney and Derek C. Sinclair
Source	J. Mater. Chem. C Volume: 5, Pages: 6300-6310 Time of Publication: 2017
Abstract	Recently, it has been reported that the Pb-free piezoelectric perovskite Na1/2Bi1/2TiO3 (NBT) can be compositionally tuned by close control of the A-site starting stoichiometry to exhibit high levels of oxide-ion conduction. The related K1/2Bi1/2TiO3 (KBT) perovskite has also drawn considerable interest as a promising Pb-free piezoelectric material; however, its conduction properties have been less extensively investigated. Here we report on the influence of the K/Bi ratio in the starting composition on the electrical properties using a combination of impedance spectroscopy and ion-transport property measurements. KBT ceramics exhibit mixed ionic–electronic (oxide-ion) conduction with tion ∼ 0.5 at 600–800 °C and although variations in the A-site starting stoichiometry can create a ∼1 order of magnitude difference in the bulk conductivity at >500 °C, the conductivity is low (ca. 0.1 to 1 mS cm−1 at 700 °C) and the activation energy for bulk conduction remains in the range ∼1.2 to 1.5 eV. The high temperature electrical transport properties of KBT are therefore much less sensitive to the starting A-site stoichiometry as compared to NBT. However, KBT ceramics exhibit non-negligible proton conduction at lower temperatures (<300 °C). For K/Bi ≥ 1 the total conductivity of KBT ceramics at room temperature can be as high as ∼0.1 mS cm−1 under wet atmospheric conditions. This study demonstrates ionic conduction to be a common feature in A1/2Bi1/2TiO3 perovskites, where A = Na, K.
Remark	DOI: 10.1039/C7TC01786C Link

ID=404

Effect of plasma spraying power on LSGM electrolyte of metal-supported solid oxide fuel cells

Authors	Chang-Sing Hwang, Te-Jung Hwang, Chun-Huang Tsai, Chun-Liang Chang, Sheng-Fu Yang, Ming-Hsiu Wu, Cheng-Yun Fu
Source	Ceramics International Volume: 43, Issue: 1, Pages: S591-S597 Time of Publication: 2017
Abstract	Four nickel-iron metal-supported solid oxide fuel cells with a diameter of 2.4 cm and a cathode active area of 1.76 cm2 are fabricated by atmospheric plasma spraying (APS) and heat-treated in air at 850 °C and 500 g cm−2 pressure for 4 h. These cells with the same functional layer materials have electrolyte layers produced by different APS torch powers, but the APS fabrication parameters for other functional layers of these cells are kept the same. XRD data show that there is a LaSrGaO4 impurity phase in the prepared dense LSGM electrolyte produced at 54 kW torch power. According to experimental data on the current-voltage-power and AC impedance measurements at temperatures ranging from 550 to 800 °C, the cell with dense LSGM electrolyte produced at 52 kW torch power has the best power performance and the lowest electrolyte resistance and the corresponding delivered power densities at 0.7 V for 550, 600, 650, 700, 750 and 800 °C temperatures are 0.147, 0.271, 0.426, 0.585, 0.716 and 0.796 W cm−2, respectively.
Keywords	Metal-supported, Solid oxide fuel cell, Atmospheric plasma spraying, LSGM electrolyte
Remark	Link

ID=403

Composite mixed ionic-electronic conducting ceramic for intermediate temperature oxygen transport membrane

Authors	Ming Wei Liao, Tai Nan Lin, Wei Xin Kao, Chun Yen Yeh, Yu Ming Chen, Hong Yi Kuo
Source	Ceramics International Volume: 43, Issue: 1, Pages: S628-S632 Time of Publication: 2017
Abstract	The dense ceramic substrate formed by a mixed ionic-electronic conducting (MIEC) material can be used as an oxygen transport membrane (OTM), enabling the transport of high flux oxygen with certain selectivity and gas separation at high temperatures (800 ~ 900 °C). In recent years, Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) has been reported to be a promising MIEC material for oxygen permeation due to its relatively high oxygen ion conductivity at high temperatures. However, the catalytic efficiency of BSCF is relatively low among the MIEC materials, resulting in the dramatic decrease of oxygen permeation at temperatures below 800 °C. In the present study, a composite MIEC ceramic consisting of a BSCF substrate and the catalytic La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) layer has been proposed. A simple method of laser surface melting is executed to fabricate the composite oxygen transport membrane. The scanning electron microscope (SEM) investigations show that LSCF powders can be well-adherent to the BSCF surface after laser scanning melting process. The oxygen permeation flux reaches 0.5 ml min−1 cm−2 for pure BSCF membrane with thickness of 420 µm, while the BSCF membrane substrate with laser scanning LSCF exhibits substantial improvement on oxygen permeation up to 60% at 700 °C. The result suggests that the composite MIEC ceramic has significant potential for intermediate temperature oxygen transport membrane.
Keywords	Membranes, Composites, Laser surface melting
Remark	https://doi.org/10.1016/j.ceramint.2017.05.222 Link

ID=401

Porous Ca3Co4O9 with enhanced thermoelectric properties derived from Sol–Gel synthesis

Authors	Michael Bittner, Lailah Helmich, Frederik Nietschke, Benjamin Geppert, Oliver Oeckler, Armin Feldhoff
Source	Journal of the European Ceramic Society Time of Publication: 2017
Abstract	Highly porous Ca3Co4O9 thermoelectric oxide ceramics for high-temperature application were fabricated by sol–gel synthesis and subsequent conventional sintering. Growth mechanism of misfit-layered Ca3Co4O9 phase, from sol–gel synthesis educts and upcoming intermediates, was characterized by in-situ X-ray diffraction, scanning electron microscopy and transmission electron microscopy investigations. The Ca3Co4O9 ceramic exhibits a relative density of 67.7%. Thermoelectric properties were measured from 373 K to 1073 K. At 1073 K a power factor of 2.46 μW cm−1 K−2, a very low heat conductivity of 0.63 W m−1 K−1 and entropy conductivity of 0.61 mW m−1 K−2 were achieved. The maintained figure of merit ZT of 0.4 from sol–gel synthesized Ca3Co4O9 is the highest obtained from conventional, non-doped Ca3Co4O9. The high porosity and consequently reduced thermal conductivity leads to a high ZT value.
Keywords	Thermoelectricity; Thermal conductivity; Porosity; Oxide; Ca3Co4O9
Remark	https://doi.org/10.1016/j.jeurceramsoc.2017.04.059 Link

ID=400

Electrochemical performance of Co3O4/CeO2 electrodes in H2S/H2O atmospheres in a proton-conducting ceramic symmetrical cell with BaZr0.7Ce0.2Y0.1O3 solid electrolyte

Authors
Source	Solid State Ionics Time of Publication: 2017
Abstract	The electrochemical performance of Co3O4/CeO2 mixed oxide materials as electrodes, when exposed to H2S/H2O atmospheres, was examined employing a proton conducting symmetrical cell, with BaZr0.7Ce0.2Y0.1O3 (BZCY72) as the solid electrolyte. The impact of temperature (700–850 °C) and H2S concentration (0–1 v/v%) in steam-rich atmospheres (90 v/v% H2O) on the overall cell performance was thoroughly assessed by means of electrochemical impedance spectroscopy (EIS) studies. The performance of the Co3O4/CeO2 electrode was significantly enhanced by increasing the H2S concentration and temperature. The obtained results were interpreted on the basis of EIS results and physicochemical characterization (XRD, SEM) studies of fresh and used electrodes. Notably, it was found that the mass transport processes, mainly associated with the adsorption and diffusion of the intermediate species resulting by the chemical and half-cell reactions taking place during cell operation, dominate the electrode polarization resistance compared with the charge transfer processes. Upon increasing temperature and H2S concentration, the electrode resistance is substantially lowered, due to the in situ activation and morphological modifications of the electrode, induced by its interaction with the reactants (H2S/H2O) and products (H2/SO2) mixtures.
Keywords	H2S-tolerant electrodes; Cobalt-ceria oxides; BZCY72
Remark	https://doi.org/10.1016/j.ssi.2017.04.010 Link

ID=399

Thermal stability and enhanced thermoelectric properties of the tetragonal tungsten bronzes Nb8−xW9+xO47 (0 < x < 5)

Authors
Source	Journal of Materials Chemistry A Time of Publication: 2017
Abstract	Thermoelectric materials are believed to play a fundamental role in the energy field over the next years thanks to their ability of directly converting heat into usable electric energy. To increase their integration in the commercial markets, improvements of the efficiencies are needed. At the same time, cheap and non-toxic materials are required along with easily upscalable production cycles. Compounds of the tetragonal tungsten bronze (TTB) series Nb8−xW9+xO47 fulfill all these requirements and are promising materials. Their adaptive structure ensures glass-like values of the thermal conductivity, and the substitution on the cation side allows a controlled manipulation of the electronic properties. In this contribution we report the stability study of the two highly substituted samples of the series, Nb5W12O47 (x = 3) and Nb4W13O47 (x = 4), when subjected to thermal cycling. Moreover, we show the results of the thermoelectric characterization of these samples. The two compounds have not been affected by the thermal treatment and showed an improvement of the thermoelectric performances up to a zT = 0.2 above 1000 K.
Remark	Link

ID=398

Influence of (Zn,Co)O/ZnO) interface amounts on ionic conduction performance of (Zn1-x,Cox)O (x=0.01, 0.05 and 0.10)

Authors
Source	Composites Part B: Engineering Time of Publication: 2017
Abstract	We investigated the effect of dopant Co atoms into ZnO lattice, on ionic conduction at internal grain and/or through the grain boundary. Influence of dopant Co amount on resistivity was associated with enhanced activation energies of ionic conductivity through the grain boundaries. The change in the activation energy indicated that the mechanism of ionic conduction through the boundaries can be manipulated with Co amount in the lattice. Three conductance mechanisms were identified from the Cole-Cole Plots in order to understand the relaxation mechanism and activation energies of ionic transportations. Formed activation energy, 395 meV, by increasing Co dopant amount up to 10 mol% was attributed to enhanced ionic conductivity through enhancing (Zn,Co)O/ZnO) interface amounts at the grain boundaries. Furthermore, increased activation energy were also enhanced the electronic stability at high temperatures due to decrease in electronic conductivity compared to undoped ZnO.
Keywords	Ionic activation energy; Oxide semiconductors; Impedance spectroscopy
Remark	https://doi.org/10.1016/j.compositesb.2017.04.020 Link

ID=396

Energetically benign synthesis of lanthanum silicate through “silica garden” route and its characterization

Authors	Kavita Parmar, Santanu Bhattacharjee
Source	Materials Chemistry and Physics Volume: 194, Pages: 147–152 Time of Publication: 2017
Abstract	Lanthanum silicate synthesis through “silica garden” route has been reported as an alternative to energy intensive milling procedure. Under optimum conditions lanthanum chloride crystals react with water glass (sodium silicate) to produce self generating hollow lanthanum silicate precipitation tube(s) (LaSPT). The micro tubes are irregular, thick, white coloured and amorphous but are hierarchically built from smaller tubules of 10–20 nm diameters. They retain their amorphous nature on being heated up to 600 °C beyond which crystallization starts. The major phase in the LaSPT heated at 900 °C is La2Si2O7. “As synthesized” LaSPT is heterogeneous and comprises non stoichiometric phases. The exterior and interior surfaces of these tubes are remarkably different in their morphology and chemical composition. LaSPT sintered at 1200 and 1300 °C show fair amount of ionic conductivity.
Keywords	Silica garden; Lanthanum silicate; Synthesis; Characterization
Remark	https://doi.org/10.1016/j.matchemphys.2017.03.021 Link

ID=390

Sm6-xMoO12-δ (x = 0, 0.5) and Sm6WO12 – Mixed electron-proton conducting materials

Authors
Source	Solid State Ionics Time of Publication: 2017
Abstract	Samarium molybdates Sm6-xMoO12-δ (x = 0, 0.5) and samarium tungstate Sm6WO12 – potential mixed electron-proton conductors have been studied by X-ray diffraction, Raman spectroscopy, SEM and impedance spectroscopy (in ambient air and in dry and wet air). Solid solutions differing in structure have been obtained in the Sm2O3-MoO3 system at 1600 °C. The samarium molybdate Sm6MoO12 has the fluorite structure (Fm¯3m). The less samarium rich solid solution Sm5.5MoO11.25 crystallizes in a rhombohedral (View the MathML sourceR3¯) structure. The morphotropic transformation is due to the change in the chemical composition of the solid solution with decreasing Sm3 + concentration. The total conductivity of the cubic fluorite phase Sm6MoO12 at 750 °C in air (1.48 × 10− 3 S/cm, Ea = 1.22 eV) is an order of magnitude higher than that of rhombohedral Sm5.5MoO11.25 (2.34 × 10− 4 S/cm, Ea = 1.11 eV). At low temperatures (T < 500 °C), the Arrhenius plot of total conductivity for Sm6MoO12 and Sm5.5MoO11.25 in air deviates from linearity, suggesting that there is a proton contribution to its conductivity at these temperatures, like in the case of the Sm5.4Zr0.6MoO12.3 zirconium-doped molybdate. Below ~ 500 °C, Sm6MoO12 fluorite and fluorite-like Sm6WO12 have identical Arrhenius plots of conductivity in ambient air. The region of dominant proton conductivity is wider for Sm6WO12 than Sm6MoO12, reaching temperatures as high as 750 °С for the former. The absolute values of total conductivity obtained for samarium tungstate and molybdate at 400 °С in wet air are virtually identical and close to 3 × 10− 6 S/cm, which suggests the conductivity of both compounds is dominated by protons at low temperatures and the proton transport numbers are similar.
Keywords	Phase transition; Fluorite; Fluorite-like phase; Proton-conducting membranes; Proton conductivity; Electron conductivity
Remark	http://dx.doi.org/10.1016/j.ssi.2017.01.020 Link

ID=389

The effect of Zr-substitution in La1‐xSrxCo0.2M0.6Zr0.2O3‐δ (M = Fe, Mn) on the crystal structure, thermal expansion and electronic transport properties

Authors
Source	Solid State Ionics Volume: 301, Pages: 53–58 Time of Publication: 2017
Abstract	The effect of Zr-substitution on the evolution of crystal structure, thermal expansion and the electronic transport properties is reported for La1‐xSrxCo0.2Fe0.6Zr0.2O3‐δ (0.1 ≤ x ≤ 1.0) and La1‐xSrxCo0.2Mn0.6Zr0.2O3-δ (x = 0.1, 0.2, 0.25, 0.3). La1‐xSrxCo0.2Fe0.6Zr0.2O3‐δ was found to be single-phase for the compositions investigated. The electrical conductivity of La1‐xSrxCo0.2Fe0.6Zr0.2O3‐δ demonstrated a maximum for x = 0.5, while the area specific resistance was shown to decrease significantly with increasing Sr-content due to an increased concentration of oxygen vacancies. No signs of oxygen vacancy ordering were observed. The area specific resistance of La0.3Sr0.7Co0.2Fe0.6Zr0.2O3‐δ at 600 °C is close to an order of magnitude lower than reported values for La0.4Sr0.6Co0.2Fe0.8O3‐δ. The series La1‐xSrxCo0.2Mn0.6Zr0.2O3‐δ was found as multiphase materials. The stability of both series is discussed with respect to the red-ox properties of the transition metals.
Keywords	Perovskite; Zr-substitution; X-ray diffraction; Electrical conductivity; Thermal expansion
Remark	http://dx.doi.org/10.1016/j.ssi.2017.01.011 Link

ID=385

The structural and electrical properties of samarium doped ceria films formed by e-beam deposition technique

Authors	Darius Virbukas, Giedrius Laukaitis
Source	Solid State Ionics Time of Publication: 2016
Abstract	Sm2O3-doped CeO2 (Sm0.15Ce0.85O1.925, SDC) thin films were formed by e-beam evaporation method. Thin films were formed evaporating micro powders (particle size varied from 0.3 to 0.5 μm). The influence of deposition rate on formed thin film structures and surface morphology were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersion spectrometry (EDS), and atomic force microscopy (AFM). The deposition rate of formed SDC thin films was changed from 2 to 16 Å/s. The electrical properties were investigated as a function of frequency (0.1–106 Hz) at different temperatures (473–873 K). The formed SDC thin ceramic films repeat the crystallographic orientation of the initial powders using different substrates and different deposition rate. It was determined that crystallites size and samarium concentration are decreasing by increasing the deposition rate. The crystallites size decreased from 17.0 nm to 10.4 nm when SDC thin films were deposited on Alloy 600 (Fe-Ni-Cr), and decreased from 13.7 nm to 8.9 nm when were used optical quartz substrate. The best ionic conductivity σtot = 1.66 Sm− 1 at 873 K temperature, activation energy ΔEa = 0.87 eV (σg = 1.66 Sm− 1, σgb = 1.66 Sm− 1) was achieved when 2 Å/s deposition rate was used. The grain size (in the formed SDC thin films) was ~ 83 nm in this case.
Keywords	Electron beam deposition; Samarium doped ceria oxide (SDC); Solid oxide fuel cells (SOFC); Ionic conductivity
Remark	http://dx.doi.org/10.1016/j.ssi.2016.12.003 Link

ID=384

Interstitial oxygen as a source of p-type conductivity in hexagonal manganites

Authors
Source	Nature Communications Time of Publication: 2016
Abstract	Hexagonal manganites, h-RMnO3 (R=Sc, Y, Ho–Lu), have been intensively studied for their multiferroic properties, magnetoelectric coupling, topological defects and electrically conducting domain walls. Although point defects strongly affect the conductivity of transition metal oxides, the defect chemistry of h-RMnO3 has received little attention. We use a combination of experiments and first principles electronic structure calculations to elucidate the effect of interstitial oxygen anions, Oi, on the electrical and structural properties of h-YMnO3. Enthalpy stabilized interstitial oxygen anions are shown to be the main source of p-type electronic conductivity, without reducing the spontaneous ferroelectric polarization. A low energy barrier interstitialcy mechanism is inferred from Density Functional Theory calculations to be the microscopic migration path of Oi. Since the Oi content governs the concentration of charge carrier holes, controlling the thermal and atmospheric history provides a simple and fully reversible way of tuning the electrical properties of h-RMnO3.
Remark	doi:10.1038/ncomms13745 Link

ID=383

Oxygen ion conductivity in samarium and gadolinium stabilized cerium oxide heterostructures

Authors	Marius Zienius, Kristina Bockute, Darius Virbukas, Giedrius Laukaitis
Source	Solid State Ionics Time of Publication: 2016
Abstract	Gadolinium (GDC) and samarium (SDC) doped ceria were investigated in terms of multilayer systems, evaporated by e-beam technique on optical quartz, Alloy600 and sapphire substrate. GDC-SDC heterostructures of 1.3 μm thicknesses, composed of 1, 2, 3, 5 and 7 layers and they were investigated by structural and ionic conductivity techniques. Bragg peaks show nanocrystalline state of Gd and Sm doped ceria thin films. XRD patterns show fluorite type structure with space group Fm3m. The XRD analysis of thin films, deposited on quartz substrate, reveals the increase of (220) peak with increasing number of layers. The decrease of (111) peak is slightly notable, also. Thin film heterostructures have a face-centered cubic cell with the following lattice parameters, such as 5.4180 nm for GDC of and of 5.4245 nm for SDC. The scanning electron microscopy cross sectional analysis of three-layered structure clearly indicates the interfaces of different material. There are no visually distinct discontinuities in higher layer structures (5–7 layers). Total conductivity increases linearly with increasing of temperature, but decreases with the increase of number of layers. The highest total ionic conductivity at 1214 K temperature for SDC and GDC thin monolayers was 1.62 S/m and 1.02 S/m, respectively. The activation energy increases with the increase of number of layer as well.
Keywords	Multilayer electrolyte; SDC; GDC; e-Beam deposition
Remark	http://dx.doi.org/10.1016/j.ssi.2016.11.025 Link

ID=382

A multistep model for the kinetic analysis of the impedance spectra of a novel mixed ionic and electronic conducting cathode

Authors	A. Donazzi, M. Maestri, G. Groppi
Source	Electrochimica Acta Time of Publication: 2016
Abstract	A one-dimensional, heterogeneous and dynamic model is applied to kinetically analyze impedance experiments performed on a novel NdBa0.9Co2O5.6 (NBC) MIEC cathode. The model simulates the spectra in the time domain by accounting for the gas diffusion inside the electrode pores, and for the solid state diffusion of oxygen vacancies inside the bulk of the cathodic material. A detailed kinetic scheme is applied to describe the oxygen reduction mechanism, which includes steps for adsorption and desorption, first and second electronation at the gas/electrode interface, and ion transfer at the electrode/electrolyte interface. The kinetic investigation is based on impedance spectra collected on symmetric NBC/GDC/NBC cells, at open circuit voltage, between 550 and 700°C, and 5–100% O2 molar fraction. The vacancies diffusion coefficient and the kinetic parameters of the reaction steps are fitted to describe the data. At the highest temperatures, a sensitivity analysis reveals that the rate determining step is the first electronation of the oxygen adatom, while the second electronation and the interfacial ion transport are kinetically irrelevant. Overall, the model allows to individuate the key parameters for capturing the kinetics of a MIEC cathode.
Keywords	EIS; perovskites; kinetics; modeling
Remark	http://dx.doi.org/10.1016/j.electacta.2016.11.072 Link

ID=381

Stability of NASICON materials against water and CO2 uptake

Authors	M. Guin, S. Indris, M. Kaus, H. Ehrenberg, F. Tietz, O. Guillon
Source	Solid State Ionics Time of Publication: 2016
Abstract	The stability in ambient conditions of a scandium-based NASICON material, Na3.4Sc2Si0.4P2.6O12, was investigated using impedance spectroscopy, thermogravimetry/differential scanning calorimetry (TG/DSC) and multinuclear magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The presence of H2O and CO2 in samples stored in ambient air could be evidenced as well as its impact on the ionic conductivity of the samples. The detected amounts of water and CO2 in the samples had no influence on the measured conductivities at room temperature, which confirmed the absence of protonic conduction in hydrated samples. A loss of conductivity during heating of hydrated samples was due to a loss of contact between the ceramic and the electrode used for the conductivity measurement. The recommendation for handling of NASICON-type materials is therefore: samples require storage in an Ar-filled glove box or in a dry environment to avoid artefacts during high temperature measurements. Nevertheless, the stability of the NASICON-type materials is confirmed since their conductivity is not affected by the moisture.
Keywords	Ionic conductivity; NASICON; Sodium; Scandium; ProGasMix
Remark	http://dx.doi.org/10.1016/j.ssi.2016.11.006 Link

ID=380

AgI thin films prepared by laser ablation

Authors	Svetlana V. Fokina, Eugene N. Borisov, Vladimir V. Tomaev, Ilya I. Tumkin, Yuri S. Tveryanovich
Source	Solid State Ionics Volume: 297, Pages: 64–67 Time of Publication: 2016
Abstract	High quality and uniform morphology AgI films consisting of crystal grains about 30 nm in size were obtained by the laser (XeCl) ablation method. The designed silver iodide films have crystalline structure, optical and electrical properties corresponding to stoichiometric compound films. We have demonstrated that the laser ablation method commonly used for the preparation of thin films and nanolayered structures with the defined thickness can be successfully used for the deposition of AgI superionic conductor layers as well. The films were studied by XRD, EDA, optical absorption, photoluminescence, and impedance spectroscopies.
Keywords	Thin films; Laser ablation; Conductivity; Optical band gap; Luminescence; Morphology; Excitons; XRD; Electron microscopy
Remark	http://dx.doi.org/10.1016/j.ssi.2016.10.004 Link

ID=377

Thermodynamic properties of the Ba0.75Sr0.25TiO3 nanopowders obtained by hydrothermal synthesis

Authors	C.F. Rusti, V. Badilita, A.M. Sofronia, D. Taloi, E.M. Anghel, F. Maxim, C. Hornoiu, C. Munteanu, R.M. Piticescu, S. Tanasescu
Source	Journal of Alloys and Compounds Volume: 693, Pages: 1000–1010 Time of Publication: 2017
Abstract	The paper is devoted to the investigation of the thermodynamic properties of nanostructured Ba0.75Sr0.25TiO3 perovskite material synthesized by hydrothermal method. The thermodynamic parameters obtained by a couple of measurements in both isothermal and dynamic regimes (drop calorimetry, solid-oxide electromotive force measurements, differential scanning calorimetry and thermogravimetry), allow for the investigations of the thermodynamic stability in a large temperature range from room temperature to 1273 K. The influence of the oxygen stoichiometry on the thermodynamic properties was examined using a coulometric titration technique coupled with electromotive force measurements. The results are discussed based on the strong correlation between the thermodynamic parameters and the charge compensation of the material system. X-ray powder diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM) were used for the microstructure and morphology analyses. The variation of the thermal expansion and electrical conductivity associated with the structural changes has been evidenced by thermomechanical measurements and impedance spectroscopy, respectively. Through a combined analysis of all the results, new features related to the understanding of the strong interplay between the thermodynamic properties, microstructure, thermal expansion and electrical conductivity in the hydrothermally prepared Ba0.75Sr0.25TiO3 perovskite material have been revealed.
Keywords	Nanostructured materials; Chemical synthesis; Thermodynamic properties; Electromotive force, EMF; Calorimetry; X-ray diffraction
Remark	http://dx.doi.org/10.1016/j.jallcom.2016.09.215 Link

ID=376

Enhanced bulk conductivity of A-site divalent acceptor-doped non-stoichiometric sodium bismuth titanate

Author	Solid State Ionics
Source	Fan Yang, Patrick Wu, Derek C. Sinclair Time of Publication: 2016
Abstract	Bismuth-deficient sodium bismuth titanate (nominally Na0.5Bi0.49TiO2.985, NB0.49T) is a good oxide-ion conductor. Here we report the influence of A-site divalent ions, M2 + = Ca2 +, Sr2 + and Ba2 +, on the electrical properties of NB0.49T. A-site divalent doping for Bi3 + enhances the bulk (grain) conductivity by ~ one order of magnitude without changing the conduction mechanism, which is attributed to an increase in the oxygen vacancy concentration based on the doping mechanism Bi3 + + ½ O2 − → M2 +. Among these three dopants, Sr2 + is the most effective in increasing the bulk conductivity due to a combination of its smaller mismatch in ion size with Bi3 +, its intermediate polarisability and lower bond strength to oxygen compared to Ca2 + and Ba2 +. Doping strategies for further improvements to bulk conductivity of NBT materials are discussed based on these results. Comparison with other oxide-ion conductors and initial stability test under reducing atmosphere show the doped non-stoichiometric NBT materials are promising for low and intermediate temperature applications.
Keywords	Sodium bismuth titanate; Oxide-ion conductors; Doping; Non-stoichiometry
Remark	http://dx.doi.org/10.1016/j.ssi.2016.09.016 Link

ID=373

Solid oxide carbonate composite fuel cells: Size effect on percolation

Authors
Source	International Journal of Hydrogen Energy Time of Publication: 2016
Abstract	In the studies of solid oxide carbonate composite fuel cell, percolation behaviour of the two phases was investigated as a function of particle size of the oxide phase. The ratio of amount of samarium doped ceria (SDC; Sm0.2Ce0.8O) to Na2CO3 was varied to determine an optimum ionic conductivity as function of oxide particle size. The roles of both phases in the composite electrolyte were investigated. SDC particles were mixed in different amounts of Na2CO3 to obtain composites with carbonate ratios from 1 wt% to 50 wt%. Micro-structural investigations showed that Na2CO3 phase served as the matrix in the micro-structure gluing the oxide particles together. The lowest and the highest carbonate ratios caused low conductivities in the composite as in these samples the 3D connectivity of both phases were disrupted. Low conductivity at both ends of the mixture composition could be interpreted as none of the components of the composite dominated the ionic conductivity. The highest conductivity was obtained at 10 wt% Na2CO3 amount in the composite electrolyte when nano-sized SDC (5–10 nm) oxide powders were used. Two different particle sizes of SDC powders were used to show that the optimum phase ratio, i.e. percolation of both phases, is function of particle size as well. The conductivity in the composite showed percolation behaviour with respect to the two constituent phases.
Keywords	Composite electrolyte; SOFC; Interface; Percolation; Carbonate; Impedance
Remark	http://dx.doi.org/10.1016/j.ijhydene.2016.07.208, in press Link

ID=372

Insights into the enhancement of oxygen mass transport properties of strontium-doped lanthanum manganite interface-dominated thin films

Authors
Source	Solid State Ionics Time of Publication: 2016
Abstract	Strontium-doped lanthanum manganite thin films were deposited by pulsed laser deposition on yttria-stabilized zirconia single crystals for a comprehensive electrochemical characterization of the material acting as a cathode. A physically-meaningful electrical model was employed to fit the electrochemical impedance spectroscopy results in order to extract the main oxygen mass transport parameters as a function of the temperature and oxygen partial pressure. The oxygen diffusion and surface exchange coefficients extracted from the analysis showed several orders of magnitude of enhancement with respect to the bulk values reported in the literature and an unexpectedly low dependence with the oxygen partial pressure. Different observations were combined to propose a mechanism for the enhanced incorporation of oxygen in interface-dominated thin films mainly based on the high concentration of oxygen vacancies expected in the grain boundaries.
Remark	http://dx.doi.org/10.1016/j.ssi.2016.08.009 Link

ID=371

Formation of solid solutions in the CdSe–PbSe system under the action of high pressures and temperatures

Authors	A. Yu. Chufarov, N. V. Melnikova, N. V. Zarubina, A. N. Ermakov, E. G. Vovkotrub, L. N. Maskaeva, V. F. Markov, Yu. G. Zainulin
Source	Russian Journal of Inorganic Chemistry Volume: 61, Issue: 8, Pages: 1013–1018 Time of Publication: 2016
Abstract	A method was proposed for producing solid solutions in the CdSe–PbSe systems, which is based on heat and high pressure treatment. X-ray powder diffraction analysis showed the formation of substitutional solid solutions CdxPb1–xSe with the NaCl structure, which contained 20, 40, 60, and 80 mol % cadmium selenide. The solid solutions were characterized by scanning electron microscopy, impedance spectroscopy, gas pycnometry, and Raman spectroscopy.
Remark	DOI: 10.1134/S0036023616080052 Link

ID=369

Nanolayered solid electrolyte (GeSe2)30(Sb2Se3)30(AgI)40/AgI: A new hypothesis for the conductivity mechanism in layered AgI

Authors	Yury S. Tveryanovich, Andrei V. Bandura, Svetlana V. Fokina, Evgeny N. Borisov, Robert A. Evarestov
Source	Solid State Ionics Volume: 294, Pages: 82–89 Time of Publication: 2016
Abstract	Using the laser ablation method, films comprised of alternating layers of AgI and (GeSe2)30(Sb2Se3)30(AgI)40 glass were obtained. Individual layer thickness amounts to 10 ÷ 15 nm, and the total number of layers is about 100. X-ray diffraction (XRD) and film conductivity measurements were carried out during several cycles of heating up to 200 °C and cooling to room temperature. It was established that after three cycles of thermal processing specific lateral conductivity of the film is equal to 0.3 S cm− 1 and conductivity activation energy is equal to 0.07 eV at room temperature. Attempts to explain such a high conductivity value based on XRD results did not yield satisfactory results. However, our first-principle calculations within the density functional theory (DFT) showed that in the free layer composed of four AgI planes a rearrangement occurs, resulting in formation of the stable structure of two silver planes on the inside and two iodine planes on the outside (I–Ag–Ag–I). Rearrangement of similar stack of eight or twelve atomic planes results in formation of two or three I–Ag–Ag–I layers loosely bound to each other, accordingly. This suggests that increase in specific conductivity growth of multilayer film as a consequence of cyclic heating and cooling may be connected with AgI stratification on its boundary with chalcogenide glass and following stabilization of layered phases mentioned above. The existence of an empty space between the layers that is constrained by iodine ion planes should facilitate silver ion diffusion along the layers.
Keywords	Glass-composite; Laser-ablation method; Ionic conductivity; AgI polymorphs; DFT calculations
Remark	doi:10.1016/j.ssi.2016.07.004 Link

ID=366

Tailoring transport properties through nonstoichiometry in BaTiO3–BiScO3 and SrTiO3–Bi(Zn1/2Ti1/2)O3 for capacitor applications

Authors	Nitish Kumar, David P. Cann
Source	Journal of Materials Science Volume: 51, Issue: 20, Pages: 9404–9414 Time of Publication: 2016
Abstract	The ceramic perovskite solid solutions BaTiO3–BiScO3 (BT–BS) and SrTiO3–Bi(Zn1/2Ti1/2)O3 (ST–BZT) are promising candidates for high-temperature and high-energy density dielectric applications. A-site cation nonstoichiometry was introduced in these two ceramic systems to investigate their effects on the dielectric and transport properties using temperature- and oxygen partial pressure-dependent AC impedance spectroscopy. For p-type BT–BS ceramics, the addition of excess Bi led to effective donor doping along with a significant improvement in insulation properties. A similar effect was observed on introducing Ba vacancies onto the A-sublattice. However, Bi deficiency registered an opposite effect with effective acceptor doping and a deterioration in the bulk resistivity values. For n-type intrinsic ST–BZT ceramics, the addition of excess Sr onto the A-sublattice resulted in a decrease in resistivity values, as expected. Introduction of Sr vacancies or addition of excess Bi on A-site did not appear to affect the insulation properties in air. These results indicate that minor levels of nonstoichiometry can have an important impact on the material properties, and furthermore it demonstrates the difficulties encountered in trying to establish a general model for the defect chemistry of Bi-containing perovskite systems.
Remark	DOI: 10.1007/s10853-016-0186-z Link

ID=365

Leaching effect in gadolinia-doped ceria aqueous suspensions for ceramic processes

Authors	A. Caldarelli, E. Mercadelli, S. Presto, M. Viviani, A. Sanson
Source	Journal of Power Sources Volume: 326, Issue: 15, Pages: 70–77 Time of Publication: 2016
Abstract	Gadolinium doped ceria (CGO) is a commonly used electrolytic material for Solid Oxide Fuel Cells (SOFCs) and for this reason different shaping methods for its deposition are reported in literature. Most of these processes are based on the use of organic-based CGO suspensions, but water-based processes are acquiring increasingly interest for their economical and environmental friendly properties. In this paper we reported how the components of water-based suspension and some unexpected process parameters can deeply affect the functional properties of the final powder. In particular, we observed that CGO powders are strongly affected by ionic leaching induced by furoic acid used as dispersant: the extent of this leaching was related to the dispersant concentration and suspension’s ball-milling-time; the phenomenon was confirmed by ICP-AES analyses on suspensions surnatant. Most importantly, ionic leaching affected the electrical properties of CGO: leached powder showed a higher ionic conductivity as a consequence of a partial removal of Gd ions at the grain boundaries. This work is therefore pointing out that when considering water-based suspensions, it is extremely important to carefully consider all the process parameters, including the organic components of the ceramic suspension, as these could lead to unexpected effects on the properties of the powder, affecting the performance of the final shaped material.
Keywords	Gadolinium doped ceria; Water-based suspensions; Furoic acid; Ionic leaching; Electrical conductivity
Remark	doi:10.1016/j.jpowsour.2016.06.069 Link

ID=363

New promising NASICON material as solid electrolyte for sodium-ion batteries: Correlation between composition, crystal structure and ionic conductivity of Na3 + xSc2SixP3 − xO12

Authors	M. Guin, F. Tietz, O. Guillon
Source	Solid State Ionics Volume: 293, Pages: 18–26 Time of Publication: 2016
Abstract	In the search for novel sodium-ion conductors to be used in batteries for grid application, the thoroughly studied class of NASICON materials is of great interest due to compositional diversity and high ionic conductivity. The solid solution Na3 + xSc2(SiO4)x(PO4)3 − x with 0.05 ≤ x ≤ 0.8 was investigated for the first time. The various compositions were synthesized by solid state reaction and their crystallographic and electrical properties were measured. As a result, one of the best sodium-conductive NASICON materials to date was obtained for x = 0.4 (σNa,Total = 6.9 × 10− 4 S cm− 1 at 25 °C). Furthermore, the importance of the sodium concentration and size of lattice parameters on the ionic conductivity were investigated. The bulk ionic conductivity was correlated with the structural parameters along the conduction pathway of the sodium ions and confirm the key influence of the interatomic Na–O distances on sodium ion transport.
Keywords	Ionic conductivity; NASICON; Sodium; Scandium; Solid electrolyte; Battery
Remark	doi:10.1016/j.ssi.2016.06.005 Link

ID=362

Effect of Nb Doping on Hydration and Conductivity of La27W5O55.5−δ

Authors	Cao, Y., Duan, N., Jian, L., Evans, A. and Haugsrud, R.
Source	J. Am. Ceram. Soc. Time of Publication: 2016
Abstract	Hydration properties and electrical characteristics of the high-temperature proton conductor La27(W0.85Nb0.15)5O55.5−δ are investigated by means of thermogravimetry, impedance spectroscopy, and the electromotive force (EMF) method as a function of temperature, water vapor, and oxygen partial pressures, as well as isotope exchange measurements in order to elucidate the mechanism and thermodynamics of protons formation and transport. The highest proton conductivity, 1.3 × 10-3 S/cm, is achieved at 700°C in wet O2. Proton self-diffusion coefficients are estimated from thermogravimetric measurements of hydration and conductivity data. Comparison of the conductivity characteristics between nominally pure and Nb-substituted materials reveals that the ionic conductivity increases and the activation energy decreases with Nb doping. These differences are discussed to reflect changes in the structure promoting ionic transport rather than changing the concentration of defects to any large extent.
Keywords	Lanthanum tungstate; proton concentration; proton conductivity; H/D isotope effect
Remark	doi:10.1111/jace.14346 Link

ID=360

Electrical characterization of amorphous LiAlO2 thin films deposited by atomic layer deposition

Authors
Source	RSC Advances Volume: 6, Issue: 65, Pages: 60479-60486 Time of Publication: 2016
Abstract	LiAlO2 thin films deposited by atomic layer deposition (ALD) have a potential application as an electrolyte in three-dimensional (3D) all-solid-state microbatteries. In this study, Li-ion conductivity of such films is investigated by both in-plane and cross-plane methods. LiAlO2 thin films with a Li composition of [Li]/([Li] + [Al]) = 0.46 and an amorphous structure were grown by ALD with thicknesses of 90, 160 and 235 nm on different substrates. The electrical characterization was conducted by impedance spectroscopy using inert electrodes over a temperature range of 25–200 °C in an inert atmosphere. In-plane conductivities were obtained from films on insulating sapphire substrates, whereas cross-plane conductivities were measured from films on conducting titanium substrates. For the first time, comparison of the in-plane and cross-plane conductivities in these ALD LiAlO2 films has been achieved. More comparable results are obtained using a cross-plane method, whereas in-plane conductivity measurements demonstrate a considerable thickness-dependence with thinner film thickness. The room-temperature conductivity of the LiAlO2 films has been determined to be in the order of 10−10 S cm−1 with an activation energy of ca. 0.8 eV.
Remark	DOI: 10.1039/C6RA03137D Link

ID=358

Conduction Mechanisms in BaTiO3–Bi(Zn1/2Ti1/2)O3 Ceramics

Authors
Source	J. Am. Ceram. Soc. Time of Publication: 2016
Abstract	Polycrystalline BaTiO3–Bi(Zn1/2Ti1/2)O3 (BT–BZT) ceramics have superior dielectric properties for high-temperature and high-energy density applications as compared to the existing materials. While it has been shown that the addition of BZT to BT leads to an improvement in resistivity by two orders of magnitude, in this study impedance spectroscopy is used to demonstrate a novel change in conduction mechanism. While nominally undoped BT exhibits extrinsic-like p-type conduction, it is reported that BT–BZT ceramics exhibit intrinsic n-type conduction using atmosphere-dependent conductivity measurements. Annealing studies and Seebeck measurements were performed and confirmed this result. For BT, resistivity values were higher for samples annealed in nitrogen as compared to oxygen, whereas the opposite responses were observed for BZT-containing solid solutions. This suggests a fundamental change in the defect equilibrium conditions upon the addition of BZT to the solid solution that lowered the carrier concentration and changed the sign of the majority charge carrier. This is then also linked to the observed improvement in resistivity in BT–BZT ceramics as compared to undoped BT.
Remark	doi:10.1111/jace.14313 Link

ID=357

Effect of Nd-deficiency on electrochemical properties of NdBaCo2O6−δ cathode for intermediate-temperature solid oxide fuel cells

Authors
Source	International Journal of Hydrogen Energy Volume: 41, Issue: 24, Pages: 10228–10238 Time of Publication: 2016
Abstract	Nd1−xBaCo2O6−δ (N1−xBCO) is evaluated as cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The effects of Nd-deficiency on the crystal structure, thermal expansion behavior, electrical conductivity and electrochemical performance are studied. N1−xBCO oxides crystallize in the orthorhombic symmetry with Pmmm space group. A good chemical compatibility between N1−xBCO and CGO electrolyte is found at 1100 °C in air. Introducing Nd-deficiency promotes the formation of oxygen vacancy, and significantly improves the electrochemical performance of N1−xBCO cathodes. The lowest area specific resistance (ASR) value of 0.043 Ω cm2 is obtained on the N0.96BCO cathode at 700 °C in air. The rate limiting step for electrochemical oxygen reduction reaction (ORR) is charge transfer process at the interface. The power output of the electrolyte supported cell Ni-CGO/CGO/N0.96BCO reaches 0.6 W cm−2 at 700 °C.
Keywords	Solid oxide fuel cell; Double perovskite; Nd-deficiency; Cathode; Electrode reaction
Remark	doi:10.1016/j.ijhydene.2016.04.248 Link

ID=356

Controlling mixed conductivity in Na1/2Bi1/2TiO3 using A-site non-stoichiometry and Nb-donor doping

Authors	Linhao Li, Ming Li, Huairuo Zhang, Ian M. Reaney and Derek C. Sinclair
Source	J. Mater. Chem. C Volume: 4, Pages: 5779-5786 Time of Publication: 2016
Abstract	Precise control of electronic and/or ionic conductivity in electroceramics is crucial to achieve the desired functional properties as well as to improve manufacturing practices. We recently reported the conventional piezoelectric material Na1/2Bi1/2TiO3 (NBT) can be tuned into a novel oxide-ion conductor with an oxide-ion transport number (tion) > 0.9 by creating bismuth and oxygen vacancies. A small Bi-excess in the nominal starting composition (Na0.50Bi0.50+xTiO3+3x/2, x = 0.01) or Nb-donor doping (Na0.50Bi0.50Ti1−yNbyO3+y/2, 0.005 ≤ y ≤ 0.030) can reduce significantly the electrical conductivity to create dielectric behaviour by filling oxygen vacancies and suppressing oxide ion conduction (tion ≤ 0.10). Here we show a further increase in the starting Bi-excess content (0.02 ≤ x ≤ 0.10) reintroduces significant levels of oxide-ion conductivity and increases tion ∼ 0.4–0.6 to create mixed ionic/electronic behaviour. The switch from insulating to mixed conducting behaviour for x > 0.01 is linked to the presence of Bi-rich secondary phases and we discuss possible explanations for this effect. Mixed conducting behaviour with tion ∼ 0.5–0.6 can also be achieved with lower levels of Nb-doping (y ∼ 0.003) due to incomplete filling of oxygen vacancies without the presence of secondary phases. NBT can now be compositionally tailored to exhibit three types of electrical behaviour; Type I (oxide-ion conductor); Type II (mixed ionic-electronic conductor); Type III (insulator) and these results reveal an approach to fine-tune tion in NBT from near unity to zero. In addition to developing new oxide-ion and now mixed ionic/electronic NBT-based conductors, this flexibility in control of oxygen vacancies allows fine-tuning of both the dielectric/piezoelectric properties and design manufacturing practices for NBT-based multilayer piezoelectric devices.
Remark	DOI: 10.1039/C6TC01719C Link

ID=355

Influence of cathode functional layer composition on electrochemical performance of solid oxide fuel cells

Authors
Source	Journal of Solid State Electrochemistry Time of Publication: 2016
Abstract	In this work, anode-supported solid oxide fuel cells (SOFC) were tested with a yttria-stabilized zirconia (YSZ) (8 mol% Y2O3-ZrO2)/gadolinium-doped ceria (GDC) (Ce0.9Gd 0.1O1.95) bilayer electrolyte and two lanthanum strontium cobalt ferrite (LSCF) composition as functional cathode layer: La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF 1) and La0.60Sr0.40Co0.2Fe0.8O3-δ (LSCF 2). The functional cathode layers were made of 50 % (w/w) LSCF and 50 % (w/w) GDC. Microstructural characterization was performed by scanning electron microscopy and X-ray diffraction. Electrochemical impedance spectroscopy (EIS) and power measurements were performed under oxygen and hydrogen atmospheres. The microscopy studies showed that the LSCF 2 functional layer is more uniform and adherent to the electrolyte and the cathode collector than the LSCF 1 functional layer, which has cracks, chips, and lower adhesion. The use of the LSCF 2 layer allowed an approximately 25-fold reduction in ohmic resistance (0.06 Ω cm−2) compared with the LSCF 1 layer (1.5 Ω cm−2). The power measurements showed a considerable increase in the power cell using LSCF 2 (approximately 420 mW cm−2) compared with the power cell using LSCF 1 (approximately 180 mW cm−2).
Keywords	SOFC, LSCF, Interface, Electrochemical performance, Cathode, Functional layer
Remark	First Online: 20 May 2016. DOI: 10.1007/s10008-016-3241-4 Link

ID=354

Mechanical degradation under hydrogen of yttrium doped barium zirconate electrolyte material prepared with NiO additive

Authors
Source	Journal of Power Sources Volume: 321, Pages: 226–232 Time of Publication: 2016
Abstract	Recently, a novel process was presented to fabricate dense yttrium-doped barium zirconate electrolytes with high proton conductivity. This process was based on the use of a NiO additive during reactive sintering. We show here that materials made from this process present a fast degradation of mechanical properties when put in hydrogen-rich conditions, while material made from conventional sintering without NiO aid remains intact in the same conditions. The fast degradation of samples made from reactive sintering, leading to sample failure under highly compressive conditions, is due to the reduction of NiO nanoparticles at grain boundaries as shown from structural and chemical analyses using Transmission Electron Microscopy. By the present study, we alert about the potential risk of cell failure due to this mechanical degradation.
Keywords	PCFCs; Mechanical properties; BZY; Solid state reactive sintering
Remark	doi:10.1016/j.jpowsour.2016.05.001 Link

ID=352

Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor

Authors
Source	Science Volume: 353, Issue: 6299, Pages: 563-566 Publisher: American Association for the Advancement of Science (AAAS), ISBN: Print ISSN:0036-8075 Online ISSN:1095-9203, Time of Publication: 2016-08
Abstract	Nonoxidative methane dehydroaromatization (MDA: 6CH4 ↔ C6H6 + 9H2) using shape-selective Mo/zeolite catalysts is a key technology for exploitation of stranded natural gas reserves by direct conversion into transportable liquids. However, this reaction faces two major issues: The one-pass conversion is limited by thermodynamics, and the catalyst deactivates quickly through kinetically favored formation of coke. We show that integration of an electrochemical BaZrO3-based membrane exhibiting both proton and oxide ion conductivity into an MDA reactor gives rise to high aromatic yields and improved catalyst stability. These effects originate from the simultaneous extraction of hydrogen and distributed injection of oxide ions along the reactor length. Further, we demonstrate that the electrochemical co-ionic membrane reactor enables high carbon efficiencies (up to 80%) that improve the technoeconomic process viability. Methane gas is expensive to ship. It is usually converted into carbon monoxide and hydrogen and then liquefied. This is economically feasible only on very large scales. Hence, methane produced in small amounts at remote locations is either burned or not extracted. A promising alternative is conversion to benzene and hydrogen with molybdenumzeolite catalysts. Unfortunately, these catalysts deactivate because of carbon buildup; plus, hydrogen has to be removed to drive the reaction forward. Morejudo et al. address both of these problems with a solid-state BaZrO3 membrane reactor that electrochemically removes hydrogen and supplies oxygen to suppress carbon buildup.
Keywords	CMR, MDA, catalytic membrane reactor, ZSM-5, MCM-22, FBR, FBR-PolyM, Pd-CMR, Co-ionic CMR, FT, ProboStat CMR base unit (NORECS)
Remark	http://science.sciencemag.org/highwire/filestream/682540/field_highwire_adjunct_files/0/Morejudo.SM.pdf BaZrO3 BaZrO3 Link

ID=350

Characteristics of Cu and Mo-doped Ca3Co4O9−δ cathode materials for use in solid oxide fuel cells

Authors	Sea-Fue Wang, Yung-Fu Hsu, Jing-Han Chang, Soofin Cheng, Hsi-Chuan Lu
Source	Ceramics International Time of Publication: 2016
Abstract	In this study, Cu and Mo ions were doped in Ca3Co4O9−δ to improve the electrical conductivity and electrochemical behavior of Ca3Co4O9−δ ceramic and the performance of a solid oxide fuel cell (SOFC) single cell based on NiO-SDC/SDC/doped Ca3Co4O9−δ-SDC were examined. Cu substitution in the monoclinic Ca3Co4O9−δ ceramic effectively enhanced the densification, slightly increased the grain size, and triggered the formation of some Ca3Co2O6; however, no second phase was found in porous Mo-doped Ca3Co4O9−δ ceramics even when the sintering temperature reached 1050 °C. Substitution of Cu ions caused slight increase in the Co3+ and Co4+ contents and decrease in the Co2+ content; however, doping with Mo ions showed the opposite trend. Doping the Ca3Co4O9−δ ceramic with a small amount of Cu or Mo increased its electrical conductivity. The maximum electrical conductivity measured was 218.8 S cm−1 for the Ca3Co3.9Cu0.1O9−δ ceramic at 800 °C. The Ca3Co3.9Cu0.1O9−δ ceramic with a coefficient of thermal expansion coefficient of 12.1×10−6 K−1 was chosen as the cathode to build SOFC single cells consisting of a 20 μm SDC electrolyte layer. Without optimizing the microstructure of the cathode or hermetically sealing the cell against the gas, a power density of 0.367 Wcm−2 at 750 °C was achieved, demonstrating that Cu-doped Ca3Co4O9−δ can be used as a potential cathode material for IT-SOFCs.
Keywords	Solid oxide fuel cell; Cathode; Impedance; Cell performance
Remark	In Press, doi:10.1016/j.ceramint.2016.04.037 Link

ID=348

Fluorite-like compounds with high anionic conductivity in Nd2MoO6 – Bi2O3 system

Authors	E.P. Kharitonova, V.I. Voronkova, D.A. Belov, E.I. Orlova
Source	International Journal of Hydrogen Energy Time of Publication: 2016
Abstract	A wide range of (Bi2O3)x(Nd2O3)(1−x)/2(MoO3)(1−x)/2 solid solutions with the structure of the anion-conducting bismuth oxide was found in the Bi2O3–Nd2MoO6 join of ternary Bi2O3–MoO3–Nd2O3 system at 0.5 ≤ x ≤ 1. In said concentration range the compounds with large (0.92 ≤ x ≤ 0.98) and small (0.5 ≤ x < 0.6) bismuth content are tetragonal at room temperature. In the intermediate concentration range (0.67 ≤ x ≤ 0.9) cubic δ-Bi2O3 structure is stabilized at room temperature. It is shown that two tetragonal phases observed at different bismuth concentrations differ from each other in their polymorphism and behavior of the unit cell parameters. All the obtained compounds show high conductivity that reaches 0.1 S/cm (for a cubic sample with x = 0.8 at 800 °C).
Keywords	Bi2O3; Nd2O3; MoO3; Polymorphism; Oxygen conductivity
Remark	In press, doi:10.1016/j.ijhydene.2016.03.046 Link

ID=347

Structural study and proton conductivity in BaCe0.7Zr0.25−xYxZn0.05O3 (x = 0.05, 0.1, 0.15, 0.2 & 0.25)

Authors	Ahmed Afif, Nikdalila Radenahmad, Chee Ming Lim, Mohamad Iskandar Petra, Md. Aminul Islam, Seikh Mohammad Habibur Rahman, Sten Eriksson, Abul Kalam Azad
Source	International Journal of Hydrogen Energy Time of Publication: 2016
Abstract	Solid oxide fuel cell (SOFC) has been considered to generate power represented by conductivity. Zinc doped Barium Cerium Zirconium Yttrium oxide (BCZYZn) has been found to offer high protonic conductivity and high stability as being electrolyte for proton-conducting SOFCs. In this study, we report a new series of proton conducting materials, BaCe0.7Zr0.25−xYxZn0.05O3 (x = 0.05, 0.1, 0.15, 0.2 and 0.25). The materials were synthesized by solid state reaction route and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal expansion, particle size and impedance spectroscopy (IS). Rietveld analysis of the XRD data reveal a cubic perovskite structure with Pm-3m space group up to composition x = 0.15. For x = 0.15 and 0.20, the materials have structural phase change to orthorhombic in the Pbnm space group. Scanning electron microscopy images show high density materials. Thermal expansion measurements show that the thermal expansion coefficient is in the range 10.0–11.0 × 10−6/°C. Impedance spectroscopy shows higher ionic conduction under wet condition compared to dry condition. Y content of 25% (BCZYZn25) exhibits highest conductivity of 1.84 × 10−2 S/cm in wet Argon. This study indicated that perovskite electrolyte BCZYZn is promising material for the next generation of intermediate temperature solid oxide fuel cells (IT-SOFCs).
Keywords	Proton conductor; Sinterability; Rietveld refinement; Conductivity; SOFC electrolyte
Remark	In Press, doi:10.1016/j.ijhydene.2016.02.135 Link

ID=346

Ca-doped fluorite-like compounds based on Nd5Mo3O16

Authors	V.I. Voronkova, E.P. Kharitonova, E.I. Orlova, A.V. Levchenko, A.M. Antipin, N.I. Sorokina, D.A. Belov
Source	Journal of Alloys and Compounds Time of Publication: 2016
Abstract	We have studied phase relations in a molybdenum oxide-rich region of the ternary system CaO–Nd2O3–MoO3. Using polycrystalline samples prepared by solid-state reactions in air, the system has been shown to contain a rather broad region of cubic fluorite-like phases isostructural with Nd5Mo3O16. The atomic structure of a calcium-doped fluorite-like Nd5Mo3O16+δ single crystal grown from an off-stoichiometric melt has been studied by X-ray diffraction. The peculiarities of the structure of calcium-doped fluorite-related compounds were revealed. Experimental structural data demonstrate partial mutual substitutions of Nd and Mo cations, splitting of the O2 position into several additional positions, and the presence of excess oxygen, which occupies octahedral sites in the voids of the structure. Some of the fluorite-like samples have high electrical conductivity, on the order of 10−2 S/cm at 800 °C.
Keywords	Ceramics; Oxides; Crystal growth; Crystal structure; Ionic conductivity
Remark	doi:10.1016/j.jallcom.2016.03.013 Link

ID=345

Crystal structure and proton conductivity of BaSn0.6Sc0.4O3-δ: Insights from neutron powder diffraction and solid state NMR

Authors
Source	Journal of Materials Chemistry A Time of Publication: 2016
Remark	DOI: 10.1039/C5TA09744D Link

ID=344

Optically-transparent and electrically-conductive AgI–AgPO3–WO3 glass fibers

Authors
Source	RSC Advances Volume: 5, Pages: 40236-40248 Time of Publication: 2015
Abstract	In this study, we report to our knowledge the first optically-transparent and electrically-conductive optical glass fiber belonging to the system AgI–AgPO3–WO3. The addition of tungsten oxide (WO3) into the phosphate glassy network allowed the adjustment of the glass transition temperature, thermal expansion coefficient, refractive index, optical band edge, and electrical conductivity, which are all very important parameters in view of drawing glass fibers with a desired set of electrical and optical properties. Furthermore, the addition of WO3 can improve considerably glass stability against water and humidity in the environment. AgI–AgPO3–WO3 glass fibers with 15 mol% WO3 showed 2 dB m−1 optical propagation loss from 800 to 950 nm wavelength range, and 10−3 S cm−1 electrical conductivity at 1 MHz AC frequency. Complex impedance spectra and thermal activation energies ranging from 0.15 to 0.30 eV are indicative of a dominant conductivity mechanism being ionic in nature within the range of AC frequencies from 1 Hz to 1 MHz. Fibers exhibited higher electrical conductivities than the bulk glasses. Glasses in the AgI–AgPO3–WO3 system can be used for fibers that require a set of adjustable properties pertaining to electrical conductivity, optical transparency, and environmental stability.
Remark	DOI: 10.1039/C5RA00681C Link

ID=343

Phase Relations and Physical Properties of Layered Pb-Containing Nd2MoO6 Compounds

Authors	Valentina Voronkova, Ekaterina Orlova, Sergey Kazakov, Elena Kharitonova and Dmitry Belov
Source	European Journal of Inorganic Chemistry Volume: 2016, Issue: 7, Pages: 1022-1029 Time of Publication: 2016
Abstract	The phase relations along the Nd2MoO6–PbO join of the ternary Nd2O3–MoO3–PbO system have been studied by means of solid-state synthesis in air. The samples with high Pb content underwent a reversible first-order phase transition near 820 °C. XRD analysis revealed two tetragonal phases, the high-temperature centric phase (I41/acd) and the low-temperature acentric phase (Iequation image2m). In the region of the phase transition, the permittivity of the Pb-containing samples show a strong lambda-type anomaly and electrical conductivity increases sharply by one and half orders of magnitude. The conductivities of the Pb-containing samples reach 10–2 S/cm at 850 °C, which is two orders of magnitude greater than the conductivity of pure Nd2MoO6. The conductivity in such compounds may be due to oxygen ions. A permittivity anomaly, existence of a piezoelectric effect, and the symmetry change from acentric Iequation image2m to centric I41/acd may indicate an antiferroelectric nature of the phase transition.
Keywords	Conducting materials;Layered compounds;Lead;Rare earths;Solid-phase synthesis
Remark	DOI: 10.1002/ejic.201501167 Link

ID=342

Phase stability and thermoelectric properties of Cu10.5Zn1.5Sb4S13 tetrahedrite

Authors	Subramaniam Harish, Duraisamy Sivaprahasama, Manjusha Battabyal, Raghavan Gopalan
Source	Journal of Alloys and Compounds Volume: 667, Pages: 323–328 Time of Publication: 2016
Abstract	Cu10.5Zn1.5Sb4S13 tetrahedrite compound was prepared by mechanical milling of Cu2S, ZnS and Sb2S3 powders and spark plasma sintered (SPS) to dense samples. The phase formation, chemical homogeneity, thermal stability of the compound and the thermoelectric properties of the sintered samples were evaluated. Single phase tetrahedrite with the crystallite size of 40 nm was obtained after 30 h of milling followed by annealing at 573 K for 6 h in an argon atmosphere. In-situ high-temperature X-ray diffraction studies revealed that the phase is stable up to 773 K. The Seebeck coefficient of the sintered samples of density >98% shows p-type behavior with maximum thermopower of 170 μV/K at 573 K. The electrical resistivity (ρ) decreases with temperature up to 475 K and then increases. A low thermal conductivity of 0.5 W/(m⋅K), in combination with moderate power factor gave a maximum ZT of ∼0.038 at 573 K in Cu10.5Zn1.5Sb4S13 sample having a grain size of ∼200 nm.
Keywords	Thermoelectric; Tetrahedrite; Solid state reactions; Spark plasma sintering; Figure of merit
Remark	doi:10.1016/j.jallcom.2016.01.094 Link

ID=341

New ferroelastic K2Sr(MoO4)2: Synthesis, phase transitions, crystal and domain structures, ionic conductivity

Authors	Galina D. Tsyrenova, Erzhena Т. Pavlova, Sergey F. Solodovnikov, Nadezhda N. Popova, Tatyana Yu. Kardash, Sergey Yu. Stefanovich, Irina А. Gudkova, Zoya A. Solodovnikova, Bogdan I. Lazoryak
Source	Journal of Solid State Chemistry Volume: 237, Pages: 64–71 Time of Publication: 2016
Abstract	K2Sr(MoO4)2 crystals were synthesized and their properties examined. The distortive polymorphic transformations at 421 K (α (LT)→ β(MT)) and 744 K (β(MT)→γ (HT)) of K2Sr(MoO4)2 were studied. It has been shown that the transitions go in sequence from the high-temperature palmierite K2Pb(SO4)2-type γ-phase (R View the MathML source3¯m) to an intermediate β-phase with a probable incommensurate structure and then to a low-temperature α-phase. Domain structures peculiarities in ferroelastic α-K2Sr(MoO4)2 have been investigated. The electrical conductivity of K2Sr(MoO4)2 rises tenfold in the vicinity of the phase transition at 744 K that may be associated with a change conductivity path from quasi-one-dimensional to two-dimensional. The crystal structure of the α-phase (sp. gr. С2/c, а=14.318(3) Å, b=5.9337(12) Å, с=10.422(2) Å, β=105.83(3)°, Z=4, R=0.0219) is similar to that of α-Pb3(PO4)2. Sr-atoms are mainly located at site with the coordination number CN=8 (a tetragonal antiprism with bond lengths of 2.578(2)–2.789(2) Å) and K atoms are located at site with CN=9+1.
Keywords	Potassium; Strontium; molybdates; Phase transitions; Ferroelastics; Crystal structure; Crystal optics analysis; Domain structure; Ionic conductivity
Remark	doi:10.1016/j.jssc.2016.01.011 Link

ID=340

New methods for the preparation and dielectric properties of Lа2 − xSrxNiO4 (х = 1/8) ceramic

Authors	T.I. Chupakhina, N.I. Kadyrova, N.V. Melnikova, O.I. Gyrdasova, E.A. Yakovleva, Yu.G. Zainulin
Source	Materials Research Bulletin Volume: 77, Pages: 190–198 Time of Publication: 2016
Abstract	The perovskite-type oxide La2−xSrxNiO4 (x = 1/8) was prepared by a new precursor route. The reaction proceeds in the self-ignition mode. Single-phase powder and gas-tight ceramic samples can be produced by single annealing of decomposition products. It was shown that as a result of thermobaric treatment of La2−xSrxNiO4 (x = 1/8) the solid solution La2−xSrxNiO4 with a higher concentration of strontium and the second phase La3Ni2O7 are formed. Short-term (5 min) thermobaric treatment (P = 2.5 GPa) at t° = 900 °С changes the unit cell parameters, but is not accompanied by structural transitions. At the same time, morphological restructuring of the sample occurs—the agglomerates delaminate into thin plates crystals. It was established that the permittivity of the material exposed to thermobaric treatment is much higher compared to that of the sample annealed at atmospheric pressure and virtually does not depend on frequency in a wide temperature range.
Keywords	Oxides; X-ray diffraction; High pressure; Impedance spectroscopy; Dielectric properties
Remark	doi:10.1016/j.materresbull.2016.01.023 Link

ID=339

Chemical stability and H2 flux degradation of cercer membranes based on lanthanum tungstate and lanthanum chromite

Authors	Jonathan M. Polfus, , Zuoan Li, Wen Xing, Martin F. Sunding, John C. Walmsley, Marie-Laure Fontaine, Partow P. Henriksen, Rune Bredesen
Source	Journal of Membrane Science Volume: 503, Pages: 42–47 Time of Publication: 2016
Abstract	Ceramic–ceramic composite (cercer) membranes of (Mo-doped) lanthanum tungstate, La27(W,Mo)5O55.5−δ, and lanthanum chromite, La0.87Sr0.13CrO3−δ, have recently been shown to exhibit H2 permeabilities among state-of-the-art. The present work deals with the long-term stability of these cercer membranes in line with concern of flux degradation and phase instability observed in previous studies. The H2 permeability of disc shaped membranes with varying La/W ratio in the lanthanum tungstate phase (5.35≤La/W≤5.50) was measured at 900 and 1000 °C with a feed gas containing 49% H2 and 2.5% H2O for up to 1500 h. It was observed that the H2 permeability decreased by a factor of up to 5.3 over 1500 h at 1000 °C. Post-characterization of the membranes and similarly annealed samples was performed by SEM, STEM and XRD, and segregation of La2O3 was observed. The decrease in H2 permeability was ascribed to the compositional instability of the cation-disordered lanthanum tungstate under the measurement conditions. Equilibration of the La/W ratio by segregation of La2O3 leads to a lower ionic conductivity according to the materials inherent defect chemistry. Partial decomposition and reduction of the lanthanum tungstate phase, presumably to metallic tungsten, was also observed after exposure to nominally dry hydrogen.
Keywords	Hydrogen separation; Dense ceramic membrane; Ceramic–ceramic composite; Lanthanum tungstate; Lanthanum chromite
Remark	doi:10.1016/j.memsci.2015.12.054 Link

ID=337

Synthesis and properties of La0.05Ba0.95Ti1 −xMyO3 (M = Mn, Ce) as anode materials for solid oxide fuel cells

Authors
Source	Solid State Ionics Volume: 283, Pages: 21–29 Time of Publication: 2015
Abstract	Stoichiometric and sub-stoichiometric lanthanum barium titanates (LBT) of perovskite structure type, substituted or not with Mn and/or Ce at the Ti-site, were prepared by sol–gel route with heat treatment in air. All the compounds display a cubic Pm-3m symmetry, which remains stable in reducing atmosphere. Whereas Mn substitution highly promotes the reducibility of the material, the electrical and electrochemical performance of Mn-doped compounds is decreased with respect to non-doped sub-stoichiometric LBT. In contrast, the electrical conductivity and resistance polarization of Ce-substituted LBT are close to those of non-doped LBT and Ce-substituted LBT appears especially efficient in improving the catalytic properties for methane steam reforming and avoiding carbon formation.
Keywords	SOFC; Anode; Perovskite; Barium titanate; Impedance electrochemical spectroscopy; Methane steam reforming
Remark	doi:10.1016/j.ssi.2015.11.005 Link

ID=335

Experimental and molecular dynamics study of thermo-physical and transport properties of ThO2-5wt.%CeO2 mixed oxides

Authors	P.S. Somayajulu, P.S. Ghosh, J. Banerjee, K.L.N.C. Babu, K.M. Danny, B.P. Mandal, T. Mahata, P. Sengupta, S.K. Sali, A. Arya
Source	Journal of Nuclear Materials Volume: 467, Issue: 2, Pages: 644–659 Time of Publication: 2015
Abstract	We have determined the thermo-physical (elastic modulus, specific heat, thermal expansion and thermal conductivity) and transport (ionic conductivity) properties of ThO2-5wt.%CeO2 mixed oxide (MOX) using a combined experimental and theoretical methodology. The specific heat, ionic conductivity and elastic properties of ThO2-5wt.%CeO2 pellets prepared by conventional powder metallurgy (POP) and coated agglomerate pelletization (CAP) routes (sintered in both air and Ar-8%H2 atmosphere) are compared with respect to homogeneity (CeO2 distribution in ThO2 matrix), microstructure, porosity and oxygen to metal ratio. The effects of inhomogeneity and pore distribution on thermal expansion and thermal conductivity of the mixed-oxide pellets are identified. Molecular dynamics (MD) simulations using the Coulomb-Buckingham-Morse-many-body model based interatomic potentials are used to predict elastic properties in the temperature range between 300 and 2000 K and thermodynamic properties, viz., enthalpy increment and specific heats of ThO2. Finally, the thermal expansion coefficient and thermal conductivity of ThO2 and (Th,Ce)O2 mixed-oxides obtained from MD are compared with available experimental results.
Keywords	ThO2-5%CeO2 MOX; Specific heat; Ionic conductivity; Temperature dependent elastic properties; Molecular dynamics simulation
Remark	doi:10.1016/j.jnucmat.2015.10.053 Link

ID=334

Effect of Cerium on the Electrical Properties of a Cobalt Conversion Coating for Solid Oxide Fuel Cell Interconnects – A Study Using Impedance Spectroscopy

Authors	Jan Gustav Grolig, Jan Froitzheim, Jan-Erik Svensson
Source	Electrochimica Acta Volume: 184, Pages: 301–307 Time of Publication: 2015
Abstract	Coatings of metallic cobalt, which convert into a cobalt manganese spinel oxide are known to improve the properties of interconnects for solid oxide fuel cells (SOFCs). The addition of cerium to the cobalt coating further improves the corrosion properties of the material. For this study traditional four-point DC measurements at high temperatures were combined with impedance spectroscopy at low temperatures in order to investigate the effect of cerium on the electrical properties of a cobalt conversion coating. It was found that combination-coatings of cerium and cobalt exhibit superior electrical properties compared to pure cobalt coatings. Cerium slows down the growth of chromia and prevents the outward diffusion of iron into the cobalt spinel layer. Both effects are beneficial for the electrical properties of the interconnect. Impedance spectroscopy measurements revealed that even after more than 3000 h of exposure the outer cobalt manganese spinel layer still has a higher electrical conductivity when cerium was present.
Remark	doi:10.1016/j.electacta.2015.10.111 Link

ID=333

Lithium Polymer Electrolytes Based on Sulfonated Poly(ether ether ketone) for Lithium Polymer Batteries

Authors	Savitha Thayumanasundaram, Vijay Shankar Rangasamy, Jin Won Seo andJean-Pierre Locquet
Source	European Journal of Inorganic Chemistry Volume: 2015, Issue: 32, Pages: 5395–5404 Time of Publication: 2015
Abstract	We studied a lithium-ion conducting polymer based on sulfonated poly(ether ether ketone) (SPEEK) doped with lithium bis(trifluoromethane)sulfonimide (LiTFSI). Self-standing membranes were prepared by the solvent-casting technique with a LiTFSI loading of 0 to 30 wt.-%. The thermogravimetric analysis curves showed that the SO3H groups decompose earlier in the SPEEK–LiTFSI membranes than in pure SPEEK, owing to interactions between the Li+ ions and the SO3H groups. X-ray diffraction and differential scanning calorimetry studies showed that the addition of LiTFSI decreased the crystallinity and the glass-transition temperature of the polymer, which revealed the plasticizing effect of the lithium salt on the polymer matrix. The 7Li NMR spectroscopy results showed a single central transition line at around δ = –1.2 ppm, which indicated the presence of free mobile lithium ions. Dynamic mechanical analysis of the membrane showed it to be mechanically stable up to 100 °C, a prerequisite for flexible lithium polymer batteries. The highest room-temperature conductivity in the order of 10–5 S cm–1 was observed for the 20 wt.-% LiTFSI-doped SPEEK membrane, which increased to 5 × 10–4 S cm–1 at 100 °C.
Keywords	Lithium batteries;Polymer electrolytes;Dynamic mechanical analysis;Raman spectroscopy;Ion pairs
Remark	DOI: 10.1002/ejic.201500649 Link

ID=332

Exceptional hydrogen permeation of all-ceramic composite robust membranes based on BaCe0.65Zr0.20Y0.15O3−δ and Y- or Gd-doped ceria

Authors
Source	Energy Environ. Sci. Volume: 8, Pages: 3675-3686 Time of Publication: 2015
Abstract	Mixed proton and electron conductor ceramic composites were examined as hydrogen separation membranes at moderate temperatures (higher than 500 °C). In particular, dense ceramic composites of BaCe0.65Zr0.20Y0.15O3−δ (BCZ20Y15) and Ce0.85M0.15O2−δ (M = Y and Gd, hereafter referred to as YDC15 and GDC15), as protonic and electronic conducting phases respectively, were successfully prepared and tested as hydrogen separation membranes. The mixture of these oxides improved both chemical and mechanical stability and increased the electronic conductivity in dual-phase ceramic membranes. The synthetic method and sintering conditions were optimized to obtain dense and crack free symmetric membranes. The addition of ZnO as a sintering aid allowed achieving robust and dense composites with homogeneous grain distribution. The chemical compatibility between the precursors and the influence of membrane composition on electrical properties and H2 permeability performances were thoroughly investigated. The highest permeation flux was attained for the 50 : 50 volume ratio BCZ20Y15–GDC15 membrane when the feed and the sweep sides of the membrane were hydrated, reaching values of 0.27 mL min−1 cm−2 at 755 °C on a 0.65 mm thick membrane sample, currently one of the highest H2 fluxes obtained for bulk mixed protonic–electronic membranes. Increasing the temperature to 1040 °C, increased the hydrogen flux up to 2.40 mL min−1 cm−2 when only the sweep side was hydrated. The H2 separation process is attributed to two cooperative mechanisms, i.e. proton transport through the membrane and H2 production via the water splitting reaction coupled with oxygen ion transport. Moreover, these composite systems demonstrated a very good chemical stability under a CO2-rich atmosphere such as catalytic reactors for hydrogen generation.
Remark	DOI: 10.1039/C5EE01793A Link

ID=331

The effect of Cu2O nanoparticle dispersion on the thermoelectric properties of n-type skutterudites

Authors	M Battabyal, B Priyadarshini, D Sivaprahasam, N S Karthiselva and R Gopalan
Source	Journal of Physics D: Applied Physics Volume: 48, Issue: 45 Time of Publication: 2015
Abstract	We report the thermoelectric properties of Ba0.4Co4Sb12 and Sn0.4Ba0.4Co4Sb12 skutterudites dispersed with Cu2O nanoparticles. The samples were synthesized by ball milling and consolidated by spark plasma sintering. Dispersion of Cu2O is found to significantly influence the electrical resistivity and thermopower at high temperatures with a more pronounced effect on the electrical resistivity due to the energy filtering effect at the interface between Cu2O nanoparticles and a Ba0.4Co4Sb12 and Sn0.4Ba0.4Co4Sb12 matrix. At 573 K, the electrical resistivity of Ba0.4Co4Sb12 decreases from 5.01 × 10−5 Ωm to 2.98 × 10−5 Ωm upon dispersion of Cu2O. The dispersion of Cu2O reduces the thermal conductivity of the samples from 300 K and above by increasing the phonon scattering. The lowest observed thermal conductivity at 573 K is found to be 2.001 W mK−1 in Cu2O dispersed Ba0.4Co4Sb12 while it is 2.91 W mK−1 in the Ba0.4Co4Sb12 sample without Cu2O dispersion. Hence Cu2O dispersion plays a significant role in the thermoelectric properties and a maximum figure of merit (ZT ) ~ 0.92 is achieved in Cu2O dispersed Ba0.4Co4Sb12 at 573 K which is more than 200% compared to the pure Ba0.4Co4Sb12 sample. The results from nanoindentation experiments show that the Cu2O dispersed sample (Cu2O + Sn0.4Ba0.4Co4Sb11.6) has a higher reduced Youngs modulus (~139 GPa) than the pure Sn0.4Ba0.4Co4Sb11.6 sample (~128 GPa).
Remark	Link

ID=321

Atomic structure and ionic conductivity of glassy materials based on silver sulfide

Authors	N. V. Melnikova, K. V. Kurochka, O. L. Kheifets, N. I. Kadyrova, Ya. Yu. Volkova
Source	Volume: 79, Issue: 6, Pages: 719-722 Time of Publication: 2015
Abstract	The effect of the composition of glassy ionic conductors AgGe1 + x As1–x S3 and the composites based on these materials containing single-walled carbon nanotubes (CNT) AgGe1+x As1–x (S + CNT)3, on the atomic structure and ionic conductivity is analyzed.
Remark	Link

ID=320

Protons in piezoelectric langatate; La3Ga5.5Ta0.5O14

Authors
Source	Solid State Ionics Volume: 278, Pages: 275–280 Time of Publication: 2015
Abstract	This contribution reports the hydration and electrical transport properties of effectively acceptor doped single crystalline and polycrystalline langatate, La3Ga5.5Ta0.5O14. The electrical properties are investigated over wide ranges of pH2OpH2O, pD2OpD2O and pO2pO2 in the temperature range 400 to 1000 °C. Acceptor doped langatate is dominated by oxygen vacancies in dry atmospheres and at high temperatures, and by protonic defects in wet atmospheres and at lower temperatures. The corresponding standard hydration enthalpy and entropy are − 90 ± 5 kJ/mol and − 130 ± 5 J/mol K, respectively. Further, all compositions display pure proton conductivity in wet atmospheres below 700 °C with a proton mobility enthalpy in the range of 70–75 kJ/mol, depending on doping level and crystallographic direction. Hence, protons are important for the physiochemical properties of langatate even at 1000 °C, and could therefore influence the behavior of langatate-based resonator devices. The proton conductivity is slightly anisotropic, being higher in the X- and Y- than in the Z-direction. At high temperatures and under dry conditions, electron holes and oxide ions dominate the conductivity, and the enthalpy of mobility of vacancies is 140 ± 5 kJ/mol.
Keywords	Langatate; Piezoelectric; Defects; Protons; Conductivity
Remark	doi:10.1016/j.ssi.2015.06.024 Link

ID=319

Tetragonal tungsten bronzes Nb8−xW9+xO47−δ: optimization strategies and transport properties of a new n-type thermoelectric oxide

Authors	Christophe P. Heinrich, Matthias Schrade, Giacomo Cerretti, Ingo Lieberwirth, Patrick Leidich, Andreas Schmitz, Harald Fjeld, Eckhard Mueller, Terje G. Finstad, Truls Norby and Wolfgang Tremel
Source	Materials Horizons Issue: 5, Pages: 519-527 Time of Publication: 2015
Abstract	Engineering of nanoscaled structures may help controlling the electrical and thermal transport in solids, in particular for thermoelectric applications that require the combination of low thermal conductivity and low electrical resistivity. The tetragonal tungsten bronzes Nb8−xW9+xO47 (TTB) allow a continuous variation of the charge carrier concentration while fulfilling at the same time the concept of a “phonon-glass electron-crystal” through a layered nanostructure defined by intrinsic crystallographic shear planes. The thermoelectric properties of the tetragonal tungsten bronzes Nb8−xW9+xO47−δ (0 < x < 2) were studied in the temperature range from 373 to 973 K. Structural defects and the thermal stability under various oxygen partial pressure pO2 were investigated by means of thermogravimetry, HR-TEM, and XRD. Nb8W9O47−δ was found stable at 973 K and a pO2 of ≈10−15 atm. The oxygen nonstoichiometry δ can reach up to 0.3, depending on the applied atmosphere. By increasing the substitution level x, the electrical resistivity ρ and the Seebeck coefficient S decreased. For x = 2, ρ reached 20 mΩ cm at 973 K, combined with a Seebeck coefficient of approximately −120 μV K−1. The thermal conductivity was low for all samples, ranging from 1.6 to 2.0 W K−1 m−1, attributed to the complex crystal structure. The best thermoelectric figure of merit zT of the investigated samples was 0.043, obtained for x = 2 at 973 K, but it is expected to increase significantly upon a further increase of x. The control of the oxygen non-stoichiometry δ opens a second independent optimization strategy for tetragonal tungsten bronzes.
Remark	DOI: 10.1039/C5MH00033E Link

ID=316

Electrical conductivity of Zn-doped high temperature proton conductor LaNbO4

Authors	Yong Cao, Yuan Tan, Dong Yan, , Bo Chi, Jian Pu, Li Jian
Source	Solid State Ionics Volume: 278, Pages: 152–156 Time of Publication: 2015
Abstract	Zn-doped LaNbO4 (La1 − xZnxNbO4 − δ, LZ100x) was prepared by a solid-state reaction method with x = 0, 0.005, 0.01, 0.015, 0.03 and 0.05 and investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and conductivity measurement. There were no XRD and TEM evidences of formed secondary phases in the composition range of x ≤ 0.03 due to the sensitivity. However, the solubility of Zn, less than 1.0 mol.%, was reasonable, according the variety of the grain sizes, conductivity, as well as the activation energy for the conductivity, with the increasing concentration of Zn. The conductivity of LaNbO4 was improved by one to two orders of magnitude with Zn doping in the research range; and the highest conductivity of 9.8 × 10− 4 S cm− 1 was obtained with LZ0.5 at 900 °C in wet air.
Keywords	LaNbO4; Conductivity; Zn doping; Grain size
Remark	doi:10.1016/j.ssi.2015.06.011 Link

ID=315

Gd- and Pr-based double perovskite cobaltites as oxygen electrodes for proton ceramic fuel cells and electrolyser cells

Authors
Source	Solid State Ionics Volume: 278, Pages: 120–132 Time of Publication: 2015
Abstract	Double perovskite oxides BaGd0.8La0.2Co2O6−δ (BGLC), BaGdCo1.8Fe0.2O6−δ (BGCF), BaPrCo2O6−δ (BPC) and BaPrCo1.4Fe0.6O6−δ (BPCF) were investigated as oxygen electrodes on mixed conducting BaZr0.7Ce0.2Y0.1O3 (BZCY72) electrolyte using impedance spectroscopy vs temperature, pO2, and pH2O. We propose and have applied a novel approach to extract and parameterise the charge transfer and diffusion impedances of the electrode reactions in a system comprising charge transport of protons, oxide ions, and electrons. Given by the properties of the BZCY72, transport of protons dominates at lower temperatures and high pH2O, oxide ions at higher temperatures, and electron holes increasingly at high temperatures and high pO2. The electrodes showed good performance, with the lowest total apparent polarisation resistance for BGLC/BZCY72 being 0.05 and 10 Ωcm2 at 650 and 350 °C, respectively. The low temperature rate limiting reaction step is a surface related process, involving protonic species, with an activation energy of approximately 50 kJ mol−1 for BGLC/BZCY72. The oxide ion transport taking over at higher temperatures exhibits a higher activation energy typical of SOFC cathodes. Thermogravimetric studies revealed that BGLC exhibits considerable protonation at 300–400 °C, which may be interpreted as hydration with an enthalpy of approximately –50 kJ mol−1. The resulting mixed proton electron conduction may explain its good performance as electrode on BZCY72.
Keywords	PCFC; PCEC; P-MIEC; Proton conductor; Mixed conductivity; Double perovskite
Remark	doi:10.1016/j.ssi.2015.05.014 Link

ID=312

Reduced long term electrical resistance in Ce/Co-coated ferritic stainless steel for solid oxide fuel cell metallic interconnects

Authors
Source	International Journal of Hydrogen Energy Volume: 40, Issue: 27, Pages: 8579–8585
Abstract	The present study is focused on the influence of selected coatings on a ferritic stainless steel (Sanergy HT™, Sandvik) on the evolution of the area specific resistance (ASR) as a function of time at high temperature. The samples are exposed in humidified air at 850 °C for up to 4200 h. It combines long-term ASR measurements with the thermogravimetric behavior and microstructural analysis of the cross sections by scanning electron microscopy. The results show that uncoated and Co-coated Sanergy HT™ exhibit similar oxidation kinetics and comparable ASRs, while a combined Ce/Co coating improves oxidation resistance and, consequently, reduces the ASR significantly. Other reports have earlier shown that Co- (and Ce/Co)-coated Sanergy HT™ reduces the evaporation of volatile chromium species. Overall, the study indicates that Ce/Co-coatings will render substantially improved performance for ferritic steel interconnects for solid oxide fuel cells.
Keywords	Metallic coating; SOFC; Interconnects; Stainless steel; Conductivity; ASR
Remark	doi:10.1016/j.ijhydene.2015.04.147 Link

ID=311

Resistivity Enhancement and Transport Mechanisms in (1 − x)BaTiO3–xBi(Zn1/2Ti1/2)O3 and (1 − x)SrTiO3–xBi(Zn1/2Ti1/2)O3

Author	Nitish Kumar* andDavid P. Cann
Source	Journal of the American Ceramic Society Time of Publication: 2015
Abstract	Ceramics of composition (1−x)BaTiO3–xBi(Zn1/2Ti1/2)O3 (BT-BZT) were prepared by solid-state synthesis; they have been shown to exhibit excellent properties suited for high-temperature dielectric applications. The X-ray diffraction data showed a single-phase perovskite structure for all the compositions prepared (x ≤ 0.1 BZT). The compositions with less than 0.075 BZT exhibited tetragonal symmetry at room temperature and pseudo-cubic symmetry above it. Most notably, a significant improvement in insulation properties was measured with the addition of BZT. Both low-field AC impedance and high-field direct DC measurements indicated an increase in resistivity of at least two orders of magnitude at 400°C with the addition of just 0.03 BZT (~107 Ω-cm) into the solid solution as compared to pure BT (~105 Ω-cm). This effect was also evident in dielectric loss data, which remained low at higher temperatures as the BZT content increased. In conjunction with band gap measurements, it was also concluded that the conduction mechanism transitioned from extrinsic for pure BT to intrinsic for 0.075 BZT suggesting a change in the fundamental defect equilibrium conditions. It was also shown that this improvement in insulation properties was not limited to BT-BZT, but could also be observed in the paraelectric SrTiO3–BZT system.
Remark	DOI: 10.1111/jace.13666, Article first published online Link

ID=309

High-temperature anion and proton conduction in RE3NbO7 (RE = La, Gd, Y, Yb, Lu) compounds

Authors
Source	Journal of the European Ceramic Society Volume: 35, Issue: 11, Pages: 3051–3061 Time of Publication: 2015
Abstract	The oxide-ion and proton conduction properties of RE3NbO7 (RE = La, Gd, Y, Yb, Lu) compounds were investigated. For the bigger rare-earth cation, i.e. La3+, the compound crystallises in a weberite-type structure and the oxide-ion conductivity is low owing to the lack of intrinsic oxygen vacancies. Consequently, the resultant proton incorporation and conductivity in La3NbO7 are also low. For small rare-earth cations, i.e. from Gd3+ to Lu3+ and for RE = Y, materials adopt a fluorite-like structure confirmed from X-ray powder diffraction. In this latter case, materials include intrinsic oxygen vacancies leading to a higher oxygen conductivity. For these compounds, a proton incorporation takes place at low temperature under wet conditions giving rise to proton conductivity. Nevertheless, both oxygen and proton conductivities are low in these materials, which can be explained by the ordering of oxygen vacancies observed by Transmission Electron Microscopy.
Keywords	Protonic ceramic fuel cell; Rare-earth niobate; Combustion synthesis; Fluorite-type structure; Electrical properties
Remark	doi:10.1016/j.jeurceramsoc.2015.04.014 Link

ID=308

Proton transport properties of the RE3Ga5MO14 (RE = La, Nd and M = Si, Ti, Sn) langasite family of oxides

Authors
Source	Solid State Ionics Volume: 275, Pages: 29–34 Time of Publication: 2015
Abstract	Hydration and proton transport properties of novel, intrinsically acceptor doped compositions within the RE3Ga5MO14 family of oxides have been addressed by means of measurements of the electrical conductivity. Oxygen vacancies and protons charge compensate the acceptor in dry and wet atmospheres, respectively, and all compositions display significant proton conductivity below 1000 °C. The hydration thermodynamics is affected by M-ion substitution, and becomes more favorable in the order Si < Ti < Sn. The enthalpy of proton mobility is also strongly dependent on the M-ion; M = Si, Ti and Sn exhibit enthalpies of proton mobility of 76 ± 3, 61 ± 1 and 80 ± 2 kJ mol− 1, respectively.
Keywords	Langasites; Conductivity; Defects; Acceptor; Hydration; Protons
Remark	doi:10.1016/j.ssi.2015.03.014 Link

ID=306

Crystal structure and high-temperature properties of the Ruddlesden–Popper phases Sr3−xYx(Fe1.25Ni0.75)O7−δ (0≤x≤0.75)

Authors
Source	Journal of Solid State Chemistry Volume: 227, Pages: 45–54 Time of Publication: 2015
Abstract	Ruddlesden–Popper n=2 member phases Sr3−xYxFe1.25Ni0.75O7−δ, 0≤x≤0.75, have been investigated by X-ray and neutron powder diffraction, thermogravimetry and Mössbauer spectroscopy. Both samples as-prepared at 1300 °C under N2(g) flow and samples subsequently air-annealed at 900 °C were studied. The as-prepared x=0.75 phase is highly oxygen deficient with δ=1, the O1 atom site being vacant, and the Fe3+/Ni2+ ions having a square pyramidal coordination. For as-prepared phases with lower x values, the Mössbauer spectral data are in good agreement with the presence of both 5- and 4-coordinated Fe3+ ions, implying in addition a partial occupancy of the O3 atom sites that form the basal plane of the square pyramid. The air-annealed x=0.75 sample has a δ value of 0.61(1) and the structure has Fe/Ni ions in both square pyramids and octahedra. Mössbauer spectroscopy shows the phase to contain only Fe3+, implying that all Ni is present as Ni3+. Air-annealed phases with lower x values are found to contain both Fe3+ and Fe4+. For both the as-prepared and the air-annealed samples, the Y3+ cations are found to be mainly located in the perovskite block. The high-temperature thermal expansion of as-prepared and air-annealed x=0.75 phases were investigated by high-temperature X-ray diffraction and dilatometry and the linear thermal expansion coefficient determined to be 14.4 ppm K−1. Electrical conductivity measurements showed that the air-annealed samples have higher conductivity than the as-prepared ones.
Keywords
Remark	doi:10.1016/j.jssc.2015.03.018 Link

ID=305

Atmosphere dependence of anode reaction of intermediate temperature steam electrolysis using perovskite type proton conductor

Authors	Takaaki Sakai, Keita Arakawa, Masako Ogushi, Tatsumi Ishihara, Hiroshige Matsumoto, Yuji Okuyama
Source	Journal of Solid State Electrochemistry Volume: 19, Issue: 6, Pages: 1793-1798 Time of Publication: 2015
Abstract	The effect of oxygen partial pressure on anode reaction of steam electrolysis using SrZr0.5Ce0.4Y0.1O3-α (SZCY-541) proton conducting electrolyte was investigated by AC impedance measurement in this work. The anode reaction was enhanced by increasing oxygen partial pressure, and this result was opposite to the expectation from the conventional anode reaction (water splitting reaction). The increase in the electrode reaction conductivity with oxygen chemical potential was proportional to PO21/4 at 600 °C and at higher oxygen partial pressure region of 700 and 800 °C, suggesting the possibility that the enhancement is caused by the increase in hole concentration on the electrolyte surface near the anode.
Remark	Link

ID=304

FD Electrolysis: Co-electrolysis of steam and CO2 in full-ceramic symmetrical SOECs: A strategy for avoiding the use of Hydrogen as a safe gas

Authors
Source	Faraday Discussions Time of Publication: 2015
Abstract	The use of cermets as fuel electrodes for solid oxide electrolysis cells requires permanent circulation of reducing gas, e.g. H2 or CO, so called safe gas, in order to avoid oxidation of the metallic phase. Replacing metallic based electrodes by pure oxides is therefore proposed as an advantage for the industrial application of solid oxide electrolyzers. In this work, full-ceramic symmetrical solid oxide electrolysis cells have been investigated for steam/CO2 co-electrolysis. Electrolyte supported cells with La0.75Sr0.25Cr0.5Mn0.5O3-δ reversible electrodes have been fabricated and tested in co-electrolysis mode using different fuel compositions, from pure H2O to pure CO2, at temperatures of 850°C – 900°C. Electrochemical impedance spectroscopy and galvanostatic measurements have been carried out for the mechanistic understanding of the symmetrical cells performance. The content of H2 and CO in the product gas has been measured by in-line gas micro-chromatography. The effect of employing H2 as a safe gas has been also investigated. Maximum density currents of 750 mA/cm2 and 620 mA/cm2 have been applied at 1.7 V for pure H2O and for H2O:CO2 ratios of 1:1, respectively. Remarkable results were obtained for hydrogen-free fuel compositions, which confirmed the interest of using ceramic oxides as a fuel electrode candidate to reduce or completely avoid the use of safe gas in operation minimizing the contribution of the reverse water shift reaction (RWSR) in the process. H2:CO ratios close to two were obtained for hydrogen-free tests fulfilling the basic requirements for synthetic fuel production. An important increase of the operation voltage was detected under continuous operation leading to a dramatic failure by delamination of the oxygen electrode.
Remark	Accepted Manuscript, DOI: 10.1039/C5FD00018A Link

ID=303

Doping strategies for increased oxygen permeability of CaTiO3 based membranes

Authors	Jonathan M. Polfus, Wen Xing, Martin F. Sunding, Sidsel M. Hanetho, Paul Inge Dahl, Yngve Larring, Marie-Laure Fontaine, Rune Bredesen
Source	Journal of Membrane Science Volume: 482, Pages: 137–143 Time of Publication: 2015
Abstract	Oxygen permeation measurements are performed on dense samples of CaTi0.85Fe0.15O3−δ, CaTi0.75Fe0.15Mg0.05O3−δ and CaTi0.75Fe0.15Mn0.10O3−δ in combination with density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) in order to assess Mg and Mn as dopants for improving the O2 permeability of CaTi1−xFexO3−δ based oxygen separation membranes. The oxygen permeation measurements were carried out at temperatures ranging between 700 and 1000 °C with feed side oxygen partial pressures between 0.01 and 1 bar. The O2 permeability was experimentally found to be highest for the Mn doped sample over the whole temperature range, reaching 4.2×10−3 ml min−1 cm−1 at 900 °C and 0.21 bar O2 in the feed which corresponds to a 40% increase over the Fe-doped sample and similar to reported values for x=0.2. While the O2 permeability of the Mg doped sample was also higher than the Fe-doped sample, it approached that of the Fe-doped sample above 900 °C. According to the DFT calculations, Mn introduces electronic states within the band gap and will predominately exist in the effectively negative charge state, as indicated by XPS measurements. Mn may therefore improve the ionic and electronic conductivity of CTF based membranes. The results are discussed in terms of the limiting species for ambipolar transport and O2 permeability, i.e., oxygen vacancies and electronic charge carriers.
Keywords	Dense ceramic oxygen membrane; Ambipolar transport; Mixed ionic-electronic conduction; CaTiO3; Calcium titanate
Remark	doi:10.1016/j.memsci.2015.02.036 Link

ID=300

Electrical conductivity and thermopower of (1 − x) BiFeO3 – xBi0.5K0.5TiO3 (x = 0.1, 0.2) ceramics near the ferroelectric to paraelectric phase transition

Authors	E. T. Wefring, M.-A. Einarsrud and T. Grande
Source	Physical Chemistry Chemical Physics Volume: 17, Issue: 14, Pages: 9420-9428 Time of Publication: 2015
Abstract	Ferroelectric BiFeO3 has attractive properties such as high strain and polarization, but a wide range of applications of bulk BiFeO3 are hindered due to high leakage currents and a high coercive electric field. Here, we report on the thermal behaviour of the electrical conductivity and thermopower of BiFeO3 substituted with 10 and 20 mol% Bi0.5K0.5TiO3. A change from p-type to n-type conductivity in these semi-conducting materials was demonstrated by the change in the sign of the Seebeck coefficient and the change in the slope of the isothermal conductivity versus partial pressure of O. A minimum in the isothermal conductivity was observed at [similar]10−2 bar O2 partial pressure for both solid solutions. The strong dependence of the conductivity on the partial pressure of O2 was rationalized by a point defect model describing qualitatively the conductivity involving oxidation/reduction of Fe3+, the dominating oxidation state of Fe in stoichiometric BiFeO3. The ferroelectric to paraelectric phase transition of 80 and 90 mol% BiFeO3 was observed at 648 ± 15 and 723 ± 15 °C respectively by differential thermal analysis and confirmed by dielectric spectroscopy and high temperature powder X-ray diffraction.
Remark	DOI: 10.1039/C5CP00266D Link

ID=299

Structure and conductivity of acceptor doped La2BaZnO5 and Nd2BaZnO5

Authors	Md. Khairul Hoque, Reidar Haugsrud, Christopher S. Knee
Source	Solid State Ionics Volume: 272, Pages: 160–165 Time of Publication: 2015
Abstract	The effect of calcium substitution on the structure and electrical conductivity of Ln2 − xCaxBaZnO5 − δ, Ln = La and Nd, has been studied. Differing trends with respect to dependence of the unit cell volume were observed as a function of Ca substitution. For both series of materials the limit of Ca substitution was estimated to be x ≈ 0.2. The electrical conductivity was studied in the temperature range of 1000–350 °C using electrochemical impedance spectroscopy in argon and oxygen atmospheres and via isotherms between 400 and 1000 °C as function of oxygen pressure and the water vapour pressure. A marked increase in conductivity of approx. two orders of magnitude was explained by the presence of oxygen vacancies in the calcium doped samples. At pO2 < 10− 12 atm the x = 0.15 materials are predominantly oxygen ion conductors, and La1.85Ca0.15BaZnO5 − δ displays a peak conductivity of 0.002 S cm− 1 at 1000 °C. The materials display a rise in conductivity in oxidizing conditions, indicating a significant p-type contribution.
Keywords	Oxide ion conductor; Mixed conductor; Synthesis; Impedance spectroscopy; SOFC
Remark	doi:10.1016/j.ssi.2015.02.001 Link

ID=298

Dual atmosphere study of the K41X stainless steel for interconnect application in high temperature water vapour electrolysis

Authors	M.R. Ardigo, I. Popa, L. Combemale, S. Chevalier, F. Herbst, P. Girardon
Source	International Journal of Hydrogen Energy Volume: 40, Issue: 15, Pages: 5305–5312 Time of Publication: 2015
Abstract	High temperature water vapour electrolysis (HTE) is one of the most efficient technologies for mass hydrogen production. A major technical difficulty related to high temperature water vapour electrolysis is the development of interconnects working efficiently for a long period. Working temperature of 800 °C enables the use of metallic materials as interconnects. High temperature corrosion behaviour and electrical conductivity of a commercial stainless steel, K41X (AISI 441), were tested in HTE dual atmosphere (95%O2-5%H20/10%H2-90%H2O) at 800 °C. The alloy exhibits a very good oxidation resistance compared to single atmosphere tests. However, a supplied electrical current significantly changes the nature of the oxides that form during the test. A very good Area Specific Resistance (ASR) parameter was measured in dual atmosphere, much lower than the values obtained in single atmosphere tests.
Remark	doi:10.1016/j.ijhydene.2015.01.116 Link

ID=296

Phase equilibria in the Cs2MoO4–ZnMoO4–Zr(MoO4)2 system, Crystal structures and properties of new triple molybdates Cs2ZnZr(MoO4)4 and Cs2ZnZr2(MoO4)6

Authors	Galina D. Tsyrenova, Sergey F. Solodovnikov, Nadezhda N. Popova, Zoya A. Solodovnikova, Erzhena T. Pavlova, Dmitry Yu. Naumov, Bogdan I. Lazoryak
Source	Volume: 81, Pages: 93–99 Time of Publication: 2015
Abstract	Subsolidus phase relations in the Cs2MoO4–ZnMoO4–Zr(MoO4)2 system were determined and two new compounds, Cs2ZnZr(MoO4)4 and Cs2ZnZr2(MoO4)6, were obtained. The structure of Cs2ZnZr(MoO4)4 (a=5.7919(1) Å, c=8.0490(3) Å; space group P View the MathML source3¯m1; Z=0.5; R=0.0149) belongs to the layered glaserite-like KAl(MoO4)2 structure type where the octahedral Al3+ positions are statistically occupied by 0.5 Zn2++0.5 Zr4+. The second triple molybdate, Cs2ZnZr2(MoO4)6 (a=13.366(1) Å, c=12.253(3) Å, space group R View the MathML source3¯, Z=3, R=0.0324), is isostructural to Cs2MnZr2(MoO4)6 and Cs2M2Zr(MoO4)6 (M=Al, Fe) and contains a mixed 3D framework built of МоO4 tetrahedra and (Zn, Zr)O6 octahedra sharing common vertices. Cesium cations are located in large channels of the framework. The latter compound undergoes a first-order phase transition at 723 K with considerable increasing its ionic conductivity.
Keywords	Cesium; Zinc; Zirconium; Triple molybdates; Crystal structure; X-ray diffraction; IR and Raman spectra; Conductivity
Remark	doi:10.1016/j.jpcs.2015.01.015 Link

ID=294

Hydrogen separation membranes based on dense ceramic composites in the La27W5O55.5–LaCrO3 system

Authors	Jonathan M. Polfus, Wen Xing, Marie-Laure Fontaine, Christelle Denonville, Partow P. Henriksen, Rune Bredesen
Source	Journal of Membrane Science Volume: 479, Pages: 39–45 Time of Publication: 2015
Abstract	Some compositions of ceramic hydrogen permeable membranes are promising for integration in high temperature processes such as steam methane reforming due to their high chemical stability in large chemical gradients and CO2 containing atmospheres. In the present work, we investigate the hydrogen permeability of densely sintered ceramic composites (cercer) of two mixed ionic-electronic conductors: La27W3.5Mo1.5O55.5−δ (LWM) containing 30, 40 and 50 wt% La0.87Sr0.13CrO3−δ (LSC). Hydrogen permeation was characterized as a function of temperature, feed side hydrogen partial pressure (0.1–0.9 bar) with wet and dry sweep gas. In order to assess potentially limiting surface kinetics, measurements were also carried out after applying a catalytic Pt-coating to the feed and sweep side surfaces. The apparent hydrogen permeability, with contribution from both H2 permeation and water splitting on the sweep side, was highest for LWM70-LSC30 with both wet and dry sweep gas. The Pt-coating further enhances the apparent H2 permeability, particularly at lower temperatures. The apparent H2 permeability at 700 °C in wet 50% H2 was 1.1×10−3 mL min−1 cm−1 with wet sweep gas, which is higher than for the pure LWM material. The present work demonstrates that designing dual-phase ceramic composites of mixed ionic-electronic conductors is a promising strategy for enhancing the ambipolar conductivity and gas permeability of dense ceramic membranes.
Keywords	Hydrogen separation; Dense ceramic membrane; Ceramic–ceramic composite; Lanthanum tungstate; Lanthanum chromite
Remark	doi:10.1016/j.memsci.2015.01.027 Link

ID=293

Bi1−xNbxO1.5+x (x=0.0625, 0.12) fast ion conductors: Structures, stability and oxide ion migration pathways

Authors	Matthew L. Tate, Jennifer Hack, Xiaojun Kuang, Garry J. McIntyre, Ray L. Withers, Mark R. Johnson, Ivana Radosavljevic Evans
Source	Journal of Solid State Chemistry Volume: 225, Pages: 383–390 Time of Publication: 2015
Abstract	A combined experimental and computational study of Bi1−xNbxO1.5+x (x=0.0625 and 0.12) has been carried out using laboratory X-ray, neutron and electron diffraction, impedance measurements and ab-initio molecular dynamics. We demonstrate that Bi0.9375Nb0.0625O1.5625, previously reported to adopt a cubic fluorite-type superstructure, can form two different polymorphs depending on the synthetic method: a metastable cubic phase is produced by quenching; while slower cooling yields a stable material with a tetragonal √2×√2×1 superstructure, which undergoes a reversible phase transition into the cubic form at ~680 °C on subsequent reheating. Neutron diffraction reveals that the tetragonal superstructure arises mainly from ordering in the oxygen sublattice, with Bi and Nb remaining disordered, although structured diffuse scattering observed in the electron diffraction patterns suggests a degree of short-range ordering. Both materials are oxide ion conductors. On thermal cycling, Bi0.88Nb0.12O1.62 exhibits a decrease in conductivity of approximately an order of magnitude due to partial transformation into the tetragonal phase, but still exhibits conductivity comparable to yttria-stabilised zirconia (YSZ). Ab-initio molecular dynamics simulations performed on Bi0.9375Nb0.0625O1.5625 show that oxide ion diffusion occurs by O2− jumps between edge- and corner-sharing OM4 groups (M=Bi, Nb) via tetrahedral □M4 and octahedral □M6 vacancies.
Keywords	Functional oxides; Fast ion conductors; Complex superstructures
Remark	doi:10.1016/j.jssc.2015.01.006 Link

ID=292

Functional properties of La0.99X0.01Nb0.99Al0.01O4−δ and La0.99X0.01Nb0.99Ti0.01O4−δ proton conductors where X is an alkaline earth cation

Authors
Source	Journal of the European Ceramic Society Volume: 35, Issue: 4, Pages: 1239–1253 Time of Publication: 2015
Abstract	Lanthanum niobates with general formulas of La0.99X0.01Nb0.99Al0.01O4−δ and La0.99X0.01Nb0.99Ti0.01O4−δ (X = Mg, Ca, Sr or Ba) were synthesized via the conventional solid state reaction. Specimens with relative density above 96% were produced after sintering. Structural and phase composition studies revealed predominant monoclinic Fergusonite structure for the majority of samples. SEM and TEM studies elucidated the effect of the used dopant combinations on grain growth, micro-crack formation and secondary phase formation. Results from microstructural study were correlated to the grain interior and grain boundary conductivities for selected samples (La0.99Sr0.01Nb0.99Al0.01O4−δ and La0.99Sr0.01Nb0.99Ti0.01O4−δ). The majority of co-doped niobates exhibited appreciable protonic conductivity under humid atmospheres at intermediate temperatures. Sr- or Ca-doped compounds displayed the highest total conductivities with values for LSNA equal to 6 × 10−4 S/cm and 3 × 10−4 S/cm in wet air and in wet 4% H2–Ar (900 °C), respectively. Additionally, thermal expansion was studied to complete functional characterization of co-doped LaNbO4.
Keywords	Proton-conducting ceramic materials; Hydrogen transport ceramic membranes; Rare earth ortho-niobates; Acceptor-doped lanthanum niobates
Remark	doi:10.1016/j.jeurceramsoc.2014.11.009 Link

ID=291

Hydrogen permeation, water splitting and hydration kinetics in Nd5.4Mo0.3W0.7O12−δ

Authors
Source	Journal of Membrane Science Volume: 476, Pages: 105–111 Time of Publication: 2015
Abstract	To investigate transport properties of Mo-substituted Nd5.4Mo0.3W0.7O12−δ for hydrogen separation application, hydrogen fluxes of Nd5.4Mo0.3W0.7O12−δ have been measured in both dry and wet sweep gases. The fluxes in dry sweep gas show lower temperature dependence at high temperatures than at low temperatures. Comparing the hydrogen permeability among rare earth tungstates, it has been revealed that the larger the RE-site cation radius, the higher the hydrogen permeation. Water splitting effect for the wet sweep gas has been confirmed by mass spectrometry. Oxygen surface kinetics under oxidizing conditions has been studied by ToF-SIMS measurements, and is significantly faster under wet conditions than dry. Hydration kinetics has been studied by conductivity relaxation measurements under reducing conditions for the first time, showing a two-fold non-monotonic behavior.
Keywords	Hydrogen permeation; Hydration kinetics; Water splitting; Oxygen surface kinetics; Nd5.4Mo0.3W0.7O12−δ
Remark	doi:10.1016/j.memsci.2014.11.013 Link

ID=290

Savitha Thayumanasundaram, Vijay Shankar Rangasamy, Niels De Greef, Jin Won Seo andJean-Pierre Locquet

Author	Hybrid Polymer Electrolytes Based on a Poly(vinyl alcohol)/Poly(acrylic acid) Blend and a Pyrrolidinium-Based Ionic Liquid for Lithium-Ion Batteries
Source	European Journal of Inorganic Chemistry Volume: 2015, Issue: 7, Pages: 1290–1299 Time of Publication: 2014
Abstract	Polymer blends of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) were prepared with different molar ratios by a solvent-casting technique. The XRD patterns of the blends show that the degree of crystallinity of the PVA membranes decreases with the addition of PAA owing to the formation of interpenetrating polymer chains. The vibrational spectra of the blend membranes reveal the formation of strong hydrogen bonding between PVA and PAA. Dynamic mechanical analysis (DMA) reveals that the storage modulus of a 25 mol-% PAA sample is comparable to that of pure PVA and, therefore, confirms the mechanical stability of the blend membranes. Significant changes in the peak areas and chemical shifts of the PVA hydroxyl signal (δ = 4–5 ppm) in the 1H NMR spectra of the blend membranes confirm the strong hydrogen bonding between the OH groups of PVA and PAA. The ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) with 0.2 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was added to the polymer blend to prepare flexible, nonvolatile hybrid polymer electrolytes for lithium-ion batteries. A maximum ionic conductivity of 1 mS cm–1 is observed at 90 °C for the membrane with 70 mol-% IL.
Keywords	Polymers;Ionic liquids;Hybrid membranes;Hydrogen bonds;Lithium batteries
Remark	DOI: 10.1002/ejic.201402603 Link

ID=289

Pure and Mn-doped La4SrTi5O17 layered perovskite as potential solid oxide fuel cell material: Structure and anodic performance

Authors
Source	Journal of Power Sources Volume: 274, Pages: 806–815 Time of Publication: 2015
Abstract	Pure and 5% Mn doped layered perovskites La4SrTi5O17, members of the La4Srn-4(Ti,Mn)nO3n+2 series with n = 5, have been synthesized and investigated as anode materials for Solid Oxide Fuel Cells. The use of XRD, neutron and electron diffraction techniques allows clarifying some divergences concerning the structural characterization within the family, not only in air but also in anodic-like N2/H2(97/3) atmosphere. The electrical conductivity of both compounds is very low in air but those values increase by two orders of magnitude in diluted hydrogen. The study of catalytic properties for methane steam reforming as well as in-depth analysis of the SOFC anodic behaviour of both materials are described, for which a microstructure optimization of the electrode allows to demonstrate the potential interest of the lamellar materials upon the classical three-dimensional cubic-like LSTs.
Keywords	SOFC; Anode; Layered perovskite; Titanate; Methane steam reforming; Electrochemical impedance spectroscopy
Remark	doi:10.1016/j.jpowsour.2014.10.131 Link

ID=286

Functional properties of La0.99X0.01Nb0.99Al0.01O4−δ and La0.99X0.01Nb0.99Ti0.01O4−δ proton conductors where X is an alkaline earth cation

Authors
Source	Journal of the European Ceramic Society Time of Publication: 2014-12
Abstract	Lanthanum niobates with general formulas of La0.99X0.01Nb0.99Al0.01O4−δ and La0.99X0.01Nb0.99Ti0.01O4−δ (X = Mg, Ca, Sr or Ba) were synthesized via the conventional solid state reaction. Specimens with relative density above 96% were produced after sintering. Structural and phase composition studies revealed predominant monoclinic Fergusonite structure for the majority of samples. SEM and TEM studies elucidated the effect of the used dopant combinations on grain growth, micro-crack formation and secondary phase formation. Results from microstructural study were correlated to the grain interior and grain boundary conductivities for selected samples (La0.99Sr0.01Nb0.99Al0.01O4−δ and La0.99Sr0.01Nb0.99Ti0.01O4−δ). The majority of co-doped niobates exhibited appreciable protonic conductivity under humid atmospheres at intermediate temperatures. Sr- or Ca-doped compounds displayed the highest total conductivities with values for LSNA equal to 6 × 10−4 S/cm and 3 × 10−4 S/cm in wet air and in wet 4% H2–Ar (900 °C), respectively. Additionally, thermal expansion was studied to complete functional characterization of co-doped LaNbO4.
Keywords	Proton-conducting ceramic materials, Hydrogen transport ceramic membranes, Rare earth ortho-niobates, Acceptor-doped lanthanum niobates, ProGasMix
Remark	Link

ID=285

Versatile apparatus for thermoelectric characterization of oxides at high temperatures

Authors	Matthias Schrade, Harald Fjeld, Truls Norby and Terje G. Finstad
Source	Review of Scientific Instruments Volume: 85, Pages: 103906 Time of Publication: 2014
Abstract	An apparatus for measuring the Seebeck coefficient and electrical conductivity is presented and characterized. The device can be used in a wide temperature range from room temperature to 1050 °C and in all common atmospheres, including oxidizing, reducing, humid, and inert. The apparatus is suitable for samples with different geometries (disk-, bar-shaped), allowing a complete thermoelectric characterization (including thermal conductivity) on a single sample. The Seebeck coefficient α can be measured in both sample directions (in-plane and cross-plane) simultaneously. Electrical conductivity is measured via the van der Pauw method. Perovskite-type CaMnO3 and the misfit cobalt oxide (Ca2CoO3) q (CoO2) are studied to demonstrate the temperature range and to investigate the variation of the electrical properties as a function of the measurement atmosphere.
Remark	http://dx.doi.org/10.1063/1.4897489 Link

ID=284

Electrochemical behavior of the pyrochlore- and fluorite-like solid solutions in the Pr2O3–ZrO2 system. Part I

Authors	D.A. Belov, A.V. Shlyakhtina, J.C.C. Abrantes, S.A. Chernyak, G.A. Gasymova, O.K. Karyagina, L.G. Shcherbakova
Source	Solid State Ionics Time of Publication: 2014
Abstract	We have studied the structure, microstructure, and electrochemical properties in air of (Pr2 − xZrx)Zr2O7 + x/2 (x = 0.15, 0.32, 0.78), Pr2Zr2O7, and Pr2(Zr2 − xPrx)O7 − x/2 (x = 0.1, 0.4, 1) materials. The solid solutions were prepared through coprecipitation followed by heat treatment of the precursors at 1550 °C for 4 h. According to XRD data, the extent of the pyrochlore-like Pr2 ± xZr2 ± xO7 ± x/2 solid solutions at 1550 °C is ~ 6 mol.%, which is considerably smaller than that in the NdZrO and SmZrO systems at this temperature. Among the pyrochlores, the highest bulk conductivity was offered by the (Pr2 − xZrx)Zr2O7 + x/2 (x = 0.15): 7.15 × 10− 3 S/cm at 800 °C (Ea = 0.66 eV). The pyrochlore-like Pr2(Zr2 − xPrx)O7 − x/2 (x = 0.1) had lower conductivity (3.97 × 10− 3 S/cm at 800 °C). The highest bulk conductivity among the materials studied was found in the Pr2O3-rich fluorite-like Pr2(Zr2 − xPrx)O7 − x/2 with x = 1: ~ 0.217 S/cm at 800 °C (Ea = 0.0.31 eV). The temperature-dependent conductivity of the Pr2O3-rich fluorite-like solid solutions Pr2(Zr2 − xPrx)O7 − x/2 with x = 0.4 and 1 had a break at 560 °C, suggesting a change in the mechanism of ion transport at this temperature.
Remark	DOI: 10.1016/j.ssi.2014.09.035 Link

ID=282

Characterization and Modeling of La 1 − x Sr x CoO 3 − δ Solid Oxide Fuel Cell Cathodes Using Nonlinear Electrochemical Impedance Techniques

Author	Timothy James McDonald
Source	Time of Publication: 2014
Remark	Dissertation Link

ID=281

Structural and electrical study of samarium doped cerium oxide thin films prepared by e-beam evaporation

Authors	Darius Virbukas, Mantas Sriubas, Giedrius Laukaitis
Source	Solid State Ionics Time of Publication: 2014
Abstract	Samarium doped cerium oxide (Sm0.15Ce0.85O1.925, SDC) thin films were grown on the Alloy 600 (Fe–Ni–Cr) and optical quartz (SiO2) substrates using e-beam deposition technique. Formed SDC thin films were characterized using different X-ray diffraction (XRD) techniques, scanning electron microscope (SEM), energy-dispersive spectrometry (EDS) and impedance spectroscopy. The deposition rate of formed SDC thin films was changed from 2 Å/s to 16 Å/s. XRD analysis shows that all thin films have a cubic (FCC) structure and repeat the crystallographic orientation of the initial powders evaporated with different deposition rate and on different substrates. The crystallite size increases from 7.7 nm to 10.3 nm and from 7.2 nm to 9.2 nm on Alloy 600 substrate and optical quartz (SiO2) substrate respectively as the thin film deposition rate increases. SEM images indicate a dense and homogeneous structure of all formed SDC thin films. The ionic conductivity depends on thin films density and blocking factor. The best ionic conductivity (σg = 1.34 Sm− 1 and σgb = 2.29 Sm −1 at 873 K temperature, activation energy ΔEg = 0.91 eV and ΔEgb = 0.99 eV) was achieved for SDC thin films formed at 4 Å/s deposition rate. It was found that the highest density (5.25 g/cm3) and the lowest relaxation time in grain (τg = 9.83 × 10− 7 s), and the lowest blocking factor (0.39) is in SDC thin films formed at 4 Å/s deposition rate. The deposition rate influences the stoichiometry of the formed SDC thin ceramic films.
Keywords	Electron beam deposition; Samarium doped ceria oxide (SDC); Solid oxide fuel cells (SOFC); Ionic conductivity
Remark	DOI: 10.1016/j.ssi.2014.09.036 Link

ID=280

Electrical conductivity and TG-DSC study of hydration of Sc-doped CaSnO3 and CaZrO3

Authors
Source	Solid State Ionics Volume: 267, Pages: 61–67 Time of Publication: 2014
Abstract	Correlations linking hydration thermodynamics to materials parameters can be of vital importance for further development of proton conducting oxides. However, the currently proposed correlations are troubled by scattering limiting their predictive power. As such, the present contribution has investigated Sc-doped CaSnO3 and CaZrO3 in an attempt to further elucidate the trends in the thermodynamics of hydration for perovskites. Conductivity and impedance spectroscopy on 5 and 10% Sc-doped CaSnO3 demonstrated that it is primarily an oxygen ion conductor with a small protonic contribution at lower temperatures (below 500 °C) under wet conditions. Simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC), TG-DSC, was applied to measure the standard molar hydration enthalpy of CaSn1−xScxO3−δ and CaZr1−xScxO3−δ (x = 0.05, 0.10, 0.15 and 0.20) as a function of the Sc concentration. The hydration enthalpy becomes increasingly negative with increasing Sc substitution, which is discussed on the basis of changes in electronegativity, basicity and tolerance factor.
Keywords	Defects; Protons; Hydration; Thermodynamics; Perovskites
Remark	DOI: 10.1016/j.ssi.2014.09.006 Link

ID=279

Synthesis, crystal structure and properties of alluaudite-like triple molybdate Na25Cs8Fe5(MoO4)24

Authors	Aleksandra A. Savina, Sergey F. Solodovnikov, Dmitry A. Belov, Olga M. Basovich, Zoya A. Solodovnikova, Konstantin V. Pokholok, Sergey Yu. Stefanovich, Bogdan I. Lazoryak, Elena G. Khaikina
Source	Journal of Solid State Chemistry Volume: 220, Pages: 217–220 Time of Publication: 2014
Abstract	A new triple molybdate Na25Cs8Fe5(MoO4)24 was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na25Cs8Fe5(MoO4)24 were obtained and its structure was solved (the space group P View the MathML source1¯, a=12.5814(5), b=13.8989(5), c=28.4386(9) Å, α=90.108(2), β=90.064(2), γ=90.020(2)°, V=4973.0(3) Å3, Z=2, R=0.0440). Characteristic features of the structure are polyhedral layers composed of pairs of edge-shared FeO6 and (Fe, Na)O6 octahedra, which are connected by bridging МоО4 tetrahedra. The layers share common vertices with bridging МоО4 tetrahedra to form an open 3D framework with the cavities occupied by the Cs+ and Na+ cations. The compound undergoes first-order phase transformation at 642 K and above this phase transition, electrical conductivity reaches 10−3–10−2 S cm−1. Thus, Na25Cs8Fe5(MoO4)24 may be considered as a promising compound for developing new materials with high ionic conductivity.
Keywords	Triple molybdate; Sodium; Synthesis; Crystal structure; Phase transition; Ionic conductivity
Remark	DOI: 10.1016/j.jssc.2014.09.004 Link

ID=277

Superior electrochemical performance and oxygen reduction kinetics of layered perovskite PrBaxCo2O5+δ (x = 0.90–1.0) oxides as cathode materials for intermediate-temperature solid oxide fuel cells

Authors	Jingping Wang, Fuchang Meng, Tian Xia, Zhan Shi, Jie Lian, Chunbo Xu, Hui Zhao, Jean-Marc Bassat, Jean-Claude Grenier
Source	International Journal of Hydrogen Energy Time of Publication: 2014
Abstract	The layered perovskite PrBaxCo2O5+δ (PBxCO, x = 0.90–1.0) oxides have been synthesized by a solid-state reaction technique, and evaluated as the potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Room temperature X-ray diffraction patterns show the orthorhombic structures which double the lattice parameters from the perovskite cell parameter as a ≈ ap, b ≈ ap and c ≈ 2ap (ap is the cell parameter of the primitive perovskite) in the Pmmm space group. There is a good chemical compatibility between the PBxCO cathode and the Ce0.9Gd0.1O1.95 (CGO) electrolyte at 1000 °C. The electrical conductivity and thermal expansion coefficient of PBxCO are improved due to the increased amount of electronic holes originated from the Ba-deficiency. The results demonstrate the high electrochemical performance of PBxCO cathodes, as evidenced by the super low polarization resistances (Rp) over the intermediate temperature range. The lowest Rp value, 0.042 Ω cm2, and the cathodic overpotential, −15 mV at a current density of −25 mA cm−2, are obtained in the PrBa0.94Co2O5+δ cathode at 600 °C in air, which thus allow to be used as a highly promising cathode for IT-SOFCs. A CGO electrolyte fuel cell with the PrBa0.94Co2O5+δ cathode presents the attractive peak power density of ∼1.0 W cm−2 at 700 °C. Furthermore, the oxygen reduction kinetics of the PrBa0.94Co2O5+δ cathode is also studied, and the rate-limiting steps for oxygen reduction reaction are determined at different temperatures.
Remark	DOI: 10.1016/j.ijhydene.2014.09.041 Link

ID=276

Organic–Inorganic Hybrid Membranes Based on Sulfonated Poly(ether ether ketone) and Tetrabutylphosphonium Bromide Ionic Liquid for PEM Fuel Cell Applications

Authors	Vijay Shankar Rangasamy, Savitha Thayumanasundaram, Niels de Greef, Jin Won Seo and Jean-Pierre Locquet
Source	European Journal of Inorganic Chemistry Time of Publication: 2014
Abstract	Ionic liquids (ILs), with their inherent ionic conductivity and negligible vapor pressure, can be exploited in proton exchange membrane (PEM) fuel cells for which thermal management is a major problem and the cell operation temperature is limited by the boiling point of water. In this work, sulfonated poly(ether ether ketone) (SPEEK) membranes were modified by the incorporation of tetrabutylphosphonium bromide ([P4 4 4 4]Br) by solvent-casting. Electrochemical impedance spectroscopy (EIS) was used to study the electrical properties of the modified membranes. Simultaneous TGA and FTIR studies were used to evaluate the thermal stability and chemical structure of the modified membranes, respectively. 1H NMR spectroscopy was applied to probe the changes in the chemical environment due to the interaction between the ionic liquid and the polymer. Mechanical properties were studied by dynamic mechanical analysis. The temperature-dependent behavior of the viscosity of the [P4 4 4 4]Br ionic liquid was observed to obey the Vogel–Fulcher–Tammann (VFT) equation, and was correlated to the ion-conducting properties of the IL-doped SPEEK membranes.
Remark	DOI: 10.1002/ejic.201402558 Link

ID=275

Crystal Structure and electrical properties of complex perovskite solid solutions based on (1-x) NaNbO3-xBi (Zn0.5Ti0.5) O3

Authors	Sasiporn Prasertpalichat, David P. Cann
Source	Journal of Electroceramics Time of Publication: 2014
Abstract	Ceramics based on the perovskite solid solution (1-x) NaNbO3-xBi (Zn0.5Ti0.5) O3 were prepared using conventional solid state synthesis. The crystal structure, electrical, and optical properties were examined. According to diffraction data, a single perovskite phase could be identified up to the composition x = 0.09. As the Bi (Zn0.5Ti0.5) O3 content increased the crystal structure transitioned from orthorhombic to pseudocubic symmetry. Furthermore, dielectric data showed that the dielectric maximum shifted to lower temperatures with the addition of Bi (Zn0.5Ti0.5) O3. Polarization hysteresis data revealed a slim linear loop across the whole range of solid solutions. Optical data also showed a decrease in the optical band gap from 3.4 eV for pure NaNbO3 to 2.9 eV for the x = 0.09 composition. Using impedance spectroscopy, an electrically inhomogeneous microstructure was observed for compositions with increased Bi (Zn0.5Ti0.5) O3 content. Finally, the substitution of Ta on the B-site was shown to shift the dielectric maximum to temperatures as low as 100 K.
Remark	DOI 10.1007/s10832-014-9953-x Link

ID=274

A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3

Authors	Ming Li, Martha J. Pietrowski, Roger A. De Souza, Huairuo Zhang, Ian M. Reaney, Stuart N. Cook, John A. Kilner & Derek C. Sinclair
Source	Nature Materials Volume: 13, Pages: 31-35 Time of Publication: 2014
Abstract	Oxide ion conductors find important technical applications in electrochemical devices such as solid-oxide fuel cells (SOFCs), oxygen separation membranes and sensors1, 2, 3, 4, 5, 6, 7, 8, 9. Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material; however, it is often reported to possess high leakage conductivity that is problematic for its piezo- and ferroelectric applications10, 11, 12, 13, 14, 15. Here we report this high leakage to be oxide ion conduction due to Bi-deficiency and oxygen vacancies induced during materials processing. Mg-doping on the Ti-site increases the ionic conductivity to ~0.01 S cm−1 at 600 °C, improves the electrolyte stability in reducing atmospheres and lowers the sintering temperature. This study not only demonstrates how to adjust the nominal NBT composition for dielectric-based applications, but also, more importantly, gives NBT-based materials an unexpected role as a completely new family of oxide ion conductors with potential applications in intermediate-temperature SOFCs and opens up a new direction to design oxide ion conductors in perovskite oxides.
Remark	doi:10.1038/nmat3782 Link

ID=272

Grain Size Dependent Comparison of ZnO and ZnGa2O4 Semiconductors by Impedance Spectrometry

Authors
Source	Electrochimica Acta Time of Publication: 2014
Abstract	We investigated the electrical properties of ZnGa2O4 via AC (alternating current) Impedance Spectroscopy method comparing with ZnO reference material. Experimentally, AC electrical conductivity of ZnO and ZnGa2O4 were found to be a function of temperature and grain size; i.e., the increase in grain size of the ZnO led a decrease in room temperature conductivity from 1.35 × 10−7 S cm−1 to 9.9 × 10−8 S cm−1. The temperature dependent resistivity variation of ZnGa2O4 and ZnO were similar to each other with varied responding temperature. Likewise, the conductivity for ZnGa2O4 decrease from 2.2 × 10−8 S cm−1 to 3.8 × 10−9 S cm−1 upon an increase in grain size from ∼0.5 μm to 100 μm, accordingly. In addition, a rise in temperature caused an increase in conductivity and led to a corresponding shift in the relaxation time towards the lower values. The semicircles in Nyquist plots disappeared at temperature above 250 °C and 700 °C for ZnO and ZnGa2O4, respectively. The AC measurements were also correlated with the size dependent activation energies (171 meV for 0.5 μm ZnO and 1200 meV for 0.5 μm ZnGa2O4).
Keywords	Activation energy; Nyquist plots; AC Impedance spectrometry; Oxide semiconductors
Remark	DOI: 10.1016/j.electacta.2014.08.084 Link

ID=270

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Authors	George Tsekouras, Artur Braun
Source	Solid State Ionics Volume: 266, Pages: 19-24 Time of Publication: 2014
Abstract	On the timescale of solid oxide fuel cell (SOFC) system lifetime requirements, the thermodynamically predicted low-level substitution of chromium on the B-site of (La,Sr)MnO3 could be a source of cathode degradation underlying more overt and well-known chromium poisoning mechanisms. To study this phenomenon in isolation, electronic conductivity (σ) and electrochemical oxygen reduction activity of the (La0.8Sr0.2)0.98CrxMn1−xO3 model series (x = 0, 0.02, 0.05 or 0.1) were measured in air between 850 and 650 °C. Depending on the extent of chromium substitution and the measurement temperature, electrochemical impedance spectroscopy (EIS) results could be deconvoluted into a maximum of three contributions reflecting possible limiting processes such as oxide ion transport and dissociative adsorption. Chromium substitution resulted in lowered σ (from 174 S cm− 1 (x = 0) to 89 S cm− 1 (x = 0.1) at 850 °C) and a steady rise in associated activation energy (Ea) (from 0.105 ± 0.001 eV (x = 0) to 0.139 ± 0.001 eV (x = 0.1)). From EIS analyses, ohmic and polarisation resistances increased, whilst Ea for the overall oxygen reduction reaction also increased from 1.39 ± 0.04 eV (x = 0) to 1.48–1.54 ± 0.04 eV upon chromium substitution.
Keywords	Solid oxide fuel cell; Lanthanum strontium manganite; Chromium poisoning; Electronic conductivity; Electrochemical impedance spectroscopy
Remark	Link

ID=269

The effect of calcination temperature on the electrochemical properties of La0.3Sr0.7Fe0.7Cr0.3O3−x (LSFC) perovskite oxide anode of solid oxide fuel cells (SOFCs)

Authors	Yifei Sun, Ning Yan, Jianhui Li, Huayi Wu, Jing-Li Luo, Karl T. Chuang
Source	Sustainable Energy Technologies and Assessments Volume: 8, Pages: 92-98 Time of Publication: 2014
Abstract	A series of perovskite structure anode materials, LSFC, was successfully prepared by a glycine combustion process and further calcined at different temperatures. The electrochemical properties of anodes prepared at various calcination temperatures (1100 °C, 1200 °C and 1300 °C) were investigated. The calcination temperature had no significant influence on the morphology of the material but showed obvious influences on the particle sizes and electrochemical properties of the materials. Higher calcination temperature results in sharper X-ray diffractometer (XRD) diffraction peaks of the materials with larger particle sizes and higher electrical conductivity. However materials calcined at higher temperature had much smaller BET surface area resulting in lower triple phase boundary (TPB). The electrochemical performance test exhibited that LSFC anode material sintered at 1100 °C exhibited the smallest area specific resistance (ASR) value in H2 at operating temperatures from 700 to 900 °C. For proton conducting SOFCs (PC-SOFCs) fed by syngas, the cell with anode calcined at 1100 °C also showed highest power density output of 120 mW/cm2 at 750 °C, which was almost three times higher than that of the cell with anode calcined at 1300 °C.
Keywords	Solid oxide fuel cell; Calcination temperature; Electrochemical properties; Perovskite
Remark	Link

ID=268

Oxygen interstitial and vacancy conduction in symmetric Ln2 ± x Zr2 ± x O7 ± x/2 (Ln = Nd, Sm) solid solutions

Authors	A. V. Shlyakhtina, D. A. Belov, A. V. Knotko, I. V. Kolbanev, A. N. Streletskii, O. K. Karyagina, L. G. Shcherbakova
Source	Inorganic Materials Volume: 50, Issue: 10, Pages: 1035-1049 Time of Publication: 2014
Abstract	We have compared (Ln2 − x Zr x )Zr2O7 + x/2 (Ln = Nd, Sm) pyrochlore-like solid solutions with interstitial oxide ion conduction and Ln2(Zr2 − x Ln x )O7 − δ (Ln = Nd, Sm) pyrochlore-like solid solutions with vacancy-mediated oxide ion conduction in the symmetric systems Nd2O3-ZrO2 (NdZrO) and Sm2O3-ZrO2 (SmZrO). We have studied their structure, microstructure, and transport properties and determined the excess oxygen content of the (Sm2 − x Zr x )Zr2O7 + x/2 (x = 0.2) material using thermal analysis and mass spectrometry in a reducing atmosphere (H2/Ar-He). The Ln2 ± x Zr2 ± x O7 ± x/2 (Ln = Nd, Sm) solid solutions have almost identical maximum oxygen vacancy and interstitial conductivities: (3–4) × 10−3 S/cm at 750°C. The lower oxygen vacancy conductivity of the Ln2(Zr2 − x Ln x )O7 − δ (Ln = Nd, Sm; 0 < x ≤ 0.3) solid solutions is due to the sharp decrease in it as a result of defect association processes, whereas the interstitial oxide ion conductivity of the (Ln2 − x Zr x )Zr2O7 + x/2 (Ln = Nd, Sm; 0.2 ≤ x < 0.48) pyrochlore-like solid solutions is essentially constant in a broad range of Ln2O3 concentrations.
Remark	Link

ID=267

MICROWAVE SINTERING OF Sr AND Mg-DOPED LANTHANUM GALLATE (LSGM) SOLID ELECTROLYTES

Authors	Cristian Andronescu, Victor Fruth, Enikoe Volceanov, Rares Scurtu, Cornel Munteanu, Maria Zaharescu
Source	Romanian journal of materials Time of Publication: 2014-01
Abstract	Sr2+ and Mg2+ simultaneously doped lanthanum gallate (LSGM) powders, prepared by a modified Pechini route using polyvinyl alcohol (PVA) as polymeric alcohol, were densified using an activated microwave technique at 2.45 GHz, to develop a dense stable electrolyte for application in intermediate temperatures solid oxide fuel cells (IT-SOFC). Thermal behaviour of precursors was investigated by means of differential thermal analysis combined with thermogravimetric analysis (DTA/TGA). The powders and sintered samples were characterized using scanning electron microscopy and energy dispersive analysis (SEM-EDAX), X-ray diffraction (XRD) and infrared spectroscopy (FT-IR). The thermal expansion coefficient (TEC) and ionic conductivity of the sintered samples were also evaluated. Fine, homogeneous and high density pellets of almost pure LSGM phase were obtained after sintering at 14000C for a short period time in an activated microwave field. Using activated microwave field, due to the volumetric in situ heating, the sintering process is highly specific and instantaneous, leading to a faster kinetics compared to the conventional process (electric oven). With an optimized sintering schedule, a fine grained and dense microstructure of the samples were obtained.
Remark	Link

ID=265

Full ceramic micro solid oxide fuel cells: towards more reliable MEMS power generators operating at high temperatures

Authors
Source	Energy Environ. Sci. Time of Publication: 2014
Abstract	Batteries, with a limited capacity, have dominated the power supply of portable devices for decades. Recently, the emergence of new types of highly efficient miniaturized power generators like micro fuel cells has opened up alternatives for continuous operation on the basis of unlimited fuel feeding. This work addresses for the first time the development of a full ceramic micro solid oxide fuel cell fabricated in silicon technology. This full-ceramic device represents a new generation of miniaturized power generators able to operate at high temperatures, and therefore able to work with a hydrocarbon fuel supply. Dense yttria-stabilized zirconia free-standing large-area membranes on micromachined silicon were used as the electrolyte. Thin-film porous electrodes of La0.6Sr0.4CoO3−δ and gadolinia-doped ceria were employed as cathode and anode materials, respectively. The electrochemical performance of all the components was evaluated by partial characterization using symmetrical cells, yielding excellent performance for the electrolyte (area specific resistance of 0.15 Ω cm2 at temperatures as low as 450 °C) and the electrodes (area specific resistance of the cathode and anode below 0.3 Ω cm2 at 700 °C). A micro solid oxide fuel cell with an active area of 2 mm2 and less than 1 micrometer in thickness was characterized under fuel cell conditions, using hydrogen as a fuel and air as an oxidant. A maximum power density of 100 mW cm−2 and 2 mW per single membrane was generated at 750 °C, having an open circuit voltage of 1.05 V. Impedance spectroscopy of the all-ceramic membrane showed a total area-specific resistance of [similar]3.5 Ω cm2.
Remark	DOI: 10.1039/C4EE00748D Link

ID=264

Proton conductivity of hexagonal and cubic BaTi1−xScxO3−δ (0.1 ≤ x ≤ 0.8)

Authors	Seikh M. H. Rahman, Stefan T. Norberg, Christopher S. Knee, Jordi J. Biendicho, Stephen Hull and Sten G. Eriksson
Source	Dalton Transactions Time of Publication: 2014
Abstract	BaTi1−xScxO3−δ (x = 0.1–0.8) was prepared via solid state reaction. High resolution X-ray powder diffraction was used to characterise the synthesised materials. It was found that low substitution (x = 0.1 and 0.2) of Ti4+ for Sc3+ gives a hexagonal perovskite structure, whereas high substitution (x = 0.5–0.7) results in a cubic perovskite structure. Thermogravimetric analysis revealed significant levels of protons in both as-prepared and hydrated samples. Electrical conductivity was measured by AC impedance methods under oxygen, argon and under dry and humid, both H2O and D2O, conditions for BaTi1−xScxO3−δ (x = 0.2, 0.6 and 0.7). In the temperature range of 150–600 °C, under humid conditions, the conductivity is significantly higher than that under the dry conditions. The increase in conductivity is especially prominent for the cubic phases, indicating that protons are the dominant charge carriers. The proton conductivity of hexagonal BaTi0.8Sc0.2O3−δ is approx. two orders of magnitude lower than that of the more heavily substituted cubic phases. Conductivity is also found to be higher in dry O2 than in Ar in the whole temperature range of 150–1000 °C, characteristic of a significant contribution from p-type charge carriers under oxidising atmospheres. Greater Sc3+ substitution leads to a higher proton concentration and the highest proton conductivity (σ [similar] 2 × 10−3 S cm−1 at 600 °C) is found for the BaTi0.3Sc0.7O3−δ composition.
Remark	DOI: 10.1039/C4DT01280A Link

ID=263

Protons in acceptor doped langasite, La3Ga5SiO14

Authors
Source	Solid State Ionics Volume: 264, Pages: 76–84 Time of Publication: 2014
Abstract	The electrical and defect chemical properties of acceptor doped langasite have been investigated over wide ranges of pH2O, pO2 and temperature. All compositions are pure proton conductors up to 800 °C in wet atmospheres and mixed oxide ion-p-type conductors at higher temperatures. The enthalpy of mobility of protons is 75 ± 3 kJ/mol, while that of oxygen vacancies is 125 ± 7 kJ/mol. The standard enthalpy and entropy of hydration are -100 ± 3 kJ/mol and -157 ± 5 J/mol K, respectively. Langasite based sensors may therefore be affected by dissolution of protons from H2O in the bulk crystal lattice up to temperatures as high as 1000 °C.
Keywords	Langasite; Piezoelectric; DFT; Defects; Hydrogen; Conductivity

ID=259

Hydrogen flux in La0.87Sr0.13CrO3–δ

Authors	Camilla K. Vigen, Reidar Haugsrud
Source	Journal of Membrane Science Volume: 468, Pages: 317–323 Time of Publication: 2014
Abstract	Acceptor doped LaCrO3 is a promising material for dense, ceramic hydrogen permeable membranes, displaying hydrogen flux in the order of 10−4 ml min−1 cm−1 in a 10% H2+2.5% H2O/dry Ar gradient at 1000 °C. In this work we have characterized the ambipolar proton electron hole conductivity in La0.87Sr0.13CrO3–δ by means of hydrogen flux measurements. Proton transport parameters were extracted, yielding a pre-exponential factor of 3 cm2 K V−1 s−1 and an enthalpy of mobility of 65 kJ mol−1. Hydrogen flux measurements showed that applying a layer of Pt on both feed and sweep side surfaces significantly altered the temperature dependency and increased the hydrogen flux in a 550 μm thick membrane. This indicates that surface kinetics will limit the hydrogen flux in uncoated membranes. From hydrogen surface exchange measurements, a surface exchange coefficient ranging from 10−10 to 10−8 mol cm−2 s−1 at 325–600 °C was obtained.
Keywords	Hydrogen permeation; LaCrO3; Proton conductivity; Surface kinetics
Remark	Link

ID=257

Hydrogen permeation characteristics of La27Mo1.5W3.5O55.5

Authors
Source	Journal of Membrane Science Volume: 461, Pages: 81–88 Time of Publication: 2014
Abstract	Hydrogen permeation in 30% Mo-substituted lanthanum tungsten oxide membranes, La27Mo1.5W3.5O55.5 (LWMo), has been measured as a function of temperature, hydrogen partial pressure gradient, and water vapor pressure in the sweep gas. Transport of hydrogen by means of ambipolar proton–electron conductivity and – with wet sweep gas – water splitting contributes to the measured hydrogen content in the permeate. At 700 °C under dry sweep conditions, the H2 permeability in LWMo was 6×10−46×10−4 mL min−1 cm-1, which is significantly higher than that for state-of-the-art SrCeO3-based membranes. Proton conductivity was identified as rate limiting for ambipolar bulk transport across the membrane. On these bases it is evident that Mo-substitution is a successful doping strategy to increase the n-type conductivity and H2 permeability compared to nominally unsubstituted lanthanum tungsten oxide. A steady-state model based on the Wagner transport theory with partial conductivities as input parameters predicted H2 permeabilities in good agreement with the measured data. LWMo is a highly competitive mixed proton–electron conducting oxide for hydrogen transport membrane applications provided that long term stability can be ensured.
Remark	http://dx.doi.org/10.1016/j.memsci.2014.03.011 Link

ID=255

Oxide ion transport in (Nd2−xZrx)Zr2O7+δ electrolytes by an interstitial mechanism

Authors	A.V. Shlyakhtina, D.A. Belov, A.V. Knotko, M. Avdeev, I.V. Kolbanev, G.A. Vorobieva, O.K. Karyagina, L.G. Shcherbakova
Source	Journal of Alloys and Compounds Volume: 603, Issue: 5, Pages: 274–281 Time of Publication: 2014
Abstract	We have studied the structure and transport properties of ten (Nd2−xZrx)Zr2O7+x/2 (x = 0–1.27) solid solutions, which lie in the ZrO2–Nd2Zr2O7 isomorphous miscibility range. Major attention has been focused on the pyrochlore-like (Nd2−xZrx)Zr2O7+x/2 solid solutions with x = 0–0.78, which are thought to be potential interstitial oxide ion conductors. The X-ray and neutron diffraction results demonstrate that the (Nd2−xZrx)Zr2O7+x/2 (x = 0–1.27) solid solutions undergo an order–disorder (pyrochlore–defect fluorite) structural phase transition. The (Nd2−xZrx)Zr2O7+x/2 (x = 0.2–0.78) have the bulk conductivity, ∼(1.2–4) × 10–3 S/cm at 750 °C, which is two orders of magnitude higher than that of the ordered pyrochlore Nd2Zr2O7. An attempt has been made to determine the interstitial oxygen content of (Nd2−xZrx)Zr2O7+x/2 (x = 0.2; 0.67) in a reducing atmosphere using thermogravimetry and mass spectrometry. It has been shown that no reduction occurs in the NdZrO system, where neodymium has only one oxidation state, 3+.
Keywords	Fuel cells; Ionic conduction; Electrochemical impedance spectroscopy; Neutron diffraction; X-ray diffraction; SEM
Remark	http://dx.doi.org/10.1016/j.jallcom.2014.03.068 Link

ID=253

Proton conduction in oxygen deficient Ba3In1.4Y0.3M0.3ZrO8 (M = Ga3+ or Gd3+) perovskites

Authors	Francis G. Kinyanjui, Stefan T. Norberg, Christopher S. Knee, Sten-G. Eriksson
Source	Journal of Alloys and Compounds Volume: 605, Pages: 56-62 Time of Publication: 2014
Abstract	B -site disordered, oxygen deficient Ba3In1.4Y0.3M 0.3ZrO8 (M = Gd3+ or Ga3+) perovskites of space group View the MathML sourcePm3‾m, were prepared by a solid-state reactive sintering method. Thermogravimetric analysis of the as-prepared samples revealed 79.3% and 55.5% protonation of the available oxygen vacancies by OH groups in the Gd3+ and Ga3+ containing samples, respectively. Conductivity was found to be in the range of 0.3–1.1 × 10−3 S cm−1 (M = Gd3+) and 1.1–4.6 × 10−4 S cm−1 (M = Ga3+) for the temperature interval 300–600 °C in wet Argon. Ba3In1.4Y0.3Ga0.3ZrO8 shows an approximate one order of magnitude increase in conductivity at T > 600 °C under dry oxygen indicating a significant p-type contribution whereas Ba3In1.4Y0.3Gd0.3ZrO8 reveals a smaller enhancement. Ba3In1.4Y0.3Ga0.3ZrO8 displays considerable mixed proton–electronic conduction in the interval 400–800 °C under wet oxidising conditions suggesting possibility of Ga-containing compositions as a cathode materials in a proton conducting fuel cell.
Keywords	Proton conducting electrolyte; Oxygen deficient perovskite; Mixed conductor; Cathode material; Impedance spectroscopy

ID=252

Role of point defects in bipolar fatigue behavior of Bi(Mg1/2Ti1/2)O3 modified (Bi1/2K1/2)TiO3-(Bi1/2Na1/2)TiO3 relaxor ceramics

Authors	Nitish Kumar, Troy Y. Ansell and David P. Cann
Source	J. Applied Physics Volume: 115, Pages: 154104 Time of Publication: 2014
Abstract	Lead-free Bi(Mg1/2Ti1/2)O3-(Bi1/2K1/2)TiO3-(Bi1/2 Na 1/2)TiO3 (BMT-BKT-BNT) ceramics have been shown to exhibit large electromechanical strains under high electric fields along with negligible fatigue under strong electric fields. To investigate the role of point defects on the fatigue characteristics, the composition 5BMT-40BKT-55BNT was doped to incorporate acceptor and donor defects on the A and B sites by adjusting the Bi/Na and Ti/Mg stoichiometries. All samples had pseudo-cubic symmetries based on x-ray diffraction, typical of relaxors. Dielectric measurements showed that the high and low temperature phase transitions were largely unaffected by doping. Acceptor doping resulted in the observation of a typical ferroelectric-like polarization with a remnant polarization and strain hysteresis loops with significant negative strain. Donor-doped compositions exhibited characteristics that were indicative of an ergodic relaxor phase. Fatigue measurements were carried out on all of the compositions. While the A-site acceptor-doped composition showed a small degradation in maximum strain after 106 cycles, the other compositions were essentially fatigue free. Impedance measurements were used to identify the important conduction mechanisms in these compositions. As expected, the presence of defects did not strongly influence the fatigue behavior in donor-doped compositions owing to the nature of their reversible field-induced phase transformation. Even for the acceptor-doped compositions, which had stable domains in the absence of an electric field at room temperature, there was negligible degradation in the maximum strain due to fatigue. This suggests that either the defects introduced through stoichiometric variations do not play a prominent role in fatigue in these systems or it is compensated by factors like decrease in coercive field, an increase in ergodicity, symmetry change, or other factors.
Remark	http://dx.doi.org/10.1063/1.487167 Link

ID=251

Structure and transport properties in un-doped and acceptor-doped gadolinium tungstates

Authors	Wen Xing, Protima Rauwel, Charles H. Hervoches, Zuoan Li, Reidar Haugsrud
Source	Solid State Ionics Volume: 261, Pages: 87-94 Time of Publication: 2014
Abstract	Nominal Gd6WO12, Gd5.94Ca0.06WO12 − δ, Gd5.7Ca0.3WO12 − δ and Gd5.7WO12 − δ were synthesized by solid state reaction and wet chemistry methods. The structure and morphology of the materials were analyzed by XRD, SEM and TEM and the electrical conductivity was measured as a function of temperature in reducing and oxidizing atmospheres under wet and dry conditions. The total conductivity is essentially independent of composition above 700 °C. Below 700 °C, the conductivity of Ca-doped samples is higher than that of Gd6WO12 and Gd5.7WO12 − δ and increases with increasing doping concentration. The conductivity below 700 °C is also higher under wet compared to dry conditions and, moreover, the H–D isotope effect on the conductivity is significant. Based on this, and on conductivity characterization as a function of pO2pO2 and pH2OpH2O, it was concluded that the materials are mixed ionic and electronic conductors where electrons and holes dominate at high temperatures and intermediate temperatures under sufficiently reducing and oxidizing conditions, respectively. Protons are the predominating ionic charge carriers below approximately 700 °C. The hydrogen flux through Gd5.7Ca0.3WO12 − δ was measured as a function of temperature under wet and dry sweep gas conditions, as well as with varying pH2pH2 on the feed side, confirming the picture outlined by the conductivity measurements. A defect chemical model has been derived to which the conductivity data were fitted yielding thermodynamic and transport parameters describing the functional characteristics of the materials.
Keywords	Proton; Structure; Gd6WO12; Ambipolar conductivity; Hydrogen flux
Remark	Link

ID=250

Solid Oxide-Molten Carbonate Nano-composite Fuel Cells: Particle Size Effect

Authors	Shalima Shawuti, Mehmet A. Gulgun
Source	Journal of Power Sources Time of Publication: 2014
Abstract	Varying the amount of specific interface area in the CeO2-Na2CO3 nano-composite fuel cell electrolyte helped reveal the role of interfaces in ionic conductivity. We mixed ceria particles with micrometer or nanometer size distributions to obtain a specific surface area (SSA) in the composite from 47 m2/g to 203 m2/g. Micro-structural investigations of the nano-composite showed that the Na2CO3 phase serves as the glue in the microstructure, while thermal analysis revealed a glass transition-like behavior at 350 °C. High SSA enhanced the ionic conductivity significantly at temperatures below 400 °C. Moreover, the activation energy for the Arrhenius conductivity (σT) of the composites was lower than that of the Na2CO3 phase. This difference in the activation energies is consistent with the calculated dissociation energy of the carbonate phase. The strong dependence of conductivity on the SSA, along with differences in the activation energies, suggests that the oxide surface acted as a dissociation agent for the carbonate phase. A model for the solid composite electrolyte is proposed: in the nano-composite electrolyte, the oxide surface helps Na2CO3 dissociate, so that the "liberated" ions can move more easily in the interaction region around the oxide particles, thus giving rise to high ionic conductivities.
Keywords	composite electrolyte; ionic conductivity; impedance spectroscopy; SOFC; interphase; activation energy
Remark	in press, http://dx.doi.org/10.1016/j.jpowsour.2014.05.010 Link

ID=249

Hydrogen permeation characteristics of La27Mo1.5W3.5O55.5

Authors
Source	Journal of Membrane Science Time of Publication: 2014
Abstract	Hydrogen permeation in 30 % Mo-substituted lanthanum tungsten oxide membranes, La27Mo1.5W3.5O55.5 (LWMo), has been measured as a function of temperature, hydrogen partial pressure gradient, and water vapour pressure in the sweep gas. Transport of hydrogen by means of ambipolar proton-electron conductivity and – with wet sweep gas – water splitting contribute to the measured hydrogen content in the permeate. At 700 °C under dry sweep conditions, the H2 permeability in LWMo was 6×10−46×10−4 mL min−1 cm-1, which is significantly higher than for state-of-the-art SrCeO3-based membranes. Proton conductivity was identified as rate limiting for ambipolar bulk transport across the membrane. On these bases it is evident that Mo-substitution is a successful doping strategy to increase the n-type conductivity and H2 permeability compared to nominally unsubstituted lanthanum tungsten oxide. A steady-state model based on Wagner transport theory with partial conductivities as input parameters predicted H2 permeabilities in good agreement with the measured data. LWMo is a highly competitive mixed proton-electron conducting oxide for hydrogen transport membrane applications provided that long term stability can be ensured.
Remark	Available online 14 March 2014 Link

ID=248

Performance Variability and Degradation in Porous La1-xSrxCoO3-δ Electrodes

Authors	Yunxiang Lu, Cortney R. Kreller, Stuart B. Adler, James R. Wilson, Scott A. Barnett, Peter W. Voorhees, Hsun-Yi Chen and Katsuyo Thornton
Source	J. of the Electrochemical Society Volume: 161, Issue: 4, Pages: F561-F568 Time of Publication: 2014
Abstract	Porous La1-xSrxCoO3-δ (LSC) electrodes with Sr composition x = 0.2 (LSC-82) and x = 0.4 (LSC-64) were prepared by screenprinting LSC powders onto rare-earth doped ceria electrolytes, followed by sintering at 950 ∼ 1100°C, and characterization using scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface-area analysis, 3-D morphological imaging based on focused ion beam scanning electron microscopy (FIB-SEM), and energy dispersion X-ray spectroscopy (EDX/EDS). The batch-to-batch variability and degradation (over 1000 ∼ 2000 hours) of the electrochemical performance of these cells were studied using electrochemical impedance spectroscopy (EIS) and measurements of nonlinear electrochemical impedance (NLEIS). These measurements reveal a strong correlation between the characteristic frequency (ωc) and characteristic resistance (Rc) of the electrodes, which, when analyzed in light of microstructural data, indicates that performance variability and degradation are caused primarily by variations in the surface rate coefficient k(T) for O2 exchange.
Remark	doi: 10.1149/2.101404jes Link

ID=247

Doped Germanate-Based Apatites as Electrolyte for Use in Solid Oxide Fuel Cells

Authors	S.-F. Wang, Y.-F. Hsu, W.-J. Lin and K. Kobayashi
Source	Fuel Cells Time of Publication: 2014
Abstract	Apatite ceramics, known for their good electrical conductivities, have garnered substantial attention as an alternative electrolyte for solid oxide fuel cells (SOFCs). However, studies focusing on the electrochemical performances of SOFCs with apatities as electrolytes remain rare, partly due to their high sintering temperature. In this study, the effects of Mg2+, Al3+, Ga3+, and Sn4+ dopants on the characteristics of La9.5Ge6O26 ± δ are examined and their potential for use as SOFC electrolytes evaluated. The results indicate that La9.5Ge5.5Al0.5O26 is stabilized into a hexagonal structure, while the La9.5Ge5.5Sn0.5O26.25, La9.5Ge5.5Ga0.5O26, and La9.5Ge5.5Mg0.5O25.75 ceramics reveal triclinic cells accompanied with the second phase La2Sn2O7 or La2GeO5. The study further demonstrates that a high sintering temperature is needed for both the La9.5Ge5.5Mg0.5O25.75 and the La9.5Ge5.5Sn0.5O26.25 ceramics, and the worst electrical conductivity among the examined systems appears in the La9.5Ge5.5Ga0.5O26 ceramic. The La9.5Ge5.5Al0.5O26 ceramic is accordingly selected for cell evaluation due to its ability to reach densification at 1,350 °C, its good electrical conductivity of 0.026 S cm–1 at 800 °C, and its acceptable thermal expansion coefficient of 10.1 × 10–6 K–1. The maximum power densities of the NiO-SDC/La9.5Ge5.5Al0.5O26/LSCF-SDC single cell are found to be respectively 0.22, 0.16, 0.11, and 0.07 W cm–2 at 950, 900, 850, and 800 °C.
Keywords	Apatites; Cell Performance; Electrolyte; Impedance; Solid Oxide Fuel Cell
Remark	Article first published online: 19 FEB 2014 DOI: 10.1002/fuce.201300093 Link

ID=246

Effect of Nb substitution for Ti on the electrical properties of Yb2Ti2O7-based oxygen ion conductors

Authors	L.G. Shcherbakova, J.C.C. Abrantes, D.A. Belov, E.A. Nesterova, O.K. Karyagina, A.V. Shlyakhtina
Source	Solid State Ionics Time of Publication: 2014
Abstract	We have studied the effect of niobium doping on the electrical conductivity of Yb2Ti2O7-based oxygen ion conductors. Yb2[Ti1 − xNbx]2O7 (x = 0.01, 0.04, 0.1) and (Yb0.8Tb0.1Ca0.1)2[Ti1 − xNbx]2O6.9 (x = 0; 0.05; 0.1) pyrochlore solid solutions were synthesized through coprecipitation followed by firing at 1550 °C for 4 h. The materials were examined by XPS, XRD, scanning electron microscopy and impedance spectroscopy. Yb2(Ti0.99Nb0.01)2O7 was shown to have the highest oxygen ion conductivity in air (2.3 × 10− 3 S/cm at 750 °C), which is however markedly lower than that of undoped Yb2Ti2O7. In the (Yb0.8Tb0.1Ca0.1)2[Ti1 − xNbx]2O6.9 (x = 0; 0.05; 0.1) system, the highest conductivity is offered by (Yb0.8Tb0.1Ca0.1)2[Ti0.95Nb0.05]2O6.9 (σ = 4.44 × 10− 3 S/cm at 650 °C). Additional oxygen vacancies created by Ca doping in pyrochlore structure reduce the detrimental effect of Nb4 + doping on the oxide ion transport up to 5% Nb. The conductivity of the Yb2(Ti0.99Nb0.01)2O7 and (Yb0.8Tb0.1Ca0.1)2[Ti0.95Nb0.05]2O6.9 solid solutions was measured both in air and under reducing conditions (5% H2 in N2 and CO2 atmospheres). A comparative study of both these compositions under 5% H2 in N2 atmosphere showed that the transport mechanism was not affected by complex doping of the lanthanide and titanium sublattices in the Yb2Ti2O7-based materials and was related to oxygen vacancies. Conductivity measurements in CO2 were done to ensure correct evaluation of the ionic conductivity of (Yb0.8Tb0.1Ca0.1)2[Ti0.95Nb0.05]2O6.9, because in air it seems to be a mixed p-type and ionic conductor.
Keywords	Oxide ion conductivity; Pyrochlore; Acceptor doping; Donor doping; Impedance spectroscopy
Remark	Available online 1 February 2014; http://dx.doi.org/10.1016/j.ssi.2014.01.019 Link

ID=245

Zr-doped samarium molybdates — potential mixed electron–proton conductors

Authors
Source	Solid State Ionics Time of Publication: 2014
Abstract	Two Zr-doped samarium molybdates View the MathML sourceSm6−x7Zrx7Mo17O127+x24−δ corresponding to x = 0.6 and 1 (SZMO) have been synthesized at 1600 °C for 3 h using mechanically activated mixtures of starting oxides. Fluorite-like Sm0.771Zr0.086Mo0.143O1.739 − δ (06SZMO) and Sm0.714Zr0.143Mo0.143O1.756 − δ (10SZMO) have similar total conductivity of about 4 × 10− 4 S/cm at 800 °C in air. Below 600 °C, the total conductivity of 06SZMO in air exceeds that of 10SZMO. An increase in bulk and grain boundary conductivity of 06SZMO observed at low temperate under wet conditions suggests there may be a proton contribution to the total conductivity. Under reducing conditions (5% H2–Ar) 06SZMO becomes essentially an electronic conductor. Its conductivity reaches 0.25 S/cm at 800 °C and the activation energy decreases to 0.3 eV.
Keywords	Rare-earth; Sm molybdate; Fluorite; Oxide ion conductivity; Proton conductivity; Electron conductivity; Impedance spectroscopy
Remark	Available online 6 February 2014; http://dx.doi.org/10.1016/j.ssi.2014.01.031 Link

ID=244

Interstitial oxide ion conduction in (Sm2 − xZrx)Zr2O7 + δ

Authors	A.V. Shlyakhtina, D.A. Belov, A.V. Knotko, I.V. Kolbanev, A.N. Streletskii
Source	Solid State Ionics Time of Publication: 2014
Abstract	The crystal structure and transport properties of (Sm2 − xZrx)Zr2O7 + x/2 (x = 0; 0.2; 0.32; 0.39; 0.48; 0.67; 0.78; 0.96; 1.14; 1.27) solid solutions have been investigated by X-ray techniques and impedance spectroscopy, respectively. The excess oxygen content of the composition with x = 0.2 has been determined by thermal analysis and mass spectrometry in a reducing atmosphere. The SmZrO system includes a two-phase (fluorite + pyrochlore) region for the (Sm2 − xZrx)Zr2O7 + x/2 (0.48 ≤ x < 0.96) solid solutions. The interstitial oxide ion conductivity of the (Sm2 − xZrx)Zr2O7 + x/2 (0.2 ≤ x < 0.48), 3 × 10− 3 S/cm at 750 °C, is comparable to the vacancy-mediated conductivity of undoped Sm2Zr2O7. The bulk conductivity of the interstitial oxide ion conductors (Sm2 − xZrx)Zr2O7 + x/2 (0.2 ≤ x < 0.48) was shown to vary little in a wide range of Sm2O3 concentrations in contrast to the vacancy mediated oxide ion conductors Sm2(Zr2 − xSmx)O7 − δ (0 ≤ x < 0.29).
Remark	Available online 2 February 2014; http://dx.doi.org/10.1016/j.ssi.2014.01.028 Link

ID=243

Atmosphere controlled conductivity and Maxwell-Wagner relaxation in Bi0.5K0.5TiO3—BiFeO3 ceramics

Authors	Morozov, Maxim I.; Einarsrud, Mari-Ann; Grande, Tor
Source	Journal of Applied Physics Volume: 115, Issue: 4, Pages: 044104 - 044104-6 Time of Publication: 2014
Abstract	Here, we report on a giant dielectric relaxation in (1 − x)Bi0.5K0.5TiO3—xBiFeO3 ceramics below ∼300 °C, which becomes more pronounced with increasing BiFeO3 content. The relaxation was shown to be of Maxwell-Wagner type and associated with charge depletion at the electroded interfaces. It was also shown that the relaxation could be controlled or, eventually, removed by heat treatment in controlled partial pressure of oxygen. This was rationalized by the relationship between the electrical conductivity and variation in the oxidation state of Fe, which is strongly coupled to the partial pressure of oxygen. The results are discussed with emphasis on oxygen diffusion and point defect equilibria involving oxygen vacancies and iron in divalent and tetravalent state. Finally, the barrier-free dielectric properties of the (1 − x)Bi0.5K0.5TiO3—xBiFeO3 ceramics are reported.
Remark	Link

ID=242

Atmosphere controlled conductivity and Maxwell-Wagner relaxation in Bi0.5K0.5TiO3—BiFeO3 ceramics

Authors	Maxim I. Morozov, Mari-Ann Einarsrud and Tor Grande
Source	J. Appl. Phys. Volume: 115, Pages: 044104 Time of Publication: 2014
Abstract	Here, we report on a giant dielectric relaxation in (1 − x)Bi0.5K0.5TiO3 — xBiFeO3 ceramics below ∼300 °C, which becomes more pronounced with increasing BiFeO3 content. The relaxation was shown to be of Maxwell-Wagner type and associated with charge depletion at the electroded interfaces. It was also shown that the relaxation could be controlled or, eventually, removed by heat treatment in controlled partial pressure of oxygen. This was rationalized by the relationship between the electrical conductivity and variation in the oxidation state of Fe, which is strongly coupled to the partial pressure of oxygen. The results are discussed with emphasis on oxygen diffusion and point defect equilibria involving oxygen vacancies and iron in divalent and tetravalent state. Finally, the barrier-free dielectric properties of the (1 − x)Bi0.5K0.5TiO3 — xBiFeO3 ceramics are reported.
Remark	Link

ID=241

Characterisation of structure and conductivity of BaTi0.5Sc0.5O3 − δ

Authors	S.M.H. Rahman, I. Ahmed, R. Haugsrud, S.G. Eriksson, C.S. Knee
Source	Solid State Ionics Volume: 225, Pages: 140–146 Time of Publication: 2014
Abstract	BaTi0.5Sc0.5O3 − δ was prepared via solid state reaction route and final sintering at 1550 °C. High resolution X-ray powder diffraction on the as-prepared material reveals a cubic perovskite structure with a unit cell parameter, a = 4.1343(1) Å. Thermogravimetric analysis revealed the presence of significant levels of protons in the as-prepared material and 74% of the theoretically achievable protonation through filling of oxide ion vacancies was attained on exposure to a humid environment at 185 °C. Infrared spectroscopy revealed a broad Osingle bondH stretching band confirming the presence of OHO• defects. Electrical conductivity was measured with variable frequency AC impedance methods in oxygen, argon, and hydrogen under dry, hydrated (H2O) and heavy water (D2O) conditions. In the temperature range of 150–550 °C in a wet gas atmosphere the conductivity is significantly higher than that observed for dry conditions, indicating that protons are the dominant charge carriers. Conductivity is also found to be higher in dry oxygen in comparison with dry argon over the whole temperature range of 150–1000 °C, characteristic of contribution from p-type charge carriers under oxidising atmospheres. At 550 °C the proton conductivity was estimated to be 2.89 × 10− 4 S cm− 1 in wet Ar. Fitting of conductivity data provides a hydration enthalpy change (ΔHhydr0) of − 100 ± 5 kJ/mol and hydration entropy change (ΔShydr0) of − 160 ± 10 J/mol K.
Keywords	Barium titanate; BaTiO3; Perovskite; Proton conductivity; X-ray diffraction; Hydration
Remark	Link

ID=238

Polymorphism and properties of Bi2WO6 doped with pentavalent antimony

Authors	E.P. Kharitonova, D.A. Belov, A.B. Gagor, A.P. Pietraszko, O.A. Alekseeva, V.I. Voronkova
Source	Journal of Alloys and Compounds Time of Publication: 2014
Abstract	Antimony-containing solid solutions isostructural with bismuth tungstate, Bi2WO6, have been prepared in air as polycrystalline samples by solid-state reactions and as single crystals by unseeded flux growth. The antimony in the solid solutions is in a pentavalent state and substitutes for tungsten in the structure of Bi2WO6. The Bi2W1–xSbxO6–y solid solutions have been shown to exist in the composition range 0 ⩽ x ⩽ 0.05. We have examined the effect of Sb5+ doping on the polymorphism and properties of Bi2WO6. In contrast to undoped Bi2WO6, antimony-substituted bismuth tungstate does not completely transform into its high-temperature, monoclinic phase at 960 °C and remains two-phase up to temperatures approaching its melting point. Antimony substitution for tungsten has a weak effect on the temperatures of the ferroelectric phase transitions. Heterovalent substitution of Sb5+ for W6+ is accompanied by the formation of extra oxygen vacancies and an increase in the electrical conductivity of the solid solutions by one to two orders of magnitude relative to undoped Bi2WO6.
Keywords	Aurivillius phases; Bi2WO6; Ceramics; Phase transitions; Electrophysical properties; Differential scanning calorimetry
Remark	Available online 3 January 2014 Link

ID=237

Effect of Ni Concentration on Phase Stability, Microstructure and Electrical Properties of BaCe0.8Y0.2O3-δ - Ni Cermet SOFC Anode and its application in proton conducting ITSOFC

Authors	Pooja Sawant, S. Varma, M.R. Gonal, B.N. Wani, Deep Prakash, S.R. Bharadwaj
Source	Electrochimica Acta Time of Publication: 2013
Abstract	In this work we have studied the effect of Ni concentration on phase stability, microstructure and electrical properties of BaCe0.8Y0.2O3-δ (BCY)-Ni cermet SOFC anode. It has been seen that Ni forms composite with BCY without forming any solid solution in both oxidized and reduced state. Also, microstructural analysis reveals the effect of Ni on porosity and triple phase boundaries necessary for electrochemical reactions during cell operation. Electrical conductivity values obtained from dc four probe technique in H2 atmosphere increase with an increase in Ni content. Composites with low vol% of Ni contents i.e. 19% (Ni19) and 26% (Ni26) show predominantly semiconductor-like behaviour whereas higher vol% viz. 35% (Ni35), 45% (Ni45) and 56% (Ni56) composites show electronic conductivity behaviour. This confirms that electronic conduction occurs through metallic Ni phase. Also, anode supported single cell for proton conducting SOFC has been fabricated using Ni35 composition and its current-potential characteristics measured at different temperatures.
Keywords	Cermet; X-ray diffraction; Electrical conductivity; Four probe; Single Cell
Remark	Available online 25 December 2013 Link

ID=236

Cathode compatibility, operation, and stability of LaNbO4-based proton conducting fuel cells

Authors
Source	Solid State Ionics Time of Publication: 2013
Abstract	Cathodes compatible with Ca-doped LaNbO4 (LCNO) and the operation of a complete proton conducting fuel cell based on this electrolyte are presented. The best performing cathode was a 50 vol.% La0.8Sr0.2MnO3 (LSM)–50 vol.% LCNO composite, with an overall area specific resistance (ASR) of ~ 10 Ω cm2 at 800 °C in wet air. Pt and La0.8Sr0.2(Cr0.5Mn0.5)O3-based cathodes exhibit higher ASRs. The performance of a complete Ni–LCNO//LCNO//LSM–LCNO fuel cell shows a high open circuit voltage but with relatively low performance, in agreement with the modest proton conductivity of LaNbO4-based materials and cathode performances. The cell exhibits stable operation with CO2 containing atmosphere on the cathode side, confirming the chemical robustness of LaNbO4-based electrolytes.
Keywords	Proton conducting fuel cells; Manufacturing; Impedance spectroscopy; LaNbO4; Characterization; Cathode performance
Remark	Available online 22 December 2013; Link

ID=235

Determination of Oxygen Diffusion Coefficients in La1-xSrxFe1-yGayO3-δ Perovskites Using Oxygen Semi-Permeation and Conductivity Relaxation Methods

Authors	P. M. Geffroy, Y. Hu, A. Vivet, T. Chartier and G. Dezanneau
Source	Journal of the Electrochemical Society Volume: 161, Issue: 3, Pages: F153-F160 Time of Publication: 2014
Abstract	This paper reports new evidence that oxygen surface exchange and bulk diffusion in a mixed conductor can be simultaneously determined via the oxygen semi-permeation method. Herein, we report the use of an original apparatus for oxygen activity measurements at both membrane surfaces to evaluate the oxygen surface exchange and bulk diffusion coefficients. Oxygen surface exchange and bulk diffusion in the La1-xSrxFe1-yGayO3-δ perovskite series are also determined and compared with the results from three different methods: isotopic exchange, conductivity relaxation, and oxygen semi-permeation. Although the thermodynamic conditions for these methods are not exactly the same, the values obtained for the oxygen surface exchange and bulk diffusion coefficients are in good agreement.
Remark	Link

ID=233

Porous La 0.6 Sr 0.4 CoO 3-δ thin film cathodes for large area micro solid oxide fuel cell MEMS power generators

Authors
Source	Journal of Power Sources Time of Publication: 2013
Abstract	Porous La0.6Sr0.4CoO3-δ thin films were fabricated by pulsed laser deposition for being used as a cathode for micro solid oxide fuel cell applications as MEMS power generators. Symmetrical La0.6Sr0.4CoO3-δ/yttria-stabilized zirconia/La0.6Sr0.4CoO3-δ free-standing membranes were fabricated using silicon as a substrate. A novel large-area membrane design based on grids of doped-silicon slabs. Thermo-mechanical stability of the tri-layer membranes was ensured in the intermediate range of temperatures up to 700°C. In-plane conductivity of ca. 300 S/cm was measured for the cathode within the whole range of application temperatures. Finally, area specific resistance values below 0.3 Ω·cm2 were measured for the cathode/electrolyte bi-layer at 700°C in the exact final micro solid oxide fuel cell device configuration, thus presenting La0.6Sr0.4CoO3-δ as a good alternative for fabricating reliable micro solid oxide fuel cells for intermediate temperature applications.
Keywords	Micro Solid Oxide Fuel Cell, thin film cathode, self-supported electrolyte
Remark	DOI: 10.1016/j.jpowsour.2013.10.038

ID=228

Nanocrystalline Sm0.5Sr0.5CoO3−δ synthesized using a chelating route for use in IT-SOFC cathodes: microstructure, surface chemistry and electrical conductivity

Authors	Rares Scurtu, Simona Somacescu, Jose Maria Calderon-Moreno, Daniela Culita, Ion Bulimestru, Nelea Popa, Aurelian Gulea, Petre Osiceanu
Source	Journal of Solid State Chemistry Time of Publication: 2013
Abstract	Nanocrystalline Sm0.5Sr0.5CoO3−δ powders were synthesized by a chelating route using different polyfunctional HxAPC acids (APC=aminopolycarboxylate; x= 3, 4, 5). Different homologous aminopolycarboxylic acids, namely nitrilotriacetic (H3nta), ethylenediaminetetraacetic (H4edta), 1,2-cyclohexanediaminetetracetic (H4cdta) and diethylenetriaminepentaacetic (H5dtpa) acid, were used as chelating agents to combine Sm, Sr, Co elements into a perovskite structure. The effects of the chelating agents on the crystalline structure, porosity, surface chemistry and electrical properties were investigated. The electrical properties of the perovskite-type materials emphasized that their conductivities in the temperature range of interest (600–800 °C) depend on the nature of the precursors as well as on the presence of a residual Co oxide phase as shown by XRD and XPS analysis. The surface chemistry and the surface stoichiometries were determined by XPS revealing a complex chemical behavior of Sr that exhibits a peculiar „surface phase” and „bulk phase” chemistry within the detected volume (<10 nm).
Keywords	Cathode; Perovkites; Electrical Conductivity; XPS; IT-SOFC
Remark	Available online 5 November 2013 Link

ID=223

Porous La0.6Sr0.4CoO3-δ thin film cathodes for large area micro solid oxide fuel cell MEMS power generators

Authors
Source	Journal of Power Sources Time of Publication: 2013
Abstract	Porous La0.6Sr0.4CoO3-δ thin films were fabricated by pulsed laser deposition for being used as a cathode for micro solid oxide fuel cell applications as MEMS power generators. Symmetrical La0.6Sr0.4CoO3-δ/yttria-stabilized zirconia/La0.6Sr0.4CoO3-δ free-standing membranes were fabricated using silicon as a substrate. A novel large-area membrane design based on grids of doped-silicon slabs. Thermo-mechanical stability of the tri-layer membranes was ensured in the intermediate range of temperatures up to 700°C. In-plane conductivity of ca. 300 S/cm was measured for the cathode within the whole range of application temperatures. Finally, area specific resistance values below 0.3 Ω·cm2 were measured for the cathode/electrolyte bi-layer at 700°C in the exact final micro solid oxide fuel cell device configuration, thus presenting La0.6Sr0.4CoO3-δ as a good alternative for fabricating reliable micro solid oxide fuel cells for intermediate temperature applications.
Remark	Available online 18 October 2013 Link

ID=220

Application of FIB-TOF-SIMS and FIB-SEM-EDX Methods for the Analysis of Element Mobility in Solid Oxide Fuel Cells

Authors
Source	ECS Transactions Volume: 57, Issue: 1, Pages: 581-587 Time of Publication: 2013
Abstract	The solid oxide fuel cell single cells with porous Pr0.6Sr0.4CoO3-δ and La0.6Sr0.4CoO3-δ (PSCO, LSCO respectively) cathodes on compact Ce0.9Gd0.1O2-δ\|Zr0.85Y0.15O2-δ or Ce0.9Gd0.1O2-δ\|Zr0.85Sc0.15O2-δ bi-layered electrolytes deposited onto Ni-Zr0.85Y0.15O2-δ (Ni-ZYO) or Ni- Ce0.9Gd0.1O2-δ (Ni-CGO) supporting anode were prepared for ion (element) mobility studies. Focused ion beam - time of flight - secondary ion mass spectrometry (FIB-TOF-SIMS) method in addition to FIB-SEM, SEM-EDX and XRD methods has been used for analysis of mass-transfer (interlayer diffusion) of cathode electrode elements, demonstrating that during PSCO and LSCO sintering at 1100°C on to CGO\|ZYO or CGO\|ZScO bilayered electrolyte, noticeable mass-transfer of Sr2+ cations through the partially microporous CGO has been verified using FIB-TOF-SIMS and SEM-EDX methods. The single cells have been additionally studied using cyclic voltammetry, electrochemical impedance and chronoamperometry methods and high power densities have been demonstrated.
Remark	Link

ID=219

Chromium Poisoning of La2NiO4+δ Cathodes

Authors	Soo-Na Lee, Alan Atkinson and John A. Kilner
Source	ECS Transactions Volume: 57, Issue: 1, Pages: 605-613 Time of Publication: 2013
Abstract	It has been reported that Sr-containing materials (such as LSCF) are susceptible to Cr-poisoning by the formation of SrCrO4 and therefore there is interest in Sr-free cathodes such as La2NiO4+δ (LNO). In this study, La2NiO4+δ electrodes were deposited symmetrically onto Ce0.9Gd0.1O1.95 electrolytes by screen printing. The LNO electrodes were solution impregnated with targeted amounts of chromium and then characterised by impedance spectroscopy (520- 800°C). XRD of LNO/Cr2O3 powder mixtures annealed at 900°C showed that there is a reaction between them. Nevertheless, the impedance results indicate that LNO is less prone to chromium deactivation than LSCF.
Remark	Link

ID=217

Synthesis, properties and phase transitions of pyrochlore- and fluorite-like Ln2RMO7 (Ln=Sm, Ho; R=Lu, Sc; M= Nb, Ta)

Authors	A.V. Shlyakhtina, D.A. Belov, K.S. Pigalskiy, A.N. Shchegolikhin, I.V. Kolbanev, O.K. Karyagina
Source	Materials Research Bulletin Time of Publication: 2013
Abstract	We have studied the new compounds with fluorite-like (Ho2RNbO7 (R = Lu, Sc)) and pyrochlore-like (Sm2ScTaO7) structure as potential oxide ion conductors. The phase formation process (from 1200 to 1600 °C) and physical properties (electrical, thermo mechanical, and magnetic) for these compounds were investigated. Among the niobate materials the highest bulk conductivity is offered by the fluorite-like Ho2ScNbO7 synthesized at 1600 °C: 3.8 × 10−5 S/cm at 750 °C, whereas in Sm system the highest bulk conductivity, 7.3 × 10−6 S/cm at 750 °C, is offered by the pyrochlore Sm2ScTaO7 synthesized at 1400 °C. In Sm2ScTaO7 pyrochlore we have observed the first-order phase transformation at ∼650–700 °C is related to rearrangement process in the oxygen sublattice of the pyrochlore structure containing B-site cations in different valence state and actually is absent in the defect fluorites. The two holmium niobates show Curie–Weiss paramagnetic behavior, with the prevalence of antiferromagnetic coupling. The magnetic susceptibility of Sm2ScTaO7 is a weak function of temperature, corresponding to Van Vleck paramagnetism.
Keywords	Pyrochlore; Fluorite; Phase transition; Ionic conductivity; Thermo mechanical analysis; Dielectric permittivity; Loss tangent; Magnetic susceptibility
Remark	Available online 11 October 2013 Link

ID=216

Proton Conductivity in Solid Solution 0.7(CaWO4)–0.3(La0.99Ca0.01NbO4) and Ca(1−x)LaxW(1−y)TayO4

Authors	Camilla K. Vigen, Reidar Haugsrud
Source	Journal of the American Ceramic Society Time of Publication: 2013
Abstract	The conductivity of nominal CaWO4, CaW0.99Ta0.01O4–δ, 0.7(CaWO4)–0.3(La0.99Ca0.01NbO4–δ), and Ca0.9La0.1WO4+δ has been studied by means of a.c. impedance measurements. Proton conductivity was observed for CaW0.99Ta0.01O4–δ, which displayed exothermic hydration with enthalpy and entropy of –82 kJ/mol and –120 J/molK, respectively. The proton mobility in CaW0.99Ta0.01O4–δ was low, with enthalpy and preexponential factor of mobility of 82 kJ/mol and 0.7 cm2K/Vs. The high enthalpy of mobility is interpreted to reflect association between the acceptor dopant and protonic defects, whereas the low preexponential factor of mobility may reflect a lower proton concentration than assumed. Rietveld refinement indicated low solubilities of La on Ca-site and Ta on W-site. Proton conductivity was also observed in undoped CaWO4, however, not in Ca0.9La0.1WO4+δ. The conductivity of 0.7(CaWO4)–0.3(La0.99Ca0.01NbO4–δ) behaved much like that of undoped LaNbO4, likely due to a very low acceptor dopant concentration.
Remark	Article first published online: 1 OCT 2013. DOI: 10.1111/jace.12587 Link

ID=215

The Investigation of E-beam Deposited Titanium Dioxide and Calcium Titanate Thin Films

Authors	Kristina BOČKUTĖ, Giedrius LAUKAITIS, Darius VIRBUKAS, Darius MILČIUS
Source	Volume: 19, Issue: 3, Pages: 245-249 Time of Publication: 2013
Abstract	Thin titanium dioxide and calcium titanate films were deposited using electron beam evaporation technique. The substrate temperature during the deposition was changed from room temperature to 600 °C to test its influence on TiO2 film formation and optical properties. The properties of CaTiO3 were investigated also. For the evaluation of the structural properties the formed thin ceramic films were studied by X-ray diffraction (XRD), energy dispersive spectrometry (EDS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Optical properties of thin TiO2 ceramics were investigated using optical spectroscope and the experimental data were collected in the ultraviolet-visible and near-infrared ranges with a step width of 1 nm. Electrical properties were investigated by impedance spectroscopy.It was found that substrate temperature has influence on the formed thin films density. The density increased when the substrate temperature increased. Substrate temperature had influence on the crystallographic, structural and optical properties also.
Keywords	electron beam evaporation; titanium oxide; calcium titanate; optical properties
Remark	DOI: http://dx.doi.org/10.5755/j01.ms.19.3.1805 Link

ID=214

Synthesis and Characterization of Nonsubstituted and Substituted Proton-Conducting La6–xWO12–y

Authors
Source	Inorganic Chemistry Publisher: ACS Publications, Time of Publication: 2013
Abstract	Mixed proton–electron conductors (MPEC) can be used as gas separation membranes to extract hydrogen from a gas stream, for example, in a power plant. From the different MPEC, the ceramic material lanthanum tungstate presents an important mixed protonic–electronic conductivity. Lanthanum tungstate La6–xWO12–y (with y = 1.5x + δ and x = 0.5–0.8) compounds were prepared with La/W ratios between 4.8 and 6.0 and sintered at temperatures between 1300 and 1500 °C in order to study the dependence of the single-phase formation region on the La/W ratio and temperature. Furthermore, compounds substituted in the La or W position were prepared. Ce, Nd, Tb, and Y were used for partial substitution at the La site, while Ir, Re, and Mo were applied for W substitution. All substituents were applied in different concentrations. The electrical conductivity of nonsubstituted La6–xWO12–y and for all substituted La6–xWO12–y compounds was measured in the temperature range of 400–900 °C in wet (2.5% H2O) and dry mixtures of 4% H2 in Ar. The greatest improvement in the electrical characteristics was found in the case of 20 mol % substitution with both Re and Mo. After treatment in 100% H2 at 800 °C, the compounds remained unchanged as confirmed with XRD, Raman, and SEM.
Keywords	ProGasMix
Remark	lanthanum tungstate La6–xWO12–y Link

ID=213

Synthesis and Characterization of Nonsubstituted and Substituted Proton-Conducting La6–xWO12–y

Authors
Source	Inorg. Chem. Time of Publication: 2013
Abstract	Mixed proton–electron conductors (MPEC) can be used as gas separation membranes to extract hydrogen from a gas stream, for example, in a power plant. From the different MPEC, the ceramic material lanthanum tungstate presents an important mixed protonic–electronic conductivity. Lanthanum tungstate La6–xWO12–y (with y = 1.5x + δ and x = 0.5–0.8) compounds were prepared with La/W ratios between 4.8 and 6.0 and sintered at temperatures between 1300 and 1500 °C in order to study the dependence of the single-phase formation region on the La/W ratio and temperature. Furthermore, compounds substituted in the La or W position were prepared. Ce, Nd, Tb, and Y were used for partial substitution at the La site, while Ir, Re, and Mo were applied for W substitution. All substituents were applied in different concentrations. The electrical conductivity of nonsubstituted La6–xWO12–y and for all substituted La6–xWO12–y compounds was measured in the temperature range of 400–900 °C in wet (2.5% H2O) and dry mixtures of 4% H2 in Ar. The greatest improvement in the electrical characteristics was found in the case of 20 mol % substitution with both Re and Mo. After treatment in 100% H2 at 800 °C, the compounds remained unchanged as confirmed with XRD, Raman, and SEM.
Remark	DOI: 10.1021/ic401104m; Publication Date (Web): September 3, 2013 Link

ID=212

Defects and Transport Properties in TiNb2O7

Authors	Wen Xing, Liv-Elisif Kalland, Zuoan Li, Reidar Haugsrud
Source	Journal of the American Ceramic Society Time of Publication: 2013
Abstract	The electrical conductivity of TiNb2O7 was characterized as a function of temperature, inline image and inline image. The total conductivity was independent of inline image in the low oxygen partial pressure regime, while a dependency of inline image was observed at higher oxygen partial pressures. The conductivity increased with increasing inline image under oxidizing conditions below 700°C. Mixed electronic and protonic conduction was indicated by H/D isotope exchange and transport number measurements. A defect model based on interstitial type of hydration was established and fitted to the conductivity data allowing for determination of physicochemical parameters of hydration and electron migration.
Remark	Article first published online. DOI: 10.1111/jace.12558 Link

ID=208

Effects of Nb5+, Mo6+, and W6+ dopants on the germanate-based apatites as electrolyte for use in solid oxide fuel cells

Authors	Sea-Fue Wang, Yung-Fu Hsu, Wan-Ju Lin
Source	International Journal of Hydrogen Energy Volume: 38, Issue: 27, Pages: 12015–12023 Time of Publication: 2013-09
Abstract	Rare information is available in the literature on the cell performance of the solid oxide fuel cells (SOFCs) using apatites known for their good electrical conductivity as electrolyte materials. In this study, La9.5Ge5.5Nb0.5O26.5, La9.5Ge5.5Mo0.5O26.75, and La9.5Ge5.5W0.5O26.75 ceramics were prepared and characterized. The results indicated that the La9.5Ge5.5Nb0.5O26.5 and La9.5Ge5.5W0.5O26.75 ceramics reported hexagonal phase, while the La9.5Ge5.5Mo0.5O26.75 ceramic demonstrated triclinic symmetry. Among the apatities evaluated, La9.5Ge5.5Nb0.5O26.5 sintered at 1450 °C showed the best conduction with an electrical conductivity value of 0.045 S/cm at 800 °C. Button cells of NiO–SDC/La9.5Ge5.5Nb0.5O26.5/LSCF–SDC were built and revealed good structural integrity. The total ohmic resistance (R0) and interfacial polarization resistance (RP) of the cell read 0.428 and 0.174 Ω cm2 and 0.871 and 1.164 Ω cm2, respectively at 950 and 800 °C. The maximum power densities (MPD) of the single cell at 950 and 800 °C were respectively 0.363 and 0.095 W cm−2. Without optimizing the anode and cathode as well as hermetic sealing of the cell against the gas, the study found the performance of the single cell with the pure La9.5Ge5.5Nb0.5O26.5 as its electrolyte material superior to those of the SOFC cells with a YSZ electrolyte of comparable thickness shown in the literature.
Keywords	Solid oxide fuel cell; Apatite; Impedance; Cell performance
Remark	Link

ID=207

Transformation from insulating p-type to semiconducting n-type conduction in CaCu3Ti4O12-related Na(Cu5/2Ti1/2)Ti4O12 ceramics

Authors	Li, Ming, Sinclair, Derek C.
Source	Journal of Applied Physics Volume: 114, Issue: 3, Pages: 034106 - 034106-8 Time of Publication: 2013-07
Abstract	A double doping mechanism of Na+ + ½ Ti4+ → Ca2+ + ½ Cu2+ on the general formula Ca1-xNax(Cu3-x/2Tix/2)Ti4O12 has been used to prepare a series of isostructural CaCu3Ti4O12 (CCTO)-type perovskites. A complete solid solution exists for 0 ≤ x ≤ 1 and all compositions exhibit incipient ferroelectric behaviour with higher than expected intrinsic relative permittivity. Although CCTO ceramics typically exhibit n-type semiconductivity (room temperature, RT, resistivity of ∼10–100 Ω cm), Na(Cu5/2Ti1/2)Ti4O12 (NCTO) ceramics sintered at 950 °C consist of two insulating bulk phases (RT resistivity > 1 GΩ cm), one p-type and the other n-type. With increasing sintering temperature/period, the p-type phase transforms into the n-type phase. During the transformation, the resistivity and activation energy for electrical conduction (Ea ∼ 1.0 eV) of the p-type phase remain unchanged, whereas the n-type phase becomes increasingly conductive with Ea decreasing from ∼ 0.71 to 0.11 eV with increasing sintering temperature. These changes are attributed to small variations in stoichiometry that occur during high temperature ceramic processing with oxygen-loss playing a crucial role.
Remark	Link

ID=206

New double molybdate Na9Fe(MoO4)6: Synthesis, structure, properties

Authors	Aleksandra A. Savina, Sergey F. Solodovnikov, Olga M. Basovich, Zoya A. Solodovnikova, Dmitry A. Belov, Konstantin V. Pokholok, Irina A. Gudkova, Sergey Yu. Stefanovich, Bogdan I. Lazoryak, Elena G. Khaikina
Source	Journal of Solid State Chemistry Volume: 205, Pages: 149–153 Time of Publication: 2013-09
Abstract	A new double molybdate Na9Fe(MoO4)6 was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, X-ray fluorescence analysis, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na9Fe(MoO4)6 were obtained and its structure was solved (the space group RView the MathML source3¯, a=14.8264(2), c=19.2402(3) Å, V=3662.79(9) Å3, Z=6, R=0.0132). The structure is related to that of sodium ion conductor II-Na3Fe2(AsO4)3. The basic structure units are polyhedral clusters composed of central FeО6 octahedron sharing edges with three Na(1)О6 octahedra. The clusters share common vertices with bridging МоО4 tetrahedra to form an open 3D framework where the cavities are occupied by Na(2) and Na(3) atoms. The compound melts incongruently at 904.7±0.2 K. Arrhenius type temperature dependence of electric conductivity σ has been registered in solid state (σ=6.8×10−2 S сm−1 at 800 K), thus allowing considering Na9Fe(MoO4)6 as a new sodium ion conductor.
Keywords	Sodium–iron molybdate; Crystal structure; Solid-state electrolyte
Remark	Link

ID=205

Study of bulk and grain-boundary conductivity of Ln2+xHf2−xO7−δ (Ln = Sm-Gd; x = 0, 0.096) pyrochlores

Authors	A. V. Shlyakhtina, S. N. Savvin, A. V. Levchenko, A. V. Knotko, Petra Fedtke, Andreas Busch, Torsten Barfels, Marion Wienecke, L. G. Shcherbakova
Source	Journal of Electroceramics Volume: 24, Issue: 4, Pages: 300-307 Time of Publication: 2010-06
Abstract	The electrical conductivity of new solid electrolytes Eu2.096Hf1.904O6.952 and Gd2Hf2O7 have been compared with those for different pyrochlores including titanates and zirconates Ln2+xМ2−xO7−δ (Ln = Sm-Lu; M = Ti, Zr; x = 0−0.81). Impedance spectroscopy data demonstrate that Eu2.096Hf1.904O6.952 and Gd2Hf2O7 synthesized from mechanically activated oxides have high ionic conductivity, comparable to that of their zirconate analogues. The bulk and grain-boundary components of conductivity in Sm2.096Hf1.904O6.952 (Тsynth = 1600°С), Eu2.096Hf1.904O6.952 and Gd2Hf2O7 (Тsynth = 1670°С) have been determined. The highest bulk conductivity is offered by the disordered pyrochlores prepared at 1600°C and 1670°C: ~1.5 × 10−4 S/cm for Sm2.096Hf1.904O6.952, 5 × 10−3 S/cm for Eu2.096Hf1.904O6.952 and 3 × 10−3 S/cm for Gd2Hf2O7 at 780°С, respectively. The conductivity of the fluorite-like phases at the phase boundaries of the Ln2+xМ2−xO7−δ (Ln = Eu, Gd; M = Zr, Hf; x ~ 0.286) solid solutions, as well as that of the high-temperature fluorite-like phases Ln2+xМ2−xO7−δ (Ln = Eu, Gd; M = Zr, Hf; x = 0−0.286), is lower than the conductivity of the disordered pyrochlores Ln2+xМ2−xO7−δ (Ln = Eu, Gd; M = Zr, Hf; x = 0−0.096).
Remark	Link

ID=204

Ionic conduction in glasses in the MnNbOF5-BaF2-BiF3 system

Authors	S. A. Polyshchuk, L. N. Ignat’eva, S. L. Sinebryukhov, S. V. Gnedenkov, A. B. Podgorbunsky, N. N. Savchenko, A. B. Slobodyuk, V. M. Bouznik
Source	Russian Journal of Inorganic Chemistry Volume: 58, Issue: 4, Pages: 387-391 Time of Publication: 2013-04
Abstract	The electrical conductivity of oxyfluoride glasses in the MnNbOF5-BaF2-BiF3 system in the temperature range 299–550 K was studied by impedance spectroscopy. It was shown that the conductivity is mainly caused by fluoride ions forming fluorobismuth polyhedra in the glass structure, being as high as 7.46 × 10−3 S/cm (533 K) in the 20MnNbOF5-30BaF2-50BiF3 system reaches, which is at the level of the best values for fluoride glasses.
Remark	Link

ID=203

Solid-state photoelectrochemical H2 generation with gaseous reactants

Authors	Kingsley O. Iwu, Augustinas Galeckas, Andrej Yu. Kuznetsov, Truls Norby
Source	Electrochimica Acta Volume: 97, Pages: 320–325 Time of Publication: 2013-05
Abstract	Photocurrent and H2 production were demonstrated in an all solid-state photoelectrochemical cell employing gaseous methanol and water vapour at the photoanode. Open circuit photovoltage of around -0.4 V and short circuit photocurrent of up to 250 μA/cm2 were obtained. At positive bias, photocurrent generation was limited by the irradiance, i.e., the amount of photogenerated charge carriers at the anode. Time constants and impedance spectra showed an electrochemical capacitance of the cell of about 15 μF/cm2 in the dark, which increased with increasing irradiance. With only water vapour at the anode, the short circuit photocurrent was about 6% of the value with gaseous methanol and water vapour. The photoanode and electrocatalyst on carbon paper support were affixed to the proton conducting membrane using Nafion® as adhesive, an approach that yielded photocurrents up to 15 times better than that of a cell assembled by hot-pressing, in spite of the overall cell resistance of the latter being up to 5 times less than that of the former. This is attributed, at least partially, to reactants being more readily available at the photoanode of the better performing cell.
Keywords
Remark	Link

ID=201

Synthesis and characterization of perovskite-type SrxY1−xFeO3−δ (0.63≤x<1.0) and Sr0.75Y0.25Fe1−yMyO3−δ (M= Cr, Mn, Ni), (y=0.2, 0.33, 0.5)

Authors
Source	Journal of Solid State Chemistry Volume: 200, Pages: 30-38 Time of Publication: 2013-04
Abstract	Abstract Oxygen-deficient ferrates with the cubic perovskite structure SrxY1−xFeO3−δ were prepared in air (0.71≤x≤0.91) as well as in N2 (x=0.75 and 0.79) at 1573 K. The oxygen content of the compounds prepared in air increases with increasing strontium content from 3-δ=2.79(2) for x=0.75 to 3-δ=2.83(2) for x=0.91. Refinement of the crystal structure of Sr0.75Y0.25FeO2.79 using TOF neutron powder diffraction (NPD) data shows high anisotropic atomic displacement parameter (ADP) for the oxygen atom resulting from a substantial cation and anion disorder. Electron diffraction (ED) and high-resolution electron microscopy (HREM) studies of Sr0.75Y0.25FeO2.79 reveal a modulation along <1 0 0>p with G± ~0.4<1 0 0>p indicating a local ordering of oxygen vacancies. Magnetic susceptibility measurements at 5–390 K show spin-glass behaviour with dominating antiferromagnetic coupling between the magnetic moments of Fe cations. Among the studied compositions, Sr0.75Y0.25FeO2.79 shows the lowest thermal expansion coefficient (TEC) of 10.5 ppm K−1 in air at 298–673 K. At 773–1173 K TEC increases up to 17.2 ppm K−1 due to substantial reduction of oxygen content. The latter also results in a dramatic decrease of the electrical conductivity in air above 673 K. Partial substitution of Fe by Cr, Mn and Ni according to the formula Sr0.75Y0.25Fe1−yMyO3−δ (y=0.2, 0.33, 0.5) leads to cubic perovskites for all substituents with y=0.2. Their TECs are higher in comparison with un-doped Sr0.75Y0.25FeO2.79. Only M=Ni has increased electrical conductivity compared to un-doped Sr0.75Y0.25FeO2.79.
Keywords	Perovskites; Neutron diffraction; Electron diffraction; High-temperature conductivity; Thermal expansion; Magnetic susceptibility
Remark	Link

ID=200

Optimization of synthesis conditions for rare-earth titanate based oxygen ion conductors

Authors	A.V. Shlyakhtina, D.A. Belov, S.Yu. Steafanovich, E.A. Nesterova, O.K. Karyagina, L.G. Shcherbakova
Source	Solid State Ionics Volume: 230, Pages: 52-58 Time of Publication: 2013-01
Abstract	High-density (Yb0.9Ca0.1)2Ti2O6.9, (Yb0.8Ca0.1Tb0.1)2Ti2O7 − δ, and (Dy0.8Ca0.1Tb0.1)2Ti2O7 − δ solid solutions have been prepared through co-precipitation followed by firing for 4 h at 1500 and 1550 °C, and their crystal structure (XRD), microstructure (SEM), and oxygen ion conductivity (impedance spectroscopy) have been studied in relation to the firing temperature and precipitant used. As in the case of (Yb0.9Ca0.1)2Ti2O6.9 and (Yb0.8Ca0.1Tb0.1)2Ti2O7 − δ, the optimal synthesis temperature for (Dy0.8Ca0.1Tb0.1)2Ti2O7 − δ is 1500 °C. The bulk oxygen ion conductivity of the pyrochlore-like solid solutions (Yb0.9Ca0.1)2Ti2O6.9 is a stronger function of synthesis temperature than that of the (Dy0.8Ca0.1Tb0.1)2Ti2O7 − δ and (Yb0.8Ca0.1Tb0.1)2Ti2O7 − δ solid solutions with more complex A sublattice. The rise of the synthesis temperature from 1500 to 1550 °C has detrimental effect on the grain boundary conductivity of the (Yb0.9Ca0.1)2Ti2O6.9 and (Dy0.8Ca0.1Tb0.1)2Ti2O7 − δ ceramics. That effect is connected with a considerable grain-boundary segregation of a calcium-containing phase in the (Yb0.9Ca0.1)2Ti2O6.9 and (Dy0.8Ca0.1Tb0.1)2Ti2O7 − δ. The bulk and grain boundary conductivity of (Dy0.8Ca0.1Tb0.1)2Ti2O7 − δ are independent of the precursor synthesis conditions (homogeneous and non-homogeneous co-precipitation).
Keywords	Synthesis; Co-precipitation; Pyrochlore; Doping; Oxide ion conductivity; Impedance spectroscopy
Remark	Link

ID=196

Oxygen ion conductivity of (Yb0.9 − xTbxCa0.1)2Ti2O7 − δ solid solutions

Authors	A. V. Shlyakhtina, D. A. Belov, S. Yu. Stefanovich, O. K. Karyagina and L. G. Shcherbakova
Source	Inorganic Materials Volume: 48, Issue: 11, Pages: 1126-1130 Time of Publication: 2012-11
Abstract	We have studied terbium substitution for ytterbium in (Yb0.9 − x Tb x Ca0.1)2Ti2O7 − δ (x = 0.1, 0.2, 0.3, 0.4) pyrochlore solid solutions synthesized through coprecipitation followed by firing at 1550°C. The results indicate that only a small amount of terbium (less than 10%) can be incorporated into the pyrochlore structure of (Yb0.9Ca0.1)2Ti2O6.9 because of the large difference in ionic radius between the terbium and ytterbium cations: Δr = r(TbCN 83+) − r(YbCN 83+) = 0.055 Å. The oxygen ion conductivity of the (Yb0.9 − x Tb x Ca0.1)2Ti2O7 − δ solid solutions has been determined by impedance spectroscopy in air in the temperature range 300 to 900°C. At high temperatures (t > 640°C), their bulk conductivity was essentially independent of the Yb/Tb ratio. The observed decrease in density and microstructural changes were insignificant. At relatively low temperatures (t < 640°C), the bulk conductivity decreased slightly, and the decrease depended little on terbium concentration.
Remark	Link

ID=195

H and Li Related Defects in ZnO and their Effect on Electrical Properties

Authors
Source	J. Phys. Chem. C Volume: 166, Issue: 44, Pages: 23764–23772 Time of Publication: 2012-10
Abstract	Li and H are important electrically active impurities in ZnO and this work presents a detailed experimental and computational study of the behavior of H and Li in ZnO, and their effect on its defect structure. We employ AC conductivity measurements as a function of temperature and partial pressure of O2, H2O and D2O, which is combined with first principles density functional theory (DFT) calculations and thermodynamic modeling (TDM) of finite temperature defect structures in undoped and Li doped ZnO. Undoped ZnO is dominated by protons as hydroxide defects (OH_O^•), oxygen vacancies (v_O^(••)) and electrons under a large variety of atmospheric conditions, and we also predict from DFT and TDM the substitutional hydride ion (H_O^•) to dominate concentration-wise under the most reducing conditions at temperatures above 500 °C. The equilibrium concentrations of defects in ZnO are small, and dopants such as Li strongly affect the electrical properties. Experimentally, Li doped ZnO is found to be n-type under all available atmospheric conditions and temperatures, with a n-type conductivity significantly lower than that of as-grown ZnO. The n-type conductivity also increases with decreasing p_(O_2 ) and with increasing p_(H_2 O). The observed electrical properties of Li doped ZnO are attributed to dominance of the ionic defects Li_Zn^/, OH_O^•, Li_i^•, v_O^(••), and the neutral complexes (Li_Zn OH_O)^× and (Li_Zn Li_i)^×. Although Li doping lowers the Fermi level of as-grown ZnO significantly, low formation energy of the ionic donors, and passivation of Li_Zn^/ in the form of (Li_Zn OH_O)^× and (Li_Zn Li_i)^×, prevents realization of significant/stable p-type activity in Li doped ZnO under equilibrium conditions.
Remark	Link

ID=194

Crystal structure, hydration and ionic conductivity of the inherently oxygen-deficient La2Ce2O7

Authors	Vasileios Besikiotis, Christopher S. Knee, Istaq Ahmed, Reidar Haugsrud, Truls Norby
Source	Solid State Ionics Volume: 228, Pages: 1–7 Time of Publication: 2012-11
Abstract	The crystal structure, hydration and ionic conductivity of the inherently oxygen deficient La2Ce2O7 system have been investigated. On the basis of Rietveld analysis of neutron diffraction data, the material is found to adopt a cation disordered oxygen-deficient fluorite structure. Impedance spectroscopy, performed in the temperature range 1000–200 °C and as a function of water vapor and oxygen partial pressure, suggests that oxide ion conductivity dominates at high temperatures, while protons are the main charge carrier at temperatures below approximately 450 °C. Proton conductivity was confirmed by isotope shifts under H2O and D2O. The dissolution of water was measured by means of thermogravimetry (TG). A defect chemical model is developed to derive hydration thermodynamic parameters based on TG and conductivity data. The hydration enthalpy was, moreover, determined directly by simultaneous TG and differential scanning calorimetry (TG–DSC). The TG–DSC values were in good agreement with those modeled from conductivity and TG data.
Keywords	La2Ce2O7; Proton conductivity; Pyrochlore structure; Fluorite structure; Nonstoichiometric oxides
Remark	Link

ID=192

Microstructure and electrical properties of zirconia and composite nanostructured ceramics sintered by different methods

Authors	Bogdan Stefan Vasile, Ecaterina Andronescu, Cristina Ghitulica, Otilia Ruxandra Vasile, Lavinia Curechiu, Rares Scurtu, Eugeniu Vasile, Roxana Trusca, Livia Pall, Virgil Aldica
Source	Ceramics International Volume: 39, Issue: 3, Pages: 2535–2543 Time of Publication: 2013-04
Abstract	The aim of this study is the preparation and characterization of dense cubic zirconia ceramics and zirconia nanocomposites (reinforced with 5 wt% alumina). The powders were obtained through sol–gel methods and densified using classical sintering and spark plasma sintering (SPS) methods. The obtained ceramics were characterized through X-ray diffraction, scanning electron microscopy and impedance spectroscopy at room and high temperature. The average grain size of cubic zirconia particles was found to be approximately 8 and 2.5 μm for the classical sintering and 99 nm for SPS. The alumina particles in composites have an average grain size of 0.7 μm for classical sintering and 53 nm for SPS ones. The total conductivity for nanocomposites sintered through both methods was also determined.
Remark	Link

ID=191

Characteristics of SrCo1 − xSnxO3 − δ cathode materials for use in solid oxide fuel cells

Authors	Sea-Fue Wang, Yung-Fu Hsu, Chun-Ting Yeh, Chien-Chung Huang, Hsi-Chuan Lu
Source	Solid State Ionics Volume: 227, Pages: 10–16 Time of Publication: 2012-10
Abstract	In this study, introduction of tin ions in the SrCoO3 − δ oxide is attempted to modify its electrochemical behavior for serving as a cathode of intermediate-temperature solid oxide fuel cells (IT-SOFCs). Doping of tin ions appears to stabilize the cubic Pm-3m phase of the SrCo1 − ySnyO3 − δ ceramics but generates SrSnO3 precipitates and inhibits the grain growth as y value rises to a level greater than 10%. Obtained at 550 °C, the maximum electrical conductivity of SrCo0.95Sn0.05O3 − δ reads 545 S cm− 1. Single cells with a structure of NiO–Sm0.2Ce0.8O2 − δ (SDC)/SDC/SrCo0.95Sn0.05O3 − δ–SDC are built and characterized. Though SrCo0.95Sn0.05O3 − δ is regarded as an MIEC (mixed ionic/electronic conductivity material), adding SDC to SrCo0.95Sn0.05O3 − δ guarantees good adhesion to and fine electrical contact with the electrolyte layer, thereby contributing to the reduction in R0 and RP values. The single cell with the SrCo0.95Sn0.05O3 − δ–SDC composite cathode at 700 °C registers respectively an R0 value of 0.044 Ω cm2 and an RP value of 0.109 Ω cm2. In the absence of microstructure optimization and hermetic sealing of cells, a high power density of 0.847 W cm− 2 is reached. SrCo1 − ySnyO3 − δ thus emerges to be a promising cathode material for IT-SOFCs applications.
Keywords	Solid oxide fuel cell; Cathode; Impedance; Cell performance
Remark	Link

ID=190

Investigation of La1−xSrxCrO3−∂ (x ~ 0.1) as Membrane for Hydrogen Production

Authors	Yngve Larring, Camilla Vigen, Florian Ahouanto, Marie-Laure Fontaine, Thijs Peters, Jens B. Smith, Truls Norby and Rune Bredesen
Source	Membranes Volume: 2, Issue: 3, Pages: 665-686 Time of Publication: 2012-09
Abstract	Various inorganic membranes have demonstrated good capability to separate hydrogen from other gases at elevated temperatures. Hydrogen-permeable, dense, mixed proton-electron conducting ceramic oxides offer superior selectivity and thermal stability, but chemically robust candidates with higher ambipolar protonic and electronic conductivity are needed. In this work, we present for the first time the results of various investigations of La1−xSrxCrO3−∂ membranes for hydrogen production. We aim in particular to elucidate the material’s complex transport properties, involving co-ionic transport of oxide ions and protons, in addition to electron holes. This opens some new possibilities for efficient heat and mass transfer management in the production of hydrogen. Conductivity measurements as a function of pH2 at constant pO2 exhibit changes that reveal a significant hydration and presence of protons. The flux and production of hydrogen have been measured under different chemical gradients. In particular, the effect of water vapor in the feed and permeate gas stream sides was investigated with the aim of quantifying the ratio of hydrogen production by hydrogen flux from feed to permeate and oxygen flux the opposite way (“water splitting”). Deuterium labeling was used to unambiguously prove flux of hydrogen species.
Keywords	hydrogen transport membrane; proton permeation; oxygen permeation; water splitting
Remark	Link

ID=186

Effects of the microwave heating on the properties of gadolinium-doped cerium oxide prepared by polyol method

Authors	A. Gondolini, E. Mercadelli, A. Sanson, S. Albonetti, L. Doubova, S. Boldrini
Source	Journal of the European Ceramic Society Volume: 33, Issue: 1, Pages: 67–77 Time of Publication: 2013
Abstract	Gadolinium doped ceria (GDC) has received a lot of attention as possible electrolyte material for Intermediate-Temperature (500–800 °C) Solid Oxide Fuel Cells (IT-SOFC). Microwave heating has been recently considered in combination with precipitation for the production of oxide or non-oxide nano-powders. In this study, crystalline CeO2 powders doped with different amount of gadolinium were successfully prepared by microwave-assisted polyol method under mild conditions and in one single step. The microwave heating was found to strongly influence the morphological properties of the powder especially for low gadolinium content. IR and thermal analyses helped to identify the major reaction path for the formation of the as-observed complex morphologies. Regardless to the morphology, the powders showed good densification behavior and expected electrochemical properties; Ce0.9Gd0.1O1.95 exhibited the highest conductivity.
Keywords	Doped ceria; Microwave processing; Ionic conductivity; Fuel cells; Polyol method
Remark	Link

ID=184

Extending the family of oxygen ion conductors isostructural with La2Mo2O9

Authors	V.I. Voronkova, E.P. Kharitonova, E.I. Orlova, D.A. Belov
Source	Journal of Solid State Chemistry Volume: 196, Pages: 45–51 Time of Publication: 2012-12
Abstract	X-ray diffraction characterization of materials prepared by solid-state reactions in the ternary systems La2Mo2O9–Nd2W2O9–“Nd2Mo2O9” and La2Mo2O9–Pr2W2O9–Pr2Mo2O9 has shown that, in these systems, compounds isostructural with the oxygen ion conductor La2Mo2O9 exist in wide single-phase regions. Partial tungsten substitution for molybdenum may yield stable Ln2Mo2−2xW2xO9 compounds with the La2Mo2O9 structure, where Ln is a rare-earth element different from lanthanum and praseodymium, e.g., neodymium. Tungsten also stabilizes Pr2Mo2O9, which otherwise decomposes above 700 °C. A series of continuous solid solution was found in the La2Mo2O9–Pr2Mo2O9 system. Polymorphism of compounds existing in the above ternary systems was studied by differential scanning calorimetry. The conductivity of most of the compounds studied approaches that of lanthanum molybdate.
Remark	Link

ID=183

BaTiO3–Bi(Zn1/2Ti1/2)O3–BiScO3 Ceramics for High-Temperature Capacitor Applications

Authors	Natthaphon Raengthon, Tutu Sebastian, Denis Cumming, Ian M. Reaney, David P. Cann
Source	Journal of the American Ceramic Society Volume: 95, Issue: 11, Pages: 3554–3561 Time of Publication: 2012-09
Abstract	Ceramics based on solid solutions of xBaTiO3–(100−x)(0.5Bi(Zn1/2Ti1/2)O3–0.5BiScO3), where x = 50, 55, and 60 were prepared by solid-state reaction which resulted in a single perovskite phase with pseudocubic symmetry. Dielectric property measurements revealed a high relative permittivity (>1000), which could be modified with the addition of Bi(Zn1/2Ti1/2)O3 (BZT) and BiScO3 (BS) to engineer a temperature-stable dielectric response with a temperature coefficient of permittivity (TCε) as low as −182 ppm/°C. By incorporating 2 mol% Ba vacancies into the stoichiometry, the resistivity increased significantly, especially at high temperatures (>200°C). Vogel–Fulcher analysis of the permittivity data showed that the materials exhibited freezing of polar nanoregions over the range of 100–150 K. An analysis of optical absorption near the band edge for the Ba-deficient compositions suggested that the enhanced resistivity values were linked to a decrease in the concentration of defect states. An activation energy of ~1.4 eV was obtained from DC resistivity measurements suggesting that an intrinsic conduction mechanism played a major role in the high temperature conductivity. Finally, multilayer capacitors based on these compositions were fabricated, which exhibited dielectric properties comparable to the bulk material. Based on these results, this family of materials has great promise for high-temperature capacitor applications.
Remark	Link

ID=182

Sr1−xPrxCo0.95Sn0.05O3−δ ceramic as a cathode material for intermediate-temperature solid oxide fuel cells

Authors	Sea-Fue Wang, Yung-Fu Hsu, Hsi-Chuan Lu, Chien-Chung Huang, Chun-Ting Yeh
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 17, Pages: 12548–12556 Time of Publication: 2012-10
Abstract	In this study, the physical properties of the Sr1−xPrxCo0.95Sn0.05O3−δ ceramics were measured and their potential for use as a cathode material of intermediate-temperature solid oxide fuel cells (IT-SOFCs) was evaluated. A cubic phase was retained in all of the Sr1−xPrxCo0.95Sn0.05O3−δ ceramics. Analysis of the temperature-dependent conductivity found the SrCo0.95Sn0.05O3−δ and Sr0.9Pr0.1Co0.95Sn0.05O3−δ ceramics exhibiting semiconductor-like behavior below 550 °C and metal-like behavior above the same temperature. The Sr0.8Pr0.2Co0.95Sn0.05O3−δ and Sr0.7Pr0.3Co0.95Sn0.05O3−δ ceramics, however, reported a metal-like conductivity in the whole temperature range. The electrical conductivities of the Sr0.8Pr0.2Co0.95Sn0.05O3−δ ceramic at 500 °C and 700 °C read respectively 1250 S/cm and 680 S/cm, both of which were superior than those in most of the common perovskites. Single cells with a structure of NiO–Sm0.2Ce0.8O2−δ (SDC)/SDC/Sr0.8Pr0.2Co0.95Sn0.05O3−δ-SDC were built and characterized. Addition of SDC in Sr0.8Pr0.2Co0.95Sn0.05O3−δ emerged to be a crucial factor reducing the ohmic resistance (R0) and polarization resistance (RP) of the cell by facilitating a better adhesion to and electrical contact with the electrolyte layer. The R0 and RP of the cell read respectively 0.068 Ω cm2 and 0.0571 Ω cm2 at 700 °C and 0.298 Ω cm2 and 1.310 Ω cm2 at 550 °C. With no microstructure optimization and hermetic sealing of the cells, maximum power density (MPD) and open circuit voltage (OCV) reached respectively 0.872 W/cm2 and 0.77 V at 700 °C and 0.482 W/cm2 and 0.86 V at 550 °C. It is evident that Sr1−xPrxCo0.95Sn0.05O3−δ is a promising cathode material for IT-SOFCs.
Keywords	Solid oxide fuel cell; Cathode; Impedance; Cell performance
Remark	Link

ID=181

Nitrogen and hydrogen defect equilibria in Ca12Al14O33: a combined experimental and computational study

Authors	Jonathan M. Polfus , Kazuaki Toyoura , Charles H. Hervoches , Martin F. Sunding , Isao Tanaka and Reidar Haugsrud
Source	Journal of Materials Chemistry Volume: 22, Pages: 15828-15835 Time of Publication: 2012-07
Abstract	The defect structure of mayenite is investigated by Density Functional Theory (DFT) defect calculations; in situ electrical conductivity measurements in NH3 atmosphere at high temperature; and X-ray photoelectron spectroscopy (XPS) and gas phase mass spectrometry (GP-MS) of NH3 treated specimens. The computational results suggest that nitrogen is primarily incorporated substitutionally on oxygen sites as NH−2 and N3−. The concentration of nitrogen was estimated to be within the same order of magnitude by XPS, GP-MS and DFT, yielding a stoichiometry close to Ca12Al14O31.5N0.5:(NH2)0.5O0.5 which corresponds well with that obtained by Boysen et al. from similarly treated samples. Out diffusion of nitrogen was found to occur around 700 °C in Ar by XPS, GP-MS and conductivity measurements, also in accordance with Boysen et al. The conductivity measurements showed that NH3 treatment had a significant effect on the defect structure of the material which became evident only after replacing the NH3 atmosphere with Ar: the conductivity increased abruptly due to a temporary non-equilibrium reduction of the material as nitrogen diffuses out while the lack of a sufficiently large source of oxygen in the surrounding atmosphere prevents the specimen from re-oxidizing. Further, based on the computational results and the pH2 dependency on conductivity after NH3 treatment, we propose dissolution of hydride ions from H2 in the reduced and highly conductive post-NH3 state.
Remark	Link

ID=179

Fabrication, structural and electrical characterization of Lanthanum Tungstate films by Pulsed Laser Deposition

Authors	Einar Vollestad, Agnieszka Gorzkowska-Sobas, Reidar Haugsrud
Source	Thin Solid Films Volume: 520, Issue: 21, Pages: 6531–6534 Time of Publication: 2012-08
Abstract	Films of lanthanum tungstate, 3 μm in thickness, were fabricated by means of Pulsed Laser Deposition on a Pd foil. The films were characterized by X-ray diffraction, scanning electron microscopy, X-ray Photoelectron Spectroscopy and their electrical conductivity was measured at temperatures between 400 and 800 °C in different gas atmospheres. The films’ structure and electrical characteristics are close to what is reported in the literature for corresponding polycrystalline material. The films exhibit fairly high proton conductivity at elevated temperatures, which make them interesting for components in hydrogen-related technologies. Changes in microstructure and the crystallographic orientation observed at higher temperatures were accompanied by changes in the conductivity characteristics.
Keywords	Proton conducting oxide; ceramics; Hydrogen transport membrane; Films by Pulsed Laser Deposition; ionic conductor; lanthanum tungstate; La6WO12
Remark	Link

ID=178

Nd-doped Ba(Ce,Zr)O3 − δ proton conductors for application in conversion of CO2 into liquid fuels

Authors	Wojciech Zając , Emil Hanc, Agnieszka Gorzkowska-Sobas, Konrad Świerczek, Janina Molenda
Source	Solid State Ionics Volume: 225, Pages: 297–303 Time of Publication: 2012-10
Abstract	The paper presents crystal structure, transport properties, chemical stability in CO2 atmosphere and thin film membrane preparation for materials from the Ba(Ce1 − xZrx)0.9Nd0.1O2.95 (x = 0, 0.25, 0.5, 0.75, 1) group of perovskite-type structure oxides. Transformation of crystal structure from orthorhombic Pnma to orthorhombic Imma and cubic with increasing xZr was observed along with linear decrease of pseudo-cubic unit cell volume and free lattice volume. Electrical conductivity of bulk and grain boundary was determined in dry air, as well as in air humidified with H2O or D2O. The highest proton conductivity was observed for material with xZr = 0.25. Further increase of Zr content led to decrease of conductivity as high as 2 orders of magnitude. This effect was coupled with bell-shape dependence of activation energy and pre-exponential term. Such behavior was explained as superimposed effects of high proton mobility for zirconium-rich materials due to cubic symmetry and cerium-rich materials due to softness of oxygen–oxygen separation distance, along with high proton concentration for cerium-rich perovskites. The deteriorating effect of grain boundaries on total electrical conductivity was far more pronounced for Zr-rich materials than in the case of Ce-rich ones. Declining grain boundary conductivity was attributed to both increase of number of grain boundaries and decrease of inherent grain boundary conductivity for Zr-rich samples. The highest chemical stability in CO2 atmosphere was achieved for high-Zr content materials, on the contrary, for BaCe0.9Nd0.1O2.95 in CO2 atmosphere, the decomposition onset temperature was below 500 °C. 2 μm thin film membrane of Ba(Ce0.75Zr0.25)0.9Nd0.1O2.95 was successfully prepared on c-plane sapphire and fused silica substrates. Film's crystal structure matched that of the bulk material. The electrical conductivity of thermally treated film obtained on c-plane sapphire in wet air was 3.7 × 10− 4 S cm− 1 at 600 °C.
Keywords	Proton conductors; BaCeO3–BaZrO3 solid solutions; Isotope effect; Grain boundary effect; Thin films
Remark	Link

ID=176

Hydrogen permeation, transport properties and microstructure of Ca-doped LaNbO4 and LaNb3O9 composites

Authors	Wen Xing, Guttorm E. Syvertsen, Tor Grande, Zuoan Li, Reidar Haugsrud
Source	Journal of Membrane Science Volume: 415-416, Pages: 878–885 Time of Publication: 2012-10
Abstract	Two composites consisting of the proton conducting Ca-doped LaNbO4 and electron conducting LaNb3O9 with respectively 90 and 70 vol% LaNbO4 were prepared by spark plasma sintering. The amount of hydrogen produced at the sweep side was measured as a function of temperature and pH2 gradient under wet and dry sweep gas conditions. The hydrogen flux increases with increasing temperature and feed-sidepH2. The flux is significantly higher for the 70 vol% LaNbO4 composite than the 90 vol% LaNbO4 composite. Ambipolar conductivities calculated from the flux data showed the same pH2 dependence for both composites. The electrical conductivity of the 70 vol% LaNbO4 composite was characterized as a function of temperature under wet hydrogen. The microstructure and phase distribution of the two composites are analyzed and their transport properties with different flux limiting processes are discussed. An increased hydrogen production with wet compared to dry sweep gas is concluded to reflect water splitting due to transport of oxygen from the permeate to the feed side.
Keywords	Hydrogen flux; Proton conductivity; Ceramic-ceramic composite; LaNbO4; LaNb3O9; Ambipolar conductivity; Water splitting
Remark	Link

ID=174

High Power Plasma Sprayed Intermediate Temperature Solid Oxide Fuel Cells with Sm0.5Sr0.5CoO3-δ Cathode

Authors	Chang-sing Hwang , Chun-Huang Tsai, Chun-Liang Chang, Jen-Feng Yu, Sheng-Hui Nien
Source	Procedia Engineering Volume: 36, Pages: 81–87 Time of Publication: 2012-05
Abstract	The cells with porous Ni/Fe(∼10 wt%) metal plate as a supporting substrate, double layers of La0.75Sr0.25Cr0.5Mn0.5 O3-δ (LSCM) and nanostructured Ce0.55La0.45O2-δ/Ni (LDC/Ni) as an anode, LDC as an anode interlayer, La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) as an electrolyte, LSGM/Sm0.5Sr0.5CoO3-δ (SSC) as a cathode interlayer and SSC as a cathode current collector, were prepared by atmospheric plasma spraying (APS) coating processes followed by a heating treatment. The current-voltage-power and AC impedance measurement results show that the prepared cell heat-treated at 850 °C for 3 hours in air with a dead load of 1000 g cm-2 has an attracting performance. The measured maximum output power densities of this cell have reached 0.777, 0.742, 0.659, 0.542, 0.393, and 0.250 W cm-2 at 800, 750, 700, 650, 600, and 550 °C respectively. The measured ohmic and polarization resistances are 0.241, 0.254, 0.282, 0.328, 0.42, 0.62 and 0.055, 0.064, 0.083, 0.128, 0.23, 0.471 Ω cm2 at 800, 750, 700, 650, 600, and 550 °C respectively. After correction of the resistance inside the ProboStat system, the predicted actual maximum power densities that a cell can deliver are 1.95, 1.613, 1.186, 0.823, 0.512, and 0.293 W cm-2 at 800, 750, 700, 650, 600, and 550 °C respectively.
Keywords	Atmospheric plasma spray; solid oxide fuel cells; metal-supported; nanostructured; Sm0.5Sr0.5CoO3-δ
Remark	Link

ID=170

Polymorphism and Oxide Ion Migration Pathways in Fluorite-Type Bismuth Vanadate, Bi46V8O89

Authors	Xiaojun Kuang, Julia L. Payne, James D. Farrell, Mark R. Johnson, and Ivana Radosavljevic Evans
Source	Chem. Mater. Volume: 24, Issue: 11, Pages: 2162–2167 Time of Publication: 2012-05
Abstract	We report the synthesis, structural characterization, and ionic conductivity measurements for a new polymorph of bismuth vanadate Bi46V8O89, and an ab initio molecular dynamics study of this oxide ion conductor. Structure determination was carried out using synchrotron powder X-ray and neutron diffraction data; it was found that β-Bi46V8O89 crystallizes in space group C2/m and that the key differences between this and the previously reported α-form are the distribution of Bi and V cations and the arrangement of the VO4 coordination polyhedra in structure. β-Bi46V8O89 exhibits good oxide ion conductivity, with σ = 0.01–0.1 S/cm between 600 and 850 °C, which is about an order of magnitude higher than yttria stabilized zirconia. The ab initio molecular dynamics simulations suggest that the ion migration pathways include vacancy diffusion through the Bi–O sublattice, as well as the O2– exchanges between the Bi–O and the V–O sublattices, facilitated by the variability of the vanadium coordination environment and the rotational freedom of the VOx coordination polyhedra.
Keywords	Oxide ion conductors; bismuth vanadates; X-ray and neutron diffraction; AIMD simulations
Remark	Publication Date (Web): May 3, 2012 Link

ID=169

SrCo1−xSbxO3−δ cathode materials prepared by Pechini method for solid oxide fuel cell applications

Authors	Sea-Fue Wang, Hsi-Chuan Lu, Yung-Fu Hsu, Chien-Chung Huang, Chun-Ting Yeh
Source	Ceramics International Volume: 38, Issue: 7, Pages: 5941–5947 Time of Publication: 2012-09
Abstract	In this study, SrCo1−ySbyO3−δ powders were prepared by a modified Pechini method. According to the study results, the cubic Pm3m phase of the SrCo1−ySbyO3−δ ceramics was obtained as 10% of cobalt ions were substituted by antimony ions. Doping of Sb3+ ions appeared both to stabilize the Pm3m phase of the SrCo1−ySbyO3−δ ceramics and to enhance densification and retard grain growth. The coefficient of thermal expansion of the SrCo1−xSbxO3−δ ceramics increased with the content of the antimony ions, ranging from 10.17 to 15.37 ppm/°C at temperatures lower than the inflection point (ranging from 450 °C to 550 °C) and from 22.16 to 29.29 ppm/°C at higher temperatures. For the SrCo0.98Sb0.02O3−δ ceramic, electrical conductivity reached a maximum of 507 S/cm at 450 °C. The ohmic and polarization resistances of the single cell with the pure SrCo0.98Sb0.02O3−δ cathode at 700 °C read respectively 0.298 Ω cm2 and 0.560 Ω cm2. The single cell with the SrCo0.98Sb0.02O3−δ-SDC composite cathode appeared to reduce the impedances with the R0 and RP at 700 °C reading respectively 0.109 Ω cm2 and 0.127 Ω cm2. Without microstructure optimization and measured at 700 °C, the single cells with the pure SrCo0.98Sb0.02O3−δ cathode and the SrCo0.98Sb0.02O3−δ-SDC composite cathode, demonstrated maximum power densities of 0.100 W/cm2 and 0.487 W/cm2. Apparently, SrCo1−ySbyO3−δ is a potential cathode for use in IT-SOFCs.
Keywords	Solid oxide fuel cell; Cathode; Impedance; Cell performance
Remark	Available online 19 April 2012 Link

ID=168

Synthesis, Sintering, Transport Properties, and Surface Exchange of La2Ni0.9Cu0.1O4+δ

Authors	Zuoan Li, Truls Norby, Reidar Haugsrud
Source	Journal of the American Ceramic Society Volume: 95, Issue: 6, Pages: 2065–2073 Time of Publication: 2012-06
Abstract	Dense La2Ni0.9Cu0.1O4+δ ceramics were sintered from powders synthesized through a wet-chemical citrate nitrate route with optimized ratios of citrate to nitrate. Less citrate decreases the required sintering temperature and improves the oxygen permeativity. The oxygen permeation was measured as a function of oxygen activity gradient, membrane thickness (0.4–2.6 mm) and temperature (800°C–950°C). The oxygen self diffusion coefficient DO and the surface exchange coefficient k show Arrhenius-type behaviors with activation energies of ~50 and ~100 kJ/mol, respectively. The oxygen chemical diffusion coefficient Dchem and surface exchange coefficient kchem, measured by conductivity relaxation, exhibit Arrhenius-type behaviors with activation energies of 62 and 104 kJ/mol, respectively. Dchem and kchem are related to DO and k through the thermodynamic factor ωO.
Remark	Link

ID=167

LaCoO3 ceramics obtained from reactive powders

Authors	L. Predoana, B. Malic, D. Crisan, N. Dragan, M. Anastasescu, J. Calderon-Moreno, R. Scurtu, M. Zaharescu
Source	Ceramics International Volume: 38, Issue: 7, Pages: 5433–5443 Time of Publication: 2012-09
Abstract	The aim of the present study was to establishing the correlation between the structure and properties of the LaCoO3 powders obtained by aqueous sol–gel method with citric acid and their sintering behavior in order to obtain fully densified ceramics with perovskite structure. Two types of cobalt and lanthanum reagents were used in synthesis, namely nitrates and acetates. The sintering was realized at temperatures ranging between 800 and 1200 °C for 2 h. The sintered samples were investigated by classical ceramic methods (shrinkage, density, porosity) and by structural and morphological investigations: XRD, SEM, AFM and XPS. The electrical properties of the samples were determined by impedance spectroscopy. The ceramics obtained with powders starting with acetates have presented a lower sintering ability as compared with the samples obtained from powders starting with nitrates. LaCoO3 ceramics with best properties was obtained from powders starting with nitrates sintered at 1100 °C.
Remark	Available online 11 April 2012 Link

ID=166

Preparation and characterization of composite membranes based on sulfonated PEEK and AlPO4 for PEMFCs

Authors	Vijay Shankar Rangasamy, Savitha Thayumanasundaram, Niels De Greef, Jin Won Seo, Jean-Pierre Locquet
Source	Solid State Ionics Volume: 219, Pages: 83–89 Time of Publication: 2012-05
Abstract	Sulfonated poly(ether ether ketone) (PEEK) and their composites are considered one of the most promising alternatives for Nafion, the industry benchmark for electrolytic membranes in proton exchange membrane (PEM) fuel cells. In the present study, PEEK was non-homogeneously sulfonated using concentrated H2SO4 at different temperatures (room temperature, 60 °C, and 80 °C) and time durations (5, 7, 48, and 72 h). Composite membranes of SPEEK with different weight ratios of AlPO4 synthesized by sol–gel were also prepared. Depending on the degree of sulfonation (DS), the Ion Exchange Capacity (IEC) of the membranes varied from 1.06 to 2.9 meq g− 1. XRD results show the increasing amorphous nature of the membranes with increase in IEC and DS value. The water uptake of the membranes also increased with DS. Simultaneous TGA–FTIR measurement of the composite membranes showed better thermal stability compared to pure SPEEK membranes. The water uptake and proton conductivity of the composite SPEEK membranes were found to be lower than that of pure SPEEK membranes, while the composite membranes exhibited a better swelling behavior and mechanical stability than the pure SPEEK samples.
Keywords	Proton exchange membrane (PEM); Composite membranes; Sulfonated poly(etheretherketone) (SPEEK); Proton conductivity; Ion exchange capacity (IEC); Sol–gel
Remark	Link

ID=165

Synthesis and electrical properties of a new fluorite-like anionic conductor in the Nd2O3–MoO3 system (43–47 mol% Nd2O3)

Authors	V.I. Voronkova, , E.P. Kharitonova, D.A. Belov
Source	Solid State Ionics Volume: 225, Pages: 654–657 Time of Publication: 2012-10
Abstract	This work addresses phase relations in the Nd2O3–MoO3 system (25–50 mol% Nd2O3) and properties of a fluorite-like compound existing in this system in the composition range of 43–47 mol% Nd2O3. We describe for the first time the crystal growth of this compound. The composition of the crystals is Nd10Mo6O33 (Nd2O3:MoO3 = 5:6, 45.5 mol% Nd2O3), which falls within the above composition range. Dielectric spectroscopy data for polycrystalline Nd14Mo8O45 (within the homogeneity range of the fluorite-like compound) suggest a phase transition at 650–700 °C. The exact mechanism of the transition remains to be clarified. Nd14Mo8O45 has rather high bulk conductivity, approaching 10− 2 S/cm at 800 °C. The low activation energy and key structural features of the compound in question indicate that it is an anionic conductor.
Keywords	Fluorite-like compounds; Rare-earth molybdates; Single crystals; Relaxation; Anionic conductor
Remark	Available online 22 March 2012 Link

ID=164

Temperature dependent thermoelectric material power factor measurement system

Authors	Jonathan D'Angelo, Adam Downey, Timothy Hogan
Source	Review of scientific instruments Volume: 81, Issue: 075107 Publisher: American Institute of Physics, Time of Publication: 2010-06
Abstract	Thermoelectric materials can be used for cooling/heating applications, or converting waste heat into electricity. Novel thermoelectric materials have been discovered in recent years. Characterization of an electrical conductivity and thermopower of a sample from room temperature to ≥ 900 K is often necessary for thermoelectric materials. This paper describes a system built for measurement of the power factor of thermoelectric materials from 300 to 1273 K. Characterization results of the system are also presented.

ID=162

Stability of (Ln0.8Ca0.1Ln′0.1)2Ti2O7−δ (Ln=Dy, Yb; Ln′=Ce, Tb) and (Tb0.9Ca0.1)2Ti2O7−δ pyrochlores under redox conditions

Authors
Source	Solid State Ionics Volume: 225, Pages: 457–463 Time of Publication: 2012-10
Abstract	The stability of (Ln0.8Ca0.1Ln′0.1)2Ti2O7−δ (Ln=Dy, Yb; Ln′=Ce, Tb) pyrochlores under different redox conditions (air, dry and wet H2) has been studied. The bulk conductivity of the terbium-containing materials is slightly higher under reducing conditions (5% H2 + 95% Ar) than in air, reaching ~ 6 × 10− 2 and 2.5 × 10− 2 S/cm at 800 °C for (Yb0.8Ca0.1Tb0.1)2Ti2O7−δ and (Dy0.8Ca0.1Tb0.1)2Ti2O7−δ, respectively. In air–hydrogen–air cycles, the bulk conductivity returns to its original level in air: ~ 2 × 10− 2 and 1 × 10− 2 S/cm at 800 °C in (Yb0.8Ca0.1Tb0.1)2Ti2O7−δ and (Dy0.8Ca0.1Tb0.1)2Ti2O7−δ, respectively. Exposure of (Dy0.8Ca0.1Tb0.1)2Ti2O7−δ to a flowing mixture of 5% H2 and 95% Ar for 100 h slightly reduces its conductivity: from 0.029 to 0.023 S/cm at 900 °C. The cerium-containing materials (Yb0.8Ca0.1Ce0.1)2Ti2O7−δ and (Dy0.8Ca0.1Ce0.1)2Ti2O7−δ were found to be unstable under reducing conditions. The bulk conductivity of (Yb0.8Ca0.1Ce0.1)2Ti2O7−δ is practically independent on the atmosphere while the grain boundary conductivity increased from 5.6 × 10− 8 in air to ~ 1 × 10− 5 S/cm at 425 °C on reducing the sample in 5%H2–Ar gas mixture. However, after two redox cycles air–5%H2–Ar–air the sintered pellet of (Yb0.8Ca0.1Ce0.1)2Ti2O7−δ fractured whereas (Dy0.8Ca0.1Ce0.1)2Ti2O7−δ degraded immediately under reducing conditions. It was observed that the size mismatch between Ln and Ln´ cations strongly affects the bulk to grain boundary conductivity ratio in (Ln0.8Ca0.1Ln′0.1)2Ti2O7−δ (Ln=Dy, Yb; Ln′=Ce, Tb) pyrochlores.
Keywords	Pyrochlore; Donor doping; High-temperature conductivity; Ionic conductivity; Solid electrolyte; Electronic conductivity
Remark	Available online 8 March 2012; http://dx.doi.org/10.1016/j.ssi.2012.02.009 Link

ID=161

Spark Plasma Sintering and Hot Pressing of Hetero-Doped LaNbO4

Authors
Source	Journal of the American Ceramic Society Volume: 95, Issue: 5, Pages: 1563–1571 Time of Publication: 2012-05
Abstract	LaNbO4/La3NbO7 and LaNbO4/LaNb3O9 cer-cer composites were prepared by impregnating Ca-doped LaNbO4 powder, synthesized by spray pyrolysis, with La- or Nb-precursor solutions. The sintering of the calcined powders was investigated by dilatometry, and dense composites were prepared by conventional sintering, hot pressing, and spark plasma sintering. The particle size of the starting powders was about 50 nm, and the average grain size of the dense materials ranged from 100 nm and upwards, depending on the sintering temperature, sintering procedure, and the phase composition. The unit cell parameters of LaNbO4 showed a finite size effect and approached the cell parameters of tetragonal LaNbO4 with decreasing crystallite size, both for the single-phase material and the composites. The minority phase (La3NbO7 or LaNb3O9) were observed as isolated grains and accumulated at triple points and not along the grain boundaries, pointing to a large dihedral angle between the phases. The calcium-solubility in the minority phases was larger than in LaNbO4, which corresponds well with previous reports. The electrical conductivity of the hetero-doped materials was similar to, or lower than, that for Ca-doped LaNbO4.
Remark	Link

ID=160

Sandvik Sanergy HT – A potential interconnect material for LaNbO4-based proton ceramic fuel cells

Authors	Anders Werner Bredvei Skilbred, Reidar Haugsrud
Source	Journal of Power Sources Volume: 206, Pages: 70–76 Time of Publication: 2012-05
Abstract	High temperature properties of Sandvik Sanergy HT have been studied to evaluate the alloy's suitability as an interconnect material for LaNbO4 based proton ceramic fuel cells (PCFCs). The thermal expansion behavior of the alloy deviates from LaNbO4 at higher temperatures which may be unfavorable, however the average values for the two materials over the whole temperature region are rather similar. The oxidation kinetics was parabolic and the rate constants were low at temperatures below 1000 °C. Accelerated oxidation was encountered after 300 h at 1000 °C revealing that the material may undergo severe degradation at sufficiently high temperatures. A complex oxide scale containing an inner layer of chromium oxide and an outer layer of various spinel phases containing chromium, manganese and iron was formed at all temperatures. As a consequence of high oxidation resistance and an oxide with relatively high electronic conductivity, the area specific resistance (ASR) of Sandvik Sanergy HT measured at 700 °C proved to be low.
Keywords	Proton ceramic fuel cell; Interconnect; Sandvik Sanergy HT; Oxidation kinetics; Thermal expansion; Area specific resistance
Remark	Link

ID=159

A novel perovskite-based proton conductor for solid oxide fuel cells

Authors	Ramya Hariharan, T.R.S. Prasanna, Prakash Gopalan
Source	Scripta Materialia Volume: 66, Issue: 9, Pages: 658–661 Time of Publication: 2012-05
Abstract	A perovskite-based electrolyte, Ca-substituted YAlO3, has been synthesized by the citrate gel process. The conductivity of Y0.9Ca0.1AlO3-δ has been studied by AC impedance spectroscopy in controlled atmospheres in the temperature range 300–800 °C. The material has been found to be a mixed conductor with dominant p-type electronic conduction at elevated temperatures and a combined protonic conduction below 600 °C in wet conditions. The H/D isotope effect on conductivity confirms the presence of protonic conductivity between 400 and 600 °C.
Keywords	Proton conduction; Electrical properties; Solid electrolyte; Perovskite oxide; Fuel cell materials
Remark	Link

ID=158

50 mol% indium substituted BaTiO3: Characterization of structure and conductivity

Authors	S.M.H. Rahman, C.S. Knee, I. Ahmed, S.G. Eriksson, R. Haugsrud
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 7975–7982 Time of Publication: 2012-05
Abstract	BaTi0.5In0.5O3−δ was prepared by solid state reaction at 1400 °C. Rietveld analysis of high resolution X-ray powder diffraction data indicated phase pure as-prepared material that adopts a cubic perovskite structure with a = 4.1536(1) Å. Thermogravimetric analysis revealed the presence of significant levels of protons in the as-prepared material and 57% of the theoretically achievable protonation was attained on exposure to a humid environment at 185 °C. After hydration the cell parameter increased to 4.1623(1) Å. Electrical conductivity was measured both with fixed and variable frequency ac impedance methods as a function of temperature, oxygen-, water vapour- and heavy water vapour partial pressures. In the temperature range 400–800 °C a slight increase in the total conductivity with increasing oxygen partial pressure is encountered, characteristic of a contribution from p-type charge carriers. The effect of the water vapour pressure on conductivity below 600 °C is much more prominent indicative of dominant proton conduction. At 300 °C the total conductivity in wet O2 was estimated to be 9.30 × 10−5 S/cm. At T > 800 °C the material is a pure oxide ion conductor.
Keywords	Barium titanate; Perovskite; Brownmillerite; Proton conductivity; X-ray diffraction; Impedance spectroscopy
Remark	Link

ID=157

Ion mobility, phase transitions, and conductivity of crystal phases in KF-CsF-SbF3-H2O system according to data of NMR and impedance spectroscopy

Authors	V. Ya. Kavun, L. A. Zemnukhova, A. I. Ryabov, A. B. Podgorbunskii, S. V. Gnedenkov, S. L. Sinebryukhov and V. I. Sergienko
Source	Russian Journal of Electrochemistry Volume: 48, Issue: 1, Pages: 104-110 Time of Publication: 2012-01
Abstract	The methods of NMR, thermogravimetric analysis, and impedance spectroscopy were used to study ion mobility, phase transitions, and ion conductivity in crystal phases in the KF-CsF-SbF3-H2O system. Analysis of 19F NMR spectra allowed tracing the dynamics of ion movement in the fluoride sublattice under temperature variations, determining their types and temperature ranges, in which they are implemented. The observed phase transitions in potassium-cesium fluoroantimonates(III) are phase transitions to the superionic state. It is found that the predominant form of ion movement in the high-temperature modifications formed as a result of phase transitions becomes diffusion of fluoride ions. According to the results of electrophysical studies the K1−xCsx SbF4 (x ≤ 0.2) high-temperature phases are superionic. Their conductivity reaches the values of ∼10−2 to 10−3 S/cm at 463–483 K. The high-temperature phases are stabilized under cooling, which results in a significant increase in conductivity at the room temperature.
Keywords	potassium-cesium tetrafluoroantimonates(III) – ion mobility – phase transitions – conductivity – NMR spectra
Remark	DOI: 10.1134/S1023193512010090 Link

ID=156

Defect structure and its nomenclature for mixed conducting lanthanum tungstates La28–xW4+xO54+3x/2

Authors
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 8051–8055 Time of Publication: 2012-05
Abstract	Based on results from experimental and theoretical studies of the crystal structure of lanthanumtungstateView the MathML source, we present a defect model comprising an inherently disordered and partially occupied oxide ion sublattice, which rationalizes hydration and ionic conduction of the materials in the undoped state. Applying the model to experimental conductivity data enables extraction of defect thermodynamics and transport parameters of protons, oxide ions and electronic defects. The standard enthalpy and entropy changes of the hydration of inherent oxygen vacancies are estimated to be −83 kJ/mol and −125 J/mol K (per mole of H2O), respectively.
Keywords	Lanthanum tungstate; Defect structure; Inherent disorder; Partial occupancy; Mixed conductor
Remark	Link

ID=155

The role of B-site cations on proton conductivity in double perovskite oxides La2MgTiO6 and La2MgZrO6

Authors
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 7983–7994 Time of Publication: 2012-05
Abstract	Acceptor-doped La2MgTiO6 (LMTO) and La2MgZrO6 (LMZO) have been investigated to contribute to clarify the role of the B-site cations in A2B′B″O6 double perovskite oxides on formation and mobility of protons. Thermogravimetry and a.c. conductivity measurements in the temperature range 1000-300 °C, as well as DFT-calculations of LMTO, have been the basis for evaluating hydration thermodynamics and transport parameters of the materials. Both compounds show exothermic hydration of oxygen vacancies, but low concentrations of protons. The proton transport is limited by relatively high activation energies of mobility; 0.84 eV and 0.78 eV for LMTO and LMZO, respectively. This is suggested to reflect association to effectively negative charged defects formed by site exchange among the B-site cations. Consequently, the maximum proton conductivity of LMTO and LMZO is in the order of 10−5 S/cm.
Keywords	Double perovskite; La2MgTiO6; La2MgZrO6; Proton mobility; Hydration thermodynamics
Remark	Link

ID=154

Influence of Microwave-Assisted Pechini Method on La0.80Sr0.20Ga0.83Mg0.17O3–δ Ionic Conductivity

Authors
Source	Fuel Cells Volume: 12, Issue: 1, Pages: 54–60 Time of Publication: 2012-02
Abstract	With the aim of investigating the microwave influence on the electrolyte material properties, La0.80Sr0.20Ga0.83Mg0.17O2.815 was prepared by both a conventional and a microwave-assisted sol–gel Pechini method. With respect to the conventional Pechini method (hereafter SGP), the microwave assisted process (hereafter MWA-SGP) guaranteed a faster procedure, reducing the time needed to remove the excess solvents to complete the polyesterification reaction from some days to a few hours. In fact, when a MWA-SGP method was used, powders having higher phase purity were obtained. The sintering process at 1,450 °C of the powders prepared by both methods yielded pellets with similar density values (≥92% of theoretical). Nevertheless, only by microwave-assisted process single-phase products were obtained and no secondary phases such as tetragonal LaSrGaO4 and LaSrGa3O7 were detected. These by-products have been demonstrated to be detrimental for conductivity. Indeed, pellets obtained by MWA-SGP method showed oxygen ionic conductivity values higher (about 30–40%) than those checked for SGP samples, thus demonstrating the important role of the microwave process on reducing time and costs and on improving the electrolyte properties.
Keywords	Ionic Conductivity;IT-SOFC;Microwave Processing;(Sr, Mg)-Doped LaGaO3;Sol–Gel
Remark	Link

ID=152

On the hydration of grain boundaries and bulk of proton conducting BaZr0.7Pr0.2Y0.1O3-δ

Authors
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 7970–7974 Time of Publication: 2011-12
Abstract	We report here for the first time bulk and grain boundary conductivities from impedance spectra of a ceramic proton conductor (BaZr0.7Pr0.2Y0.1O3-δ) taken during hydration and H/D isotope exchange transients (at 400 °C). The results suggest that water moves quickly along grain boundary cores, and then interact from there with the space charge layers and, in turn, grain interiors. Hydration and H/D isotope exchange have simple monotonic effects on the bulk conductivity in line with what is expected from it being dominated by protons. The transients for grain boundary conductivity exhibit however hysteresis: During hydration, the core charge and grain boundary resistance appear to go through transient minima related to non-equilibrium distributions of defects between the core and grain interior – notably because protons diffuse faster than oxygen vacancies between the grain boundary and grain interior. At equilibrium, hydration increases the core charge and the depletion of positive charge carriers in the space charge layers. During H/D isotope exchange relatively fast hysteretic transients indicate that the space charge layers experience changes in charge carrier (D+ vs. H+) mobility as well as in D2O vs. H2O hydration thermodynamics.
Keywords	BaZrO3, Pr-substituted, acceptor-doped; BaZr0.7Pr0.2Y0.1O3-δ; Proton conductivity; Grain boundaries, space charge layer; Hydration; Impedance spectroscopy
Remark	Link

ID=150

Dielectric Relaxation in BaTiO3–Bi(Zn1/2Ti1/2)O3 Ceramics

Authors	Natthaphon Raengthon, David P. Cann
Source	Journal of the American Ceramic Society Volume: 95, Issue: 5, Pages: 1604–1612 Time of Publication: 2012-05
Abstract	A dramatic improvement in the dielectric and electrical properties has been observed in ceramics of 0.8BaTiO3–0.2Bi(Zn1/2Ti1/2)O3 through the introduction of Ba vacancies. It possesses a high relative permittivity (εr > 1150) along with a low dielectric loss (tan δ < 0.05) that is maintained up to temperatures as high as 460°C. It is also characterized by a high resistivity of 70 GΩ-cm, which remains constant up to 270°C. Analysis of complex impedance (Z) and complex electric modulus (M) data, measured over the frequency range of 1–106 Hz, revealed a number of important findings. At high temperatures (T > 255°C), a complex plane analysis of Z″ versus Z′ and the frequency dependence of Z″ suggests an electrically inhomogeneous microstructure for the stoichiometric composition. The stoichiometric composition exhibited activation energies of ~1 eV which suggests an extrinsic conduction mechanism. However, the introduction of Ba vacancies resulted in electrically homogeneous microstructure. An overlap of the Z″ and M″ peaks in the frequency domain and much larger activation energies were observed, on the order of half of the band gap, suggesting an intrinsic conduction mechanism. A more detailed analysis of the data reveals insights into the physical mechanisms underpinning the dielectric and ac conductivity.
Remark	Link

ID=148

Fabrication and electrochemical properties of cathode-supported solid oxide fuel cells via slurry spin coating

Authors	Min Chen, Jing-Li Luo, Karl T. Chuang, Alan R. Sanger
Source	Electrochimica Acta Volume: 63, Pages: 277–286 Time of Publication: 2012-02
Abstract	A cathode-supported SOFC consisting of LSM (La0.8Sr0.2MnO3-δ) cathode supporter, LSM-Sm0.2Ce0.8O2-δ (SDC) cathode functional layer (CFL), yttria stabilized zirconia (YSZ)/SDC bi-layered electrolyte and Ni-YSZ anode layer was fabricated by a slurry spin coating technique. The influence of the porosity in both the CFL and cathode supporter on the electrochemical properties of the cells has been investigated. It was found that properly controlling the porosity in the CFL would improve the performance of the cells using O2 in the cathode side (O2-cells), with a maximum power density (MPD) value achieving as high as 0.58 W•cm−2 at 850 °C. However, this improvement is not so evident for the cells using air in the cathode side (air-cells). When increasing the porosity in the cathode-supporter, a significant increase of the power density for the air cells due to the decreasing Rconc,c(concentration polarization to the cell resistance) can be ascertained. In terms of our analysis on various electrochemical parameters, the Ract (activation polarization to the cell resistance) is assumed to be mainly responsible for the impedance arcs measured under the OCV condition, with a negligible Rconc,cvalue being able to be detected in our impedances. In this case, a significant decreasing size of the impedance arcs due to the increasing porosity in the cathode supporter would correspond to a decrease of the Ract values, which was proved to be induced by the decreasingRconc,c.
Keywords	Slurry spin coating; Cathode-supported SOFC; Concentration polarization; Activation polarization; Power density
Remark	Link

ID=145

The effect of cation non-stoichiometry in LaNbO4 materials

Authors
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 8017–8026 Time of Publication: 2012-05
Abstract	The effect of cation non-stoichiometry in LaNbO4 was investigated by impregnating nano-crystalline LaNbO4 with small amounts of La3+, Nb5+ and Ca2+ oxide precursors. The sintering properties of the modified LaNbO4 powders were investigated by dilatometry, and the microstructure and phase composition were studied by electron microscopy and X-ray diffraction. The electrical properties of the materials were studied by 4-point DC-conductivity and 2-point 4-wire AC-conductivity at elevated temperatures in controlled atmosphere. Minor variations in the cation stoichiometry were shown to have a pronounced effect on both the sintering properties as well as the electrical conductivity. Addition of CaO, which introduced secondary phases above 0.25 mol% CaO, increased the sintering temperature and improved the conductivity of the materials. La2O3- and Nb2O5-excess materials did not show large variation in the electrical conductivity relative to pure LaNbO4, while the sintering properties were strongly affected by the nominal La/Nb ratio in LaNbO4. The present findings demonstrate the sensitivity of cation non-stoichiometry in materials with limited solid solubility.
Keywords	LaNbO4; Proton conductivity; Phase purity; Solid solubility
Remark	Link

ID=144

Effects of surface coatings on the determination of Dchem and kchem in La2NiO4+δ by conductivity relaxation

Authors	Zuoan Li, Reidar Haugsrud
Source	Solid State Ionics Volume: 206, Pages: 67-71 Time of Publication: 2012-01
Abstract	In this work, we utilize surface modification to accurately determine oxygen diffusivity and surface exchange in La2NiO4 + δ by transient conductivity. To achieve ‘instantaneous’ gas exchange in the reaction cell, a total pressure change was adopted instead of exchange of gas mixtures at 1 atm. Conductivity relaxation measurements were performed in the temperature range of 600–900 °C and at oxygen partial pressures of 0.2, 1.0 and 1.9 atm. Due to the large uncertainties associated with deriving oxygen chemical diffusion and surface coefficients simultaneously, we limited the relaxation to pure bulk diffusion control by coating nano-grained La2NiO4 + δ particles on the sample surface. After determining Dchem, kchem was derived by fitting the relaxation data of the uncoated sample. The transient experiments via both oxidation (a step change of pO2 from 0.2 to 1.0 atm) and reduction (1.9 to 1.0 atm) give consistent results of Dchem and kchem showing Arrhenius-type behaviour with activation energies of ~ 90 kJ/mol and ~ 150 kJ/mol, respectively.
Keywords	Conductivity relaxation; Surface modification; Surface exchange; Oxygen diffusion; La2NiO4 + δ
Remark	Link

ID=143

Hydration and proton conductivity in LaAsO4

Authors
Source	Journal of Materials Chemistry Volume: 22, Issue: 4, Pages: 1652-1661 Time of Publication: 2012-04
Abstract	Incorporation and transport of protonic defects have been studied in nominally undoped and 1 and 3 mol% Sr-doped LaAsO4 prepared by a co-precipitation route. AC impedance of the materials was measured as a function of temperature (1150 to 400 °C), pO2 (1 to 1 × 10−5 atm) and pH2O (0.025 to 3 × 10−5 atm). The bulk conductivities generally decrease with decreasing temperature and moreover with decreasing pH2O within the whole temperature range. At the highest temperatures, a small decrease in the conductivity with decreasing pO2 was also observed. The defect structure of Sr-doped LaAsO4 appears to be dominated by oxygen vacancies in the form of pyroarsenate ions, As2O4−7, in dry atmospheres at high temperatures and by protonic defects in the form of hydrogen arsenate ions, HAsO2−4, in wet atmospheres. A significant isotope effect shows that protons contribute to the total conductivity at all temperatures under wet conditions and predominate at temperatures below [similar]850 °C. The remaining contributions are attributed to oxide ions and electron holes. The extracted hydration thermodynamics are comparable to those determined for other LnXO4 (X = P, V, Nb, Ta) compounds, and the enthalpy of mobility of protons (86 ± 5 and 88 ± 5 kJ mol−1 for the 1 and 3 mol% doped samples, respectively) follows an apparent trend for the isostructural LaXO4 (X = P, As, V) series with the enthalpy of mobility of protons decreasing with increasing radius of the X-site cation. However, the partial proton conductivities of Sr-doped LaAsO4 are lower than those determined for acceptor doped LaPO4 and LaVO4 for which the possible reasons are discussed.
Remark	Link

ID=142

Evaluation of the electrode/electrolyte contact quality in solid oxide fuel cells

Authors	Jacqueline Amanda Figueiredo dos Santos, Michel Kleitz, Tulio Matencio, Rosana Zacarias Domingues
Source	Electrochimica Acta Volume: 60, Pages: 224–229 Time of Publication: 2012-01
Abstract	Symmetrical cells have been prepared by depositing suspensions with different active powder concentrations (50% and 60% by weight respectively) of lanthanum strontium cobalt iron oxide (La0.6Sr0.4Co0.2Fe0.8O3-δ) on identical yttria stabilized zirconia pellets (LSCF/YSZ/LSCF). Their impedance characteristics are compared to that of a symmetrical cell with platinum electrodes deposited on a similar zirconia pellet (Pt/YSZ/Pt). The LSCF cells show different values of the electrolyte resistance. Referring to the electrolyte resistance obtained with the Pt cell and assuming that this value corresponds to almost perfect electrode/electrolyte contacts, it is possible to estimate the Effective Conducting Area (ECA) of the electrodes. The use of the ECA parameter allows a better comparison of the electrode polarizations.
Keywords	solid oxide fuel cells; porous electrodes; cathode
Remark	Link

ID=141

Influence of Pr substitution on defects, transport, and grain boundary properties of acceptor-doped BaZrO3

Authors
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 7962–7969 Time of Publication: 2012-05
Abstract	We report on effects of partially substituting Zr with the multivalent Pr on the conductivity characteristics of acceptor (Gd) doped BaZrO3-based materials. BaZr0.6Pr0.3Gd0.1O3−δ was sintered 96% dense at 1550 °C with grains of 1–4 μm. The electrical conductivity was characterised by impedance spectroscopy and EMF transport number measurements as a function of temperature and the partial pressures of oxygen and water vapour. H2O/D2O exchanges were applied to further verify proton conduction. The material is mainly a mixed proton–electron conductor: the p-type electronic conductivity is ∼0.004 and ∼0.05 S/cm in wet O2 at 500 and 900 °C, respectively, while the protonic conductivity is ∼10−4 S/cm and ∼10−3 S/cm. The material is expectedly a pure proton conductor at sufficiently low temperatures and wet conditions. The specific grain boundary conductivity is essentially equal for the material with or without Pr, but the overall resistance is significantly lower for the former. We propose that replacing Pr on the Zr site reduces the grain boundary contribution due to an increased grain size after otherwise equal sintering conditions.
Keywords	BaZrO3; BaPrO3; Defects and transport; Grain boundaries; Grain boundary specific conductivity
Remark	Link

ID=140

Effects of A and B site acceptor doping on hydration and proton mobility of LaNbO4

Authors	Morten Huse, Truls Norby, and Reidar Haugsrud
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 9, Pages: 8004–8016 Time of Publication: 2012-05
Abstract	Acceptor doping of the high temperature proton conductor LaNbO4 has been studied by impedance spectroscopy in various atmospheres at 300–1100 °C and by X-ray powder diffraction and scanning electron microscopy. Doping LaNbO4 on both A and B site (with Ca and Ti, respectively) resulted in a two-phase composition of LaNbO4 and LaNb3O9. This composite is interesting as the two phases make it a mixed proton and electron conductor. The electrical characterisation of Ti-doped LaNbO4 revealed mixed electronic (n- and p-type) and ionic conductivity at temperatures above approx. 750 °C, while proton conductivity was dominating below this temperature under wet conditions. Ti-doping resulted in higher activation enthalpy and lower mobility of protons as compared to Ca-doping, attributed to stronger proton–acceptor association in the former case. Thermodynamic constants for hydration of associated protons and proton–acceptor association as well as mobility parameters were fitted to the experimental data and came out as , , , and , and . Neither B site doping nor A and B site co-doping showed indications of increased solubility relative to sole A site doping in LaNbO4.
Keywords	LaNbO4; Ti-doped LaNbO4; Defect association; Proton mobility; Proton conductivity; Hydration thermodynamics
Remark	Link

ID=139

Effects of (LaSr)(CoFeCu)O3-δ Cathodes on the Characteristics of Intermediate Temperature Solid Oxide Fuel Cells

Authors	Sea-Fue Wang, Chun-Ting Yeh, Yuh-Ruey Wang, Yung-Fu Hsu
Source	Journal of Power Sources Volume: 201, Pages: 18–25 Time of Publication: 2012-03
Abstract	In this study, Cu2+ ions doped La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes are prepared for use in solid oxide fuel cells (SOFCs). The maximum electrical conductivities of the La0.6Sr0.4Co0.2Fe0.7Cu0.1O3−δ (438 S cm−1) and the La0.6Sr0.4Co0.1Fe0.8Cu0.1O3−δ (340 S cm−1) discs are higher than that of the La0.6Sr0.4Co0.2Fe0.8O3−δ disc (LSCF; 81 S cm−1) sintered at 1100 °C. The substitution of Cu2+ over Fe3+ leads to a higher coefficients of thermal expansion (CTE), while the replacement of Co3+ by Cu2+ results in a lower CTE. Single cells with the La0.6Sr0.4Co0.2Fe0.8O3−δ, La0.6Sr0.4Co0.2Fe0.7Cu0.1O3−δ, and La0.6Sr0.4Co0.1Fe0.8Cu0.1O3−δ cathodes operating at 650 °C and 550 °C show similar ohmic resistance (R0) values while the polarization resistance (RP) values of the cells with the La0.6Sr0.4Co0.2Fe0.7Cu0.1O3−δ and a0.6Sr0.4Co0.1Fe0.8Cu0.1O3−δ cathodes are slightly lower than that of the single cell with the La0.6Sr0.4Co0.2Fe0.8O3−δ cathode, indicating that the Cu2+-doped LSCF cathode exhibits a greater electrochemical catalytic activity for oxygen reduction. Maximum power densities of the cells with the La0.6Sr0.4Co0.2Fe0.8O3−δ, La0.6Sr0.4Co0.2Fe0.7Cu0.1O3−δ, and La0.6Sr0.4Co0.1Fe0.8Cu0.1O3−δ cathodes operating at 700 °C read respectively 1.07, 1.15, and 1.24 W cm−2. It is evident that the doping of Cu2+ ions in LSCF is beneficial to the electrochemical performance of the cells.
Keywords	Solid oxide fuel cell; cathode; cathode; impedance; Cell performance
Remark	Link

ID=138

Synthesis and Enhanced Proton Conduction in a 20 mol% Ytterbium Doped Barium Zirconate Ceramic Using Zn as Sintering Aid

Authors	Seikh M.H. Rahman, Istaq Ahmed, Sten G. Eriksson
Source	Applied Mechanics and Materials Mechanical and Aerospace Engineering Volume: 110-116 Time of Publication: 2011-10
Abstract	20% Ytterbium (III)-doped perovskite structured barium zirconate, BaZrO3, was prepared by two different synthesis routes: solid state and sol-gel routes. 2 % Zinc (II) was added as an acceptor dopant at the Zr (IV) site according to stoichiometry. It was also added as 2 % excess of the formula. The purpose of this study is to see how zinc (II) acts as a sintering aid in view of synthesis route, densification and conductivity of the material. A dense ceramic (90% of theoretical density) was achieved by the sol-gel method when stoichiometry was adjusted. Phase purity of the samples was checked by X-ray powder diffraction (XRD). Thermogravimetric analysis (TGA) and Impedance spectroscopy (IS) was used to characterize hydration and electrical conductivity respectively.The data shows that the addition of stoichiometric amounts of Zn2+ via sol-gel synthesis route promotes not only densification but also water incorporation and conductivity in comparison with the solid state route, keeping the same final sintering temperature of 1500°C. For example, pre-hydrated BaZr0.78Zn0.02Yb0.2O3-δ, prepared via the sol-gel method shows total conductivity (σtot) value of 3.1410-5 and 3.810-3 Scm-1, whereas for the solid state route, σtot values are 1.7410-5 and 8.8710-4 Scm-1 under dry Ar (heating cycle) at 300° C and 600° C, respectively.
Keywords	BaZrO3, Impedance Spectroscopy, Proton Conductivity, Sintering Aid, TGA, X-Ray Diffraction (XRD)
Editor	Wu Fan
Remark	Online since October, 2011; DOI 10.4028/www.scientific.net/AMM.110-116.1181 Link

ID=137

Effect of nano-grain size on the ionic conductivity of spark plasma sintered 8YSZ electrolyte

Authors	K. Rajeswari, M. Buchi Suresh, Dibyendu Chakravarty, Dibakar Das, Roy Johnson
Source	International Journal of Hydrogen Energy Volume: 37, Issue: 1, Pages: 511–517 Time of Publication: 2012-01
Abstract	Densification and micro-structural development of ultra fine 8 mol% yttria stabilized zirconia (8YSZ) nano powder were investigated systematically by varying the SPS sintering temperature at constant applied pressure of 50 MPa. A hundred fold decrease in average grain size ranging from 10 μm to 80 nm is observed on decreasing the SPS sintering temperature from 1200 °C to 1050 °C with >99% of theoretical densities. Impedance measurements on the samples indicated an enhancement in the ionic conductivity at 700 °C from 0.004 S/cm to 0.018 S/cm with decrease in grain size from 10 μm to 0.51 μm and a significant increase in conductivity from 0.018 S/cm to 0.068 S/cm on further reduction of grain size to 80 nm. A significant change in the grain-boundary conductivity is noticed on reducing the grain sizes to nano regime. The diverse microstructure with ultra fine grain size resulting from SPS at 1050 °C could contribute to the enhanced ionic conductivity, which is supported by the activation energy data.
Keywords	Solid oxide fuel cells; Electrolyte; Microstructure; Spark plasma sintering
Remark	Link

ID=134

Post-heat treatment pressure effect on performances of metal-supported solid oxide fuel cells fabricated by atmospheric plasma spraying

Authors	Chun-Huang Tsai, Chang-sing Hwang, Chun-Liang Chang, Jen-Feng Yu, Sheng-Hui Nien
Source	Journal of Power Sources Volume: 197, Pages: 145–153 Time of Publication: 2012-01
Abstract	The nickel metal-supported cells fabricated by atmospheric plasma spraying are post-heat treated in air at 960 °C for 2 h with different pressures. The current–voltage–power and AC impedance measurements show the prepared cell with an applied pressure of 450 g cm−2 in the post-heat treatment has a better electrochemical performance at test temperatures ≥ 650 °C. For test temperatures < 650 °C, the maximum power densities at 450 g cm−2 pressure are about the same as the maximum power densities at 1250 g cm−2 pressure. The SEM micrograph indicates that the cathode including the cathode interlayer and the cathode collector is the most porous region in the cell. AC impedance results show this cathode is the most sensitive part to the applied pressure in the post-heat treatment and the cell with 450 g cm−2 pressure has the smallest low frequency intercept R2 and the polarization resistance Rp at temperatures from 600 to 800 °C. The performance durability test of the cell post-heat treated at 450 g cm−2 pressure shows a degradation rate of 0.0087 mV h−1 or 0.0026 mW h−1 at 300 mA cm−2 constant current density and 750 °C test temperature.
Keywords	Atmospheric plasma spray; Solid oxide fuel cells; Metal-supported; Nanostructured
Remark	Link

ID=130

Structure, chemical stability and mixed proton–electron conductivity in BaZr0.9−xPrxGd0.1O3−δ

Authors
Source	Journal of Power Sources Time of Publication: 2011-08
Abstract	BaZr0.9−xPrxGd0.1O3−δ (x = 0.3 and 0.6) was prepared by combustion synthesis and characterised with respect to conductivity and stability in an attempt to combine the desirable properties of the end members. The polycrystalline materials exhibit a cubic or pseudo-cubic structure as determined by X-ray synchrotron radiation and transmission electron microscopy. The chemical stability of the compositions is strongly dependent on the praseodymium content, the materials with more Pr present lower stability. Electron holes dominate the conductivity under oxidising atmospheres in BaZr0.3Pr0.6Gd0.1O3−δ, while BaZr0.6Pr0.3Gd0.1O3−δ exhibits a mixed electron hole–proton conducting behaviour. Substitution of Zr by Pr in acceptor-doped BaZrO3 decreases the sintering temperature and increases the grain growth rate.
Remark	Article in press, DOI:10.1016/j.jpowsour.2011.06.076

ID=129

Impedance and modulus spectroscopic studies on 40PrTiTaO6 + 60YTiNbO6 ceramic composite

Authors	D. B. Dhwajam, M. Buchi Suresh, U. S. Hareesh, J. K. Thomas, S. Solomon, Annamma John
Source	Journal of Materials Science: Materials in Electronics Volume: 23, Issue: 3, Pages: 653-658 Time of Publication: 2012-03
Abstract	The 40PrTiTaO6 + 60YTiNbO6 ceramic composite is prepared through the solid state ceramic route. The structure is discussed using X-ray diffraction analysis. Surface morphology is examined by Scanning Electron Microscopy (SEM). Impedance and modulus spectroscopic studies are carried out. A decrease in the resistive behavior of the sample assisted by the grain boundary conduction with rise in temperature is found. The experimental results on electrical properties indicate that the material exhibits conduction both due to bulk and grain boundary effect. The microstructure was investigated by SEM micrographs in which grains separated by grain boundaries are visible. There is a probable change in the capacitance values of the material as a function of temperature. The relaxation time is small at higher temperatures than at lower temperatures. The activation energy is found as 1.52 eV, which suggests the possibility of electrical conduction due to the mobility of oxide ions (O2−) or oxide ion vacancies at higher temperature.
Remark	Link

ID=128

Proton Conductivity in Acceptor-Doped LaVO4

Authors	Morten Huse, Truls Norby, and Reidar Haugsrud
Source	J. Electrochem. Soc. Volume: 158, Issue: 8, Pages: B857-B865 Time of Publication: 2011-06
Abstract	Electrical characterization of nominally undoped LaVO4, La0.99Ca0.01VO4− and La0.95Ca0.05VO4− was performed in various partial pressures of oxygen, water vapor and hydrogen isotopes, from 300 to 1100°C by impedance spectroscopy, AC conductivity measurements (10 kHz) and EMF-measurements. XRD, SEM and EDS were used for structural, micro structural and compositional analysis. Acceptor doped LaVO4 is a pure ionic conductor in oxidizing atmospheres in the entire measured temperature range; dominated by proton conductivity at low temperatures (T < 450°C) under wet conditions and oxide ion conductivity at high temperatures. A maximum in the partial proton conductivity of ~ 6 × 10−5 S/cm was reached at 900°C (pH2O2.5·10-2 atm). Thermodynamics of hydration and transport parameters for charge carriers in La0.99Ca0.01VO4 were derived from relations between defect chemistry, transport properties and the measured conductivity data and revealed: S=− 130 ± 10 J/mol K, S =− 142 ± 10 J/mol K, H=− 110 ± 10 kJ/mol, µ0,H+ = 50 ± 6 cm2 K/Vs, Hmob,H+ = 75 ± 10 kJ/mol, µ0,v= 120 ± 20 cm2 K/Vs and Hmob,v = 85 ± 10 kJ/mol. The tetrahedron (XO4) volume and migration enthalpy were found to be correlated for the series of monoclinic LaXO4.

ID=127

Nanostructuring phenomena in oxygen-conducting complex oxides of heavy REE

Authors	A. V. Shlyakhtina, D. A. Belov, S. Yu. Stefanovich and L. G. Shcherbakova
Source	Russian Journal of Electrochemistry Volume: 47, Issue: 5, Pages: 620-627 Time of Publication: 2011-05
Abstract	In complex oxides of REE (Ln4M3O12 (Ln = Tm, Lu; M = Zr, Hf), Ln2TiO5 (Ln = Er-Yb)) and Ho2TiO5, the following phase transitions of the order-disorder type are studied for different cooling rates: rhombohedral δ-phase-defective fluorite in Ln4M3O12 (Ln = Tm, Lu; M = Zr, Hf), pyrochlor-like phasedefective fluoride in Ln2TiO5 (Ln = Er-Yb), and hexagonal β-phase-pyrochlor in Ho2TiO5. The presence of nanostructuring phenomena typical of fluorite-like polymorphous modifications of complex oxides in the Ln2O3-MO2 (Ln = Ho-Lu; M = Ti, Zr, Hf) systems is confirmed. The conductivity of polymorphous modifications of Ln4Zr3O12 (Ln = Tm, Lu;) and Ln2TiO5 (Ln = Ho-Yb) with different thermal prehistory is studied. The comparative studies of the oxygen-ionic conductivity of fluorite- and pyrochlor-like Ln2TiO5 (Ln = Ho-Yb), pyrochlor Ho2TiO5, and β-Ho2TiO5 and also of the conductivity of fluorite-like compounds and δ-Ln4Zr3O12 (Ln = Tm, Lu) are carried out. The oxygen-ionic conductivity of complex oxides in the Ln2O3-MO2 (Ln = Er-Lu; M = Ti, Zr, Hf) system is shown to decrease in the following series: defective pyrochlor-defective fluorite-rhombohedral δ-phase ∼ hexagonal β-phase.

ID=125

Phase transition and electrical properties of gallium- and indium-doped Bi10Ti3W3O30

Authors	E. P. Kharitonova, D. A. Belov, A. V. Mosunov and V. I. Voronkova
Source	Inorganic Materials Volume: 47, Issue: 5, Pages: 513-520 Time of Publication: 2011-05
Abstract	Polycrystalline samples of gallium- and indium-doped Bi10Ti3W3O30 (mixed-layer Aurivillius phase with the Ti4+ and W6+ distributed at random over the perovskite-like slabs) have been prepared by solid-state reactions, and their polymorphism and electrical properties have been studied. Doping with both In3+ and Ga3+ yields limited solid solutions and shifts the ferroelectric phase transition to lower temperatures. The heterovalent substitutions of In3+ and Ga3+ for Ti4+ and W6+ increase the oxygen vacancy concentration and, accordingly, the conductivity of the material relative to the undoped compound.

ID=124

Lamellar Titanates: A Breakthrough in the Search for New Solid Oxide Fuel Cell Anode Materials Operating on Methane

Authors
Source	Advanced Energy Materials Volume: 1, Issue: 4, Pages: 573–576 Time of Publication: 2011-07
Abstract	Decreasing the dimensionality of the LaxSr1–xTiOmath image family structure from 3D to 2D by increasing the La content greatly enhances the electrochemical performance of the material as an SOFC anode. This is attested to by the strong decrease in the polarization resistance values deduced from the complex impedance spectra (Nyquist plot) recorded at 900 °C in H2/H2O(3%) on a symmetrical cell.
Keywords	Solid oxide fuel cells; Anode materials; Titanate; Methane
Remark	Link

ID=122

Microwave-assisted synthesis of gadolinia-doped ceria powders for solid oxide fuel cells

Authors	A. Gondolini, E. Mercadelli, A. Sanson, S. Albonetti, L. Doubova and S. Boldrini
Source	Ceramics International Volume: 37, Issue: 4, Pages: 1423-1426 Time of Publication: 2011-05
Abstract	Gadolinia doped ceria (GDC) is an attractive electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) for its high ionic conductivity at low temperature (500–700 °C). A number of different methods are currently used to prepare nano-sized doped-ceria powder. Among the others, precipitation in solution remains the best method to obtain well-dispersed particles of controlled properties. In this work, nanocrystalline Ce1−xGdxO2−δ (GDC) particles were produced by polyol microwave assisted method in very mild conditions (170 °C, 2 h, 1 atm). The as-synthesized powder showed good sinterability and ionic conductivity comparable to the ones of the corresponding nanometric commercial GDC.
Keywords	GDC; Microwave heating; Polyol method; IT-SOFC

ID=120

Conductivity, transport number measurements and hydration thermodynamics of BaCe0.2Zr0.7Y(0.1 − ξ)NiξO(3 − δ)

Authors	S. Ricotea, The Corresponding Author, N. Bonanos, H.J. Wang and R. Haugsrud
Source	Solid State Ionics Volume: 185, Issue: 1, Pages: 11-17 Time of Publication: 2011-03
Abstract	BaCe0.2Zr0.7Y(0.1 − ξ)NiξO(3 − δ) compounds with ξ = 0.01 and 0.02 have been synthesized by solid state reaction at 1400 °C and sintered at 1450 °C. TEM analyses were performed and showed a segregation of nickel at the grain boundaries for ξ = 0.02. This apparent solubility limit of Ni in the B-site of the perovskite is in agreement with similar data obtained earlier for the two compositions. The first aim of this work was to evaluate the conductivity of BaCe0.2Zr0.7Y(0.1 − ξ)NiξO(3 − δ) at temperature between 500 and 900 °C, using impedance spectroscopy at different oxygen partial pressures and water vapor pressures, as well as the emf technique. The compounds exhibit p-type conduction in oxidizing atmosphere, and ionic conduction elsewhere. The oxide ion contribution of the conductivity is negligible only for temperatures below 600 °C. The determination of hydration enthalpies, our second goal, was achieved by modelling of the conductivity data and by thermogravimetric measurements (TG-DSC).

ID=117

Structure, Water Uptake, and Electrical Conductivity of TiP2O7

Authors
Source	Journal of the American Ceramic Society Volume: 94, Issue: 5, Pages: 1514–1522 Time of Publication: 2011-05
Abstract	We report here on the structure of TiP2O7 and electrical properties of nominally acceptor (Sc, Fe)-doped TiP2O7 synthesized by an aqueous phosphoric acid route. Structural characterization, including studies of the high-temperature phase transition in TiP2O7, was carried out by powder X-ray and neutron diffraction. Ceramic disks were sintered by the spark plasma technique and their conductivities were characterized as a function of p(O2) and p(H2O) in the temperature range of 500°–1000°C by means of AC constant frequency measurements and impedance spectroscopy. As reported earlier, the acceptor doping appears not to influence the defect structure of TiP2O7 significantly. Effects of H+/D+ isotope shift were utilized to identify proton conduction. The conductivity was independent of p(O2) at 500°–900°C under oxidizing conditions suggesting predominantly protonic conduction at these temperatures. Under reducing atmosphere n-type conductivity contributed to the total conductivity at the higher temperatures. p(H2O) dependencies of the conductivities are interpreted in terms of a defect-chemical model involving protons and oxygen interstitials as the dominating defects. The uptake of water was studied by thermogravimetry at high p(H2O) and the thermodynamics of the hydration reaction was derived. Finally, parameters for the mobility of protons were extracted by combining the conductivity and thermogravimetry data.
Remark	Link

ID=116

Microstructural characterization and electrical properties of spray pyrolyzed conventionally sintered or hot-pressed BaZrO3 and BaZr0.9Y0.1O3 − δ

Authors
Source	Solid State Ionics Volume: 182, Issue: 1, Pages: 32-40 Time of Publication: 2011-02
Abstract	A spray pyrolysis route to BaZrO3 (BZ) and BaZr0.9Y0.1O2.95 (BZY) powders was developed starting from nitrate solutions. Homogeneous powders with a grain size of ~ 100 nm were achieved. A calcination of the powder was necessary to remove carbonates formed during the spray pyrolysis. Hot pressing was in comparison with conventional sintering more effective to enhance densification and suppress grain growth, and dense (> 96%) materials with homogeneous microstructure were obtained. The Y-substitution decreased the densification rate. Minor amounts of a secondary phase was observed at the grain boundary triple points of BZY, but the grain boundaries were otherwise found to be coherent and without significant secondary phase accumulation. Impedance spectroscopy vs T, pO2 and pH2O of conventionally sintered BZ and hot-pressed BZY demonstrated that the conductivity of BZ was orders of magnitude lower than compared to BZY. The conductivity of BZ displayed mixed proton and p-type electronic conduction characteristics in the grain interior which was depressed at the grain boundaries. The grain boundaries showed an additional n-type electronic conduction under reducing conditions. The conductivity characteristics were according to core-space charge layer theory. BZ seems to exhibit a larger ratio of p-type electronic to protonic conduction as compared to BZY, contrary to the prediction of simple defect chemistry.

ID=114

Synthesis and characterization of Ca-substituted YAlO3 by pechini route for solid oxide fuel cells

Authors	Ramya Hariharan, Prakash Gopalan
Source	Solid State Sciences Volume: 13, Issue: 1, Pages: 168-174 Time of Publication: 2011-01
Abstract	The high operating temperature requirement of solid oxide fuel cells demands electrolyte materials stable at temperatures around 800 °C. The perovskite material YAlO3, with yttrium ion on the A-site and the aluminium ion on the B-site is being investigated as an electrolyte for solid oxide fuel cells. This work investigates the structure and electrical conductivity of undoped and Ca-doped YAlO3 compositions that has been synthesized by the Pechini route. The samples have been investigated by X-ray diffraction studies. The electrical conductivity studies have been performed using a.c impedance spectroscopy in the range 200–800 °C in air. The doped YAlO3 of composition x = 0.1 exhibits a total conductivity of about 2.2 mS/cm at 800 °C. The microstructural evaluation of the samples has been conducted by scanning electron microscopy coupled with energy dispersive spectrum analysis.

ID=112

δ-Phase to defect fluorite (order–disorder) transition in the R2O3–MO2 (R = Sc; Tm; Lu; M = Zr; Hf) systems

Authors	A.V. Shlyakhtina, D.A. Belov, S.Yu. Stefanovich, I.V. Kolbanev, O.K. Karyagina, A.V. Egorov, S.V. Savilov and L.G. Shcherbakova
Source	Materials Research Bulletin Volume: 46, Issue: 4, Pages: 512–517 Time of Publication: 2011-04
Abstract	We have studied the δ-phase to defectfluoriteF* (order–disorder) transition in the R4M3O12 (R = Sc, Tm, Lu; M = Zr, Hf) compounds. The temperature of the δ–F* phasetransition in Tm4Zr3O12 is ∼1600 °C. The rate of this transition in R4Zr3O12 (R = Sc, Tm, Lu) decreases markedly with decreasing difference in ionic radius between the R3+ and Zr4+, leading to stabilization of the δ-phasesR4Zr3O12 with R = Sc and Lu at high temperatures (∼1600 °C). During slow cooling (5 °C/h), the high-temperature defectfluoritesF-R2Hf2O7 (R = Tm, Lu) decompose reversibly to form the δ-phasesR4Hf3O12. Some of the materials studied exhibit microdomains formation effects, typical of the fluorite-related oxide compounds in the R2O3–MO2 (M = Ti, Zr, Hf) systems of the heavy rare earths. The high-temperature defectfluoritesF-R4M3O12 (R = Tm, Lu; M = Zr, Hf) as a rule contain antiphase microdomains of δ-R4Zr3O12. After slow cooling (5 °C/h), such microdomains are large enough for the δ-phase to be detected by X-ray diffraction. The conductivity data for R4M3O12 (R = Sc, Tm, Lu; M = Zr, Hf) and Ln2Hf2O7 (Ln = Dy, Lu) prepared by different procedures show that the rhombohedral phasesδ-R4M3O12 (R = Sc, Tm, Lu; M = Zr, Hf) are poorer conductors than the defectfluorites, with 740 °C conductivity from 10−6 to 10−5 S/cm. The conductivity drops with decreasing rare-earth ionic radius and, judging from the Ea values obtained (1.04–1.37 eV), is dominated by oxygen ion transport. The highest conductivity, ∼6 × 10−4 S/cm at 740 °C, is offered by the rapidly cooled F*-Dy2Hf2O7. In the fluorite homologous series, oxygen ion conductivity decreases in the orderdefect pyrochlore > defectfluorite > δ-phase.
Keywords	Fluorite; δ-Phases R4M3O12; Pyrochlore; Order–disorder transition; Antiphase microdomains; High-temperature conductivity
Remark	Link

ID=111

Polymorphism and high-temperature conductivity of Ln2M2O7 (Ln = Sm─Lu; M = Ti, Zr, Hf) pyrochlores

Authors	A.V. Shlyakhtina, L.G. Shcherbakova
Source	Solid State Ionics Volume: 192, Issue: 1, Pages: 200–204 Time of Publication: 2011-06
	Pyrochlore; Fluorite; Order─disorder; Defects; High-temperature conductivity; Ionic conductivity; Solid electrolyte

ID=110

Proton conductivity in Sm2Sn2O7 pyrochlores

Authors	K.E.J. Eurenius, E. Ahlberg and C.S. Knee
Source	Solid State Ionics Volume: 181, Issue: 35-36, Pages: 1577-1585 Time of Publication: 2010-11
Abstract	The electrical conductivity of the pyrochlore systems, Sm2Sn2O7, Sm1.92Ca0.08Sn2O7 − δ and Sm2Sn1.92Y0.08O7 − δ was studied using impedance spectroscopy under wet and dry gas (O2 and Ar) in the temperature range 150–1000 °C. Enhancements of the bulk conductivity of all samples at temperatures up to ~ 550 °C were observed for wet conditions consistent with significant levels of proton conduction. The presence of dissolved protons in the acceptor-doped materials, Sm1.92Ca0.08Sn2O7 − δ and Sm2Sn1.92Y0.08O7 − δ, is supported by infrared spectroscopy and thermogravimetric analysis. Proton conduction was confirmed by isotope effects under heavy water (O2/D2O and Ar/D2O). The A-site substituted sample Sm1.92Ca0.08Sn2O7 − δ yielded the highest levels of proton conduction and displayed mixed ionic and electronic conduction under dry oxidising conditions. Electron hole conduction dominates in dry oxygen for Sm2Sn1.92Y0.08O7 − δ and Sm2Sn2O7. For the A-site doped sample bulk and grain boundary conduction could be separated. The specific grain boundary conduction was calculated using the brick layer model and was found to be two orders of magnitude lower compared to the bulk conductivity. The unexpected increase in conductivity seen for the undoped sample under wet gas is discussed in the context of structural disorder and possible filling of the un-occupied anion site in the pyrochlore structure by OH-groups.
Keywords	Sm2Sn2O7; Proton conductor; Pyrochlore; Oxide ion conductivity; p-type conductivity; Infra-red spectroscopy; Thermogravimetric analysis

ID=108

Directed integration of ZnO nanobridge sensors using photolithographically patterned carbonized photoresist

Authors	Chien-Chih Huang, Brian D Pelatt and John F Conley Jr
Source	Nanotechnology Volume: 21, Issue: 19 Time of Publication: 2010-05
Abstract	A method for achieving large area integration of nanowires into electrically accessible device structures remains a major challenge. We have achieved directed growth and integration of ZnO nanobridge devices using photolithographically patterned carbonized photoresist and vapor transport. This carbonized photoresist method avoids the use of metal catalysts, seed layers, and pick and place processes. Growth and electrical connection take place simultaneously for many devices. Electrical measurements on carbonized photoresist/ZnO nanobridge/carbonized photoresist structures configured as three-terminal field effect devices indicate bottom gate modulation of the conductivity of the n-type ZnO channel. Nanobridge devices were found to perform well as ultraviolet and gas sensors, and were characterized as regards ultraviolet light pulsing, oxygen concentration, and humidity. The sensitivity of the three-terminal nanobridge sensors to UV light and oxygen was enhanced by application of a negative bottom gate voltage.

ID=107

Yttria-stabilized zirconia thin film electrolyte produced by RF sputtering for solid oxide fuel cell applications

Authors	Federico Smeacetto, Milena Salvo, Lakshmi Chandru Ajitdoss, Sergio Perero, Tomasz Moskalewicz, Stefano Boldrini, Lioudmila Doubova and Monica Ferraris
Source	Materials Letters Volume: 64, Issue: 22, Pages: 2450-2453 Time of Publication: 2010-11
Abstract	Thin film (40–600 nm) yttria-stabilized zirconia (YSZ) electrolytes for solid oxide fuel cells (SOFC) were deposited on NiO-YSZ anodes and fused silica substrates by RF sputtering, using low applied power without the use of post deposition annealing heat treatment. YSZ film showed a nanocrystalline structure and consisted of the Zr.85Y.15O1.93 (fcc) phase. The film was dense and the YSZ/anode interface was continuous and crack free. According to preliminary in-plane conductivity measurements (temperature range 550–750 °C) on the YSZ film, the activation energy for ionic conduction was found to be 1.18 ± 0.01 eV.
Keywords	Thin films; Ceramics; Microstructure; Nanomaterials

ID=106

High-temperature proton conductivity and defect structure of TiP2O7

Authors	Vajeeston Nalini, Reidar Haugsrud and Truls Norby
Source	Solid State Ionics Volume: 181, Issue: 11-12, Pages: 510-516 Time of Publication: 2010-04
Abstract	Nominally undoped TiP2O7 and TiP2O7 with 2 mol-% substitution of Ti by Al were synthesized from TiO2 (Al2O3) and H3PO4(aq), sintered at 1050 °C, and characterized by XRD, TEM and SEM. The electrical conductivity was investigated at 300–1000 °C as a function of p(O2), p(H2O), and p(D2O). The material's phase transition around 700 °C is clearly visible in the conductivity curves. Al substitution hardly increased the conductivity. The conductivity was higher in H2O- than in D2O-containing and dry atmospheres, indicating the dominance of proton conduction. The conductivity was accordingly mainly independent of p(O2). A slight increase in the conductivity with decreasing p(O2) at the highest temperatures was indicative of a minor contribution of n-type electronic conduction. The p(H2O) and temperature dependencies of the conductivity have been modelled as a sum of proton and electron partial conductivities under a situation with protons charge compensated by oxygen interstitials as dominating defects.
Keywords	Titanium pyrophosphate; TiP2O7; Al-substituted TiP2O7; Proton conduction; Defect structure

ID=105

Scandium stabilized zirconium thin films formation by e-beam technique

Authors	Darius Virbukas, Giedrius Laukaitis, Julius Dudonis, Oresta Katkauskė and Darius Milčius
Source	Solid State Ionics Volume: 184, Issue: 1, Pages: 10–13 Time of Publication: 2011-03
Abstract	Scandiumstabilizedzirconium (10ScSZ) thin ceramic films were deposited by e-beam evaporation of (ZrO2)0.90(Sc2O3)0.10 micro powder (particle size 0.5 ÷ 0.7 μm). The influence of deposition rate on formed thinfilms microstructure and electrical properties was studied. 10ScSZ thinfilms were deposited on two types of different substrates: optical quartz (SiO2) and Alloy-600 (Fe–Ni–Cr) substrates. Deposition rate was changed from 2 to 16 Å/s to test its influence on thinfilmformation and its properties. The microstructure of formed 10ScSZ thin ceramic films was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrical parameters of formed thin ceramics were investigated in the frequency range from 0.1 Hz to 1.0 MHz (in temperature range from 473 to 873 K). The ionic conductivity of the deposited electrolyte 10ScSZ thinfilms was determined by impedance spectroscopy. It was determined that the deposition rate (in range from 2 to 16 Å/s) has influence on crystallite size. It increases by increasing the deposition rate from 18.4 to 26.9 nm. The XRD measurements show that the formed 10ScSZ thinfilms do not repeat the crystallographic phase of the initial evaporated powder material—it is changes from rhombohedra (initial powder) to cubic (the formed thinfilms).
Keywords	Scandium stabilized zirconium (ScSZ); Ionic conductivity; Electron beam deposition; Solid oxide fuel cells (SOFC)
Remark	Link

ID=104

Effect of sintering temperature and sintering additives on ionic conductivity of LiSi2N3

Authors	Eiichirou NARIMATSU, Yoshinobu YAMAMOTO, Toshiyuki NISHIMURA and Naoto HIROSAKI
Source	Journal of the Ceramic Society of Japan Volume: 118 , Issue: 1381 , Pages: 837-841 Time of Publication: 2010-09
Abstract	The effect of sintering temperature and sintering additives on the ionic conductivity of LiSi2N3 was studied by performing complex impedance measurements. LiSi2N3 materials were fabricated by the reaction of Li3N, Si3N4, and sintering additives at temperatures of 1873–2073 K. Dense hot-pressed bodies were obtained at 1973–2073 K in the case of undoped LiSi2N3 and at 1873 K in the case of Y2O3, CaF2, and B2O3 addition. The ionic conductivity increased greatly with increasing sintering temperature and exhibited a strong dependence on the type of sintering additive. When the sintering temperature was constant at 1873 K, although the conductivities of Y2O3-doped LiSi2N3 and CaF2-doped LiSi2N3 were lower than that of undoped LiSi2N3, the conductivity of B2O3-doped LiSi2N3 was higher than that of undoped LiSi2N3. The enhanced conductivity of B2O3-doped LiSi2N3 can be attributed to the increase in the density of the sintered material without the formation of a phase of significant resistance at the grain boundaries.
Remark	Link

ID=103

Defects and transport properties of Sr-doped LaP3O9

Authors	Vajeeston Nalini, Reidar Haugsrud and Truls Norby
Source	Solid State Ionics Volume: 181, Issue: 27-28, Pages: 1264-1269 Time of Publication: 2010-09
Abstract	LaP3O9 and 2 mol-% Sr-doped LaP3O9 have been synthesized by the solid-state reaction method and the phase purity was characterized by powder X-ray diffraction and scanning electron microscopy. The AC conductivity of sintered disks was measured with two-point electrode setup in the temperature range 300 − 700 °C under oxidizing and reducing conditions at different oxygen and water vapor (H2O or D2O) partial pressures by means of impedance spectroscopy. The water vapor dependency and isotope effect reveal that protons are the predominant charge carrier. The conductivity was mainly independent of the partial pressure of oxygen at all measured temperatures under both oxidizing and reducing conditions, suggesting only minor electronic conductivity. Hydration thermodynamics and transport parameters for the Sr-doped sample have been determined based on a defect chemical model applied to thermogravimetry and conductivity data.
Keywords	Proton conductivity; LaP3O9; Sr-doped LaP3O9; Defect structure; Thermodynamic relations; Transport parameters

ID=102

Charge carriers in grain boundaries of 0.5% Sr-doped LaNbO4

Authors	Harald Fjeld, Despoina Maria Kepaptsogloub, Reidar Haugsrud and Truls Norby
Source	Solid State Ionics Volume: 181, Issue: 3-4, Pages: 104-109 Time of Publication: 2010-02
Abstract	The grain boundary and grain interior conductivities of La0.995Sr0.005NbO4 − δ have been studied by means of impedance spectroscopy at 400 °C after quenching from different pH2O, pO2 and temperatures. Effects of H/D isotope shifts on the conductivity were, moreover, determined from 400 to 480 °C under isothermal conditions. The microstructure and composition were characterized by scanning electron microscopy and transmission electron microscopy. On basis of the effects of pH2O and H/D isotope exchange on the grain boundary and grain interior conductivities, it is concluded that protons are the major charge carrier and, furthermore, that they are relatively more predominating in the grain boundaries than in the grain interior. Ionic transport in the grain boundaries is discussed in terms of the grain boundary core–space charge layer model.
Keywords	LaNbO4; Grain boundaries; Impedance spectroscopy; TEM; Space charge effects

ID=101

Electrical Properties and Gas Sensing Characteristics of the Al2O3/4H SiC Interface Studied by Impedance Spectroscopy

Authors
Source	Materials Science Forum Silicon Carbide and Related Materials 2009 Volume: 645 - 648, Pages: 531-534 Time of Publication: 2010-04
Abstract	Using impedance spectroscopy (IS) for characterization of the electrical properties and gas sensing characteristics of Al2O3/4H-SiC (MOS) structures, insight on the capacitive and resistive contributions in the interfacial region of the MOS structures is obtained. Applying DC bias voltages between accumulation and depletion (corresponding to the interfacial region) allows investigation of the voltage shift of the capacitance versus voltage (CV) curve at different temperatures and atmospheres. This voltage shift forms the basis to use the MOS structure as a gas sensor. The MOS capacitance, as extracted from IS data, is different from the one obtained using CV measurements, due to the ability of distinguishing the resistive contribution (using IS). Voltage shifts between 1 and 2 V are clearly revealed during exposure to hydrogen and oxygen, and this shift exhibits a long-term stability of operation at temperatures up to 500°C. Hence, Al2O3 exhibits great promise as a gate dielectric in MOS-based gas detecting devices for use at elevated temperatures.
Keywords	Impedance Spectroscopy, MOS Capacitor

ID=100

Improved Proton Conductivity in Spark-Plasma Sintered Dense Ceramic BaZr0.5In0.5O3−delta

Authors	Istaq Ahmed, Francis G. Kinyanjui, Patrick Steegstra, Zhijian J. Shen, Sten-G. Eriksson, and Mats Nygren
Source	Electrochem. Solid-State Lett. Volume: 13, Issue: 11, Pages: B130-B134 Time of Publication: 2010-11
Abstract	Spark-plasma sintering method was used to prepare dense proton conducting perovskite oxide BaZr0.5In0.5O3−delta. Analysis of X-ray powder diffraction data showed that the sample adopt the cubic crystal structure having the space group Pm[overline 3]m. Thermogravimetric analysis of prehydrated samples showed significant mass losses beyond 300°C due to loss of protons as water vapor. Scanning electron microscope images show that the grain size of the spark-plasma sintered dense sample was smaller than that of solid-state sintered porous sample. The highest total proton conductivity (2×10−3 S cm−1 at 450°C) was found for dense spark-plasma sintered sample under wet H2 than the samples prepared by other routes.

ID=96

Correlation between microstructure and electrical conductivity in composite electrolytes containing Gd-doped ceria and Gd-doped barium cerate

Authors	Mudrika Khandelwal, A. Venkatasubramanian, T.R.S. Prasanna and P. Gopalan
Source	Journal of the European Ceramic Society Volume: 31, Issue: 4, Pages: 559–568 Time of Publication: 2011-04
	Composite; Ceria; Impedance spectroscopy; Electrical conductivity; Fuel cell
Remark	Link

ID=94

The properties of scandium and cerium stabilized zirconium thin films formed by e-beam technique

Authors	Darius Virbukas, Giedrius Laukaitis, Julius Dudonis and Darius Milčius
Source	Solid State Ionics Volume: 188, Issue: 1, Pages: 46–49 Time of Publication: 2011-04
Abstract	Scandium and ceriumstabilizedzirconium (10Sc1CeSZ) thin ceramic films were formed evaporating (ZrO2)0.89(CeO2)0.01(Sc2O3)0.10 micro powder using e-beam evaporation technique. The influence of deposition rate on formedthinfilms electrical properties and microstructure was studied. 10Sc1CeSZ thinfilms were deposited on two types of different substrates: optical quartz (SiO2) and Alloy 600 (Fe–Ni–Cr). Deposition rate was changed from 2 to 16 Å/s to understand its influence on thinfilm formation and other properties. The formed 10Sc1CeSZ thinfilms keep the cubic crystal structure as the initial evaporated powder material but change the main crystallographic peak from (111) to (200) for both types of substrate and used deposition rates. It was determined that the crystallites size increases from 19.0 to 24.9 nm and from 15.6 to 19.9 nm on optical quartz and Alloy 600 respectively by increasing the deposition rate (in range from 2 to 16 Å/s). The thinfilm density decreases by increasing the deposition rate. The ionic conductivity of 10Sc1CeSZ thinfilms was determined by impedance spectroscopy in the frequency range from 0.1 Hz to 1.0 MHz in temperature range from 473 K to 873 K. The best ionic conductivity σtot = 4.91 · 10− 2 Sm− 1 at 873 K temperature and the lowest value of activation energy ΔEa = 0.88 eV were found for 10Sc1CeSZ thinfilmsformed at 4 Å/s deposition rate.
Keywords	Scandium and cerium stabilized zirconium (10Sc1CeSZ); Electron beam deposition; Solid oxide fuel cells (SOFC); Ionic conductivity
Remark	Link

ID=93

Ethanol internal steam reforming in intermediate temperature solid oxide fuel cell

Authors	Stefan Diethelm, Jan Van Herle
Source	Journal of Power Sources Volume: 196, Issue: 17, Pages: 7355–7362 Time of Publication: 2011-09
Abstract	This study investigates the performance of a standard Ni–YSZ anode supported cell under ethanolsteamreforming operating conditions. Therefore, the fuelcell was directly operated with a steam/ethanol mixture (3 to 1 molar). Other gas mixtures were also used for comparison to check the conversion of ethanol and of reformate gases (H2, CO) in the fuelcell. The electrochemical properties of the fuelcell fed with four different fuel compositions were characterized between 710 and 860 °C by I–V and EIS measurements at OCV and under polarization. In order to elucidate the limiting processes, impedance spectra obtained with different gas compositions were compared using the derivative of the real part of the impedance with respect of the natural logarithm of the frequency. Results show that internalsteamreforming of ethanol takes place significantly on Ni–YSZ anode only above 760 °C. Comparisons of results obtained with reformate gas showed that the electrochemical cell performance is dominated by the conversion of hydrogen. The conversion of CO also occurs either directly or indirectly through the water–gas shift reaction but has a significant impact on the electrochemical performance only above 760 °C.
Keywords	SOFC; Ni–YSZ anode; Ethanol; Internal reforming; Coking; Impedance spectroscopy
Remark	Link

ID=92

Synthesis and electrical properties of Gd2MO5 (M = Zr, Hf)

Authors	L. P. Lyashenko, L. G. Shcherbakova, D. A. Belov, E. I. Knerel’man and N. N. Dremova
Source	Neorganicheskie Materialy Volume: Vol. 46, No. 12, Pages: pp. 1476–1482 Time of Publication: 2010-08
Abstract	Polycrystalline Gd2ZrO and Gd2HfO5 have been prepared by heat-treating coprecipitated oxide mixtures, and their order-disorder phase transitions have been studied in the range 20–1600°C. The materials have been shown to consist of nanostructured grains with a nanodomain size of ∼40 nm. Their electrical conductivity has been determined by impedance spectroscopy in air between 300 and 1000°C. The 1000°C conductivities of Gd2ZrO5 and Gd2HfO5 are 3.7 × 10−3 and 1.8 × 10−3 S/cm, and the respective effective activation energies are 1.37 and 1.56 eV.

ID=91

Proton Conductivity in Mixed B-Site Doped Perovskite Oxide BaZr0.5In0.25Yb0.25O3−delta

Authors	Istaq Ahmed,1,2 Francis G. Kinyanjui,1 Seikh M. H. Rahman,1 Patrick Steegstra,3 Sten G. Eriksson,1 and Elisabet Ahlberg3
Source	J. Electrochem. Soc. Volume: Volume 157, Issue: Issue 12, Pages: B1819-B182 Time of Publication: 2010-12
Abstract	A wet chemical route was used to prepare the oxygen deficient codoped perovskite oxide BaZr0.5In0.25Yb0.25O3−. Analysis of X-ray powder diffraction data showed that the sample belongs to the cubic crystal system with space group Pmm. Dynamic thermogravimetric (TG) analysis confirmed complete filling of oxygen vacancies (V) by protonic defects (OH) during the hydration process. The proton conductivity was investigated by impedance spectroscopy. The bulk and total conductivities of prehydrated BaZr0.5In0.25Yb0.25O3− were found to be 8.5×10−4 and 2.2×10−5 S cm−1, respectively, at 300°C. The total conductivity in the codoped perovskite oxide was higher compared to that of the respective single doped perovskite oxides with the same doping level. The bulk and grain-boundary mobility and diffusion coefficients of protons were calculated at 200°C using impedance and TG data to obtain the conductivity and proton concentration, respectively. The high bulk diffusivity (2.3×10−7 cm2 s−1) was obtained which indicates that the protons are more free to move in the heavily doped matrix compared to the lightly doped systems where trapping of protons occurs.
Keywords	barium compounds, proton exchange membrane fuel cells, thermal analysis, vacancies (crystal), X-ray diffraction, zirconium compounds
Remark	Link

ID=89

Electrical Conductivity of Nanostructured Fluorite-Like Sc2Ti3O12

Authors	L.P. Lyashenko, L.G. Shcherbakova, D.A. Belov, and A.V. Knotko
Source	Inorganic Materials Volume: 45, Issue: 5, Pages: 543-549 Time of Publication: 2009
Abstract	Single-crystal and polycrystalline samples of Sc4Ti3O12 have been shown to contain nanodomains (10–50 nm) with different degrees of ordering, coherent with the fluorite-like matrix. The oxygen-ion conductivity of this compound has been determined in the range 300–1000°C in air using impedance spectroscopy. The nanostructured single-crystal and polycrystalline samples are close in the activation energy for bulk conduction at both low and high temperatures: ≃1.26 and 1.29 eV in the range 300–775°C, ≃1.98 and 2.07 eV in the range 775–1000°C.

ID=88

Hydrogen sensitivity of doped CuO/ZnO heterocontact sensors

Author
Source	Sensors and Actuators B: Chemical Volume: 106, Issue: 2, Pages: 837-842 Time of Publication: 2005
Abstract	Heterocontact sensors based on p-type CuO and n-type ZnO ceramics have been shown to exhibit a high sensitivity to reducing gas species and an intrinsic selectivity. In this work, doped heterocontact sensors were prepared via solid state synthesis routes. CuO was doped with various monovalent (Li, Na) and isovalent (Ca, Sr, Ni) dopants at different compositions to form both single phase and two phase samples. Effects of dopants on hydrogen sensitivity through conductivity and heterogeneous microstructure were investigated using dc current–voltage measurements and ac impedance analysis. It was observed that both monovalent and divalent dopants increased the hydrogen sensitivity significantly. The highest sensitivity was observed in a 2.5 mol% Ni-CuO/ZnO heterocontact and low amounts of Li doping were shown to greatly enhance the rectifying characteristics.
Keywords	Hydrogen sensor; Heterocontact; CuO; ZnO

ID=86

Stability and conductivity study of the BaCe0.9−xZrxY0.1O2.95 systems

Author	Zhimin Zhong
Source	Solid State Ionics Volume: 178, Issue: 3-4, Pages: 213-220 Time of Publication: 2007

ID=81

Structure, defect chemistry, and proton conductivity in nominally Sr-doped Ba3La(PO4)3

Authors
Source	Solid State Ionics Volume: 180, Issue: 4-5, Pages: 338-342 Time of Publication: 2009

ID=80

Local structure and ionic conductivity in the Zr2Y2O7–Y3NbO7 system

Authors	Stefan T Norberg, Istaq Ahmed, Stephen Hull, Dario Marrocchelli and Paul A Madden
Source	Journal of Physics: Condensed Matter Volume: 21, Issue: 21, Pages: 215401 Time of Publication: 2009

ID=70

Conductivity and water uptake of Sr4(Sr2Nb2)O11·nH2O and Sr4(Sr2Ta2)O11·nH2O

Authors	Niina Jalarvo, Camilla Haavik, Camilla Kongshaug, Poul Norby and Truls Norby
Source	Solid State Ionics Volume: 180, Issue: 20-22, Pages: 1151-1156 Time of Publication: 2009

ID=69

Synthesis and characterization of nanocrystalline Ni–YSZ cermet anode for SOFC

Author	T. Priyatham and Ranjit Bauri
Source	Materials Characterization Volume: 61, Issue: 1, Pages: 54-58 Time of Publication: 2010-01
Abstract	Ni–YSZ cermet anode has been synthesized in one step using a simple and cost effective combustion synthesis process. The processed powder of NiO–YSZ is found to be nanocrystalline with crystallite sizes of 29 and 22 nm for NiO and YSZ respectively by X-ray diffraction and transmission electron microscopy analysis. X-ray diffraction analysis also shows that the precursor salts are converted to highly crystalline phases of NiO and YSZ (8 mol% Y2O3) without any intermediate calcination step and no undesirable phases are present. Comparison with the X-ray diffraction pattern of a commercial YSZ sample shows that the process is also effective in maintaining a close compositional control. The microstructure of the sintered and reduced sample shows a well defined network of pores which is necessary for the effective functioning of the anode. The electrical conductivity as a function of temperature shows metallic behavior.
Keywords	Ni–YSZ anode; Combustion synthesis; Nanocrystalline cermet; Microstructure

ID=68

A combined conductivity and DFT study of protons in PbZrO3 and alkaline earth zirconate perovskites

Authors
Source	Solid State Ionics Volume: 181, Issue: 3-4, Pages: 130-137 Time of Publication: 2010
Abstract	The electrical properties of nominally undoped and 4 mol% Y-doped PbZrO3 have been investigated by AC conductivity measurements and impedance spectroscopy under various pH2O and pO2 at high temperatures. The results indicate that the defect structures are dominated by acceptors (Y dopant and/or Pb vacancies formed during synthesis). In dry atmosphere and at high temperatures, the acceptors are compensated by oxygen vacancies. These are hydrated and replaced by protonic defects (hydroxide ions on oxide ion sites) at higher pH2O and lower temperatures. In oxidizing atmospheres, a minority concentration of electron holes dominates the conductivity. At lower temperatures and in wet atmosphere, a significant protonic conductivity contribution is also observed. Based on pO2 and pH2O isotherms, a model for incorporation of protonic defects has been applied, and the standard enthalpy of hydration of oxygen vacancies in undoped PbZrO3 has been determined (− 1.07 ± 0.13 eV). The measured total conductivities are influenced by high grain boundary resistance. Hence, the enthalpy is at the present stage assigned to the polycrystalline ceramic material as such. Rough estimates of bulk proton mobility in Y-doped PbZrO3 yield uH+0 = 17 cm2K/Vs and ΔHm,H+ = 0.93 eV. A complementary DFT study of the hydration thermodynamics of PbZrO3 and the alkaline earth zirconate perovskites AZrO3 (A = Ca, Sr, Ba) is also reported. The experimental and theoretical hydration enthalpies are compared with those of other ABO3 perovskites. Correlations between the hydration thermodynamics and other properties of the materials are discussed.
Keywords	PbZrO3; CaZrO3; SrZrO3; BaZrO3; Conductivity; Proton; Proton mobility; DFT; Thermodynamics; Defects; Hydration

ID=67

Electrical conductivity and oxygen permeation properties of SrCoFeOx membranes

Authors	Jay Kniep, Qinghua Yin, Izumi Kumakiri and Y.S. Lin
Source	Solid State Ionics Volume: 180, Issue: 40, Pages: 1633-1639 Time of Publication: 2010
Abstract	The total conductivity and oxygen permeation properties of dense SrCoFeOx membranes synthesized from the solid state method were studied in the temperature range of 700–900 °C. The SrCoFeOx membranes consist of an intergrowth (Sr4Fe6 − xCoxO13 ± δ), perovskite (SrFe1 − xCoxO3 − δ), and spinel (Co3 − xFexO4) phase. SrCoFeOx exhibits n-type and p-type conduction at low and high oxygen partial pressures, respectively, and has a total conductivity of 16.5 S/cm at 900 °C in air. The oxygen permeation fluxes for SrCoFeOx and SrFeCo0.5Ox membranes were measured with either an inert or carbon monoxide sweep gas. The oxygen permeation fluxes were higher through SrCoFeOx membranes than SrFeCo0.5Ox membranes and can be attributed to a difference in the amount and makeup of the perovskite phase present in each composition. The oxygen permeation fluxes with a carbon monoxide sweep gas were approximately two orders of magnitude larger than the fluxes measured with an inert sweep gas for both compositions. The large oxygen permeation fluxes observed with a carbon monoxide sweep are due to a higher driving force for oxygen transport and a reaction on the sweep side of the membrane that maintains a low oxygen partial pressure.
Keywords	Mixed-conducting oxide membrane; Oxygen permeation; Strontium iron cobalt oxide

ID=65

Investigation of proton conductivity in Sm1.92Ca0.08Ti2O7 − δ and Sm2Ti1.92Y0.08O7 − δ pyrochlores

Authors	K.E.J. Eurenius, E. Ahlberg, I. Ahmed, S.G. Eriksson and C.S. Knee
Source	Solid State Ionics Volume: 181, Issue: 3-4, Pages: 148-153 Time of Publication: 2010
Abstract	The results of the synthesis and characterisation of pyrochlore systems Sm1.92Ca0.08Ti2O7 − δ and Sm2Ti1.92Y0.08O7 − δ are reported. The electrical conductivity of the materials was studied using impedance spectroscopy under wet and dry oxygen and argon. Enhancements of the bulk conductivity at temperatures up to 500 °C were observed for wet conditions indicative of significant proton conductivity. The presence of dissolved protons in the materials is supported by thermogravimetric analysis and infrared spectroscopy. Proton conduction was confirmed by measurements in O2/D2O and Ar/D2O. The results reveal the importance of the correct choice of dopant site for the pyrochlore structure, with A-site substitution yielding the highest levels of proton, as well as oxide ion, conduction. For both samples bulk, rather than grain boundary, conduction is found to be dominant.
Keywords	Sm2Ti2O7; Pyrochlore; Ionic conductivity; Infrared spectroscopy; Impedance spectroscopy

ID=64

Space–charge theory applied to the grain boundary impedance of proton conducting BaZr0.9Y0.1O3 − δ

Authors	C. Kjolseth, , H. Fjeld, O. Prytz, P.I. Dahl, C. Estournes, R. Haugsrud, T. Norby
Source	Solid State Ionics Volume: 181, Issue: 5-7, Pages: 268-275 Time of Publication: 2010
Abstract	The specific grain interior and grain boundary conductivities, obtained from impedance spectroscopy and the brick layer model, are reported for BaZr0.9Y0.1O3 − δ as a function of pO2 and temperature. pO2-dependencies were indicative of dominating ionic and p-type electronic conduction for the grain interior under reducing and oxidizing conditions, respectively, while the grain boundaries showed an additional n-type electronic contribution under reducing conditions. Transmission electron microscopy revealed enrichment of Y in the grain boundary region. These findings indicate the existence of space–charge layers in the grain boundaries. A grain boundary core–space–charge layer model is therefore applied to interpret the data. Using a Mott–Schottky approximation, a Schottky barrier height of 0.5–0.6 V and an effective grain boundary width of 8–10 nm (= 2× space–charge layer thickness) is obtained at 250 °C in wet oxygen. Finite-element modelling of the complex impedance over a grain boundary with a space–charge layer depletion of protons yields a distorted semicircle as observed in the impedance spectra.
Keywords	BaZrO3; BaZr0.9Y0.1O3 − δ; Proton conductivity; Grain boundary resistance; Impedance spectroscopy; Space–charge layer

ID=60

Electrical conductivity of the proton conductor BaZr0.9Y0.1O3-δ obtained by high temperature annealing

Authors	Duval, S.B.C. / Holtappels, P. / Vogt, U.F. / Pomjakushina, E. / Conder, K. / Stimming, U. / Graule, T.
Source	Solid State Ionics, 178 (25) Pages: p.1437-1441 Time of Publication: 2007

ID=57

Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Authors	Haugsrud, R. / Kjolseth, C
Source	Journal of Physics and Chemistry of Solids, 69 (7) Pages: p.1758-1765 Time of Publication: 2008

ID=56

Heavily doped oxygen-ion conducting Ln2 + xTi2 − xO7 − δ (Ln = Ho–Lu; x = 0.44–0.81) pyrochlores: Crystal structure, microstructure and electrical conductivity

Authors	Shlyakhtina, A.V. / Savvin, S.N. / Levchenko, A.V. / Boguslavskii, M.V. / Shcherbakova, L.G.
Source	Solid State Ionics, 179 (21) Pages: p.985-990 Time of Publication: 2008

ID=48

Measurement of oxygen exchange kinetics on thin-filmLa0.6Sr0.4CoO3-δ using non-linear electrochemical impedance spectroscopy

Authors	J.R. Wilson, M. Sase, T. Kawada, S.B. Adler
Source	Electrochem. Solid State Lett. Volume: 10, Issue: 5, Pages: B81-86 Time of Publication: 2007

ID=47

Role of protons in the electrical conductivity of acceptor-doped BaPrO3, BaTbO3, and BaThO3

Authors
Source	Solid State Ionics Volume: 178, Issue: 7-10, Pages: 461-467 Time of Publication: 2007
Remark	Disk samples, impedance spectrocopy, transport number measurements

ID=46

High-Temperature Proton Conductivity in Acceptor-Substituted Rare-Earth Ortho-Tantalates, LnTaO4

Authors	R. Haugsrud, A. Tarancón, T. Norby, G. Dezanneau, A. Morata, F. Peiró, J.R. Morante
Source	J. Am. Ceram. Soc. Volume: 90, Issue: 4, Pages: 1116-1121 Time of Publication: 2007
Remark	Disk samples, impedance spectrocopy, transport number measurements

ID=45

Mixed ionic and electronic conductivity of undoped and acceptor doped Er6WO12

Authors	R. Haugsrud, H. Fjeld, K. R. Haug, T. Norby
Source	J. Electrochem. Soc. Volume: 154, Issue: 1, Pages: B77-81 Time of Publication: 2007
Remark	Disk samples, impedance spectrocopy, transport number measurements

ID=43

High-temperature proton conductivity in acceptor-doped LaNbO4

Authors	R. Haugsrud, T. Norby
Source	Solid State Ionics Volume: 177, Issue: 13-14, Pages: 1129-1135 Time of Publication: 2006
Remark	Disk samples, impedance spectrocopy, transport number measurements

ID=42

Ionic and Electronic Conductivity of 5% Ca-Doped GdNbO4

Authors
Source	J. Electrochem. Soc. Volume: 153, Issue: 8, Pages: J87-90 Time of Publication: 2006
Remark	Disk samples, impedance spetroscopy

ID=36

Proton conductivity of Ca-doped Tb2O3

Authors	R. Haugsrud, Y. Larring, T. Norby
Source	Solid State Ionics Volume: 176, Issue: 39-40, Pages: 2957-2961 Time of Publication: 2005
Remark	Disk samples: 2-electrode AC conductivity & impedance spectroscopy vs T, transport number measurements of protons by EMF of concentration cells.

ID=35

On the mixed ionic-electronic conductivity in Ca-doped La2Ti2O7

Authors	R. Haugsrud, T. Norby
Source	Pages: 209-214 Time of Publication: 2005
Editors	S. Linderoth, A. Smith, N. Bonanos, A. Hagen, L. Mikkelsen, K. Kammer, D. Lybye, P.V. Hendriksen, F.W. Poulsen, M. Mogensen, W.G. Wang
Remark	Disk samples: 2-electrode AC conductivity & impedance spectroscopy vs T, transport number measurements of protons and oxygen ions by EMF of concentration cells. Link

ID=29

Conductivity dependence on oxygen partial pressure and oxide-ion transport numbers determination for La2Mo2O9

Authors
Source	Electrochemical and Solid-State Letters Volume: 10, Issue: 7, Pages: A373-375 Time of Publication: 2004
Remark	Disk samples: 4-point van der Pauw conductivity, 2-electrode impedance spectroscopy, transport numbers of oxygen ions by EMF of oxygen concentration cell

ID=28

Impedance spectroscopy and proton transport number measurements on Sr-substituted LaPO4 prepared by combustion synthesis

Authors
Source	Solid State Ionics Volume: 162-163, Pages: 167-173 Time of Publication: 2003
Remark	Disk samples: 2-electrode AC conductivity, transport numbers of protons by EMF of hydrogen concentration cell

ID=27

HT Corrosion of a Cr-5wt%Fe1wt%Y2O3 Alloy and Conductivity of the Oxide Scale

Authors	Y. Larring, R. Haugsrud, T. Norby, J. Electrochem. Soc., 150 [8] (2003) B374-79
Source	J. Electrochem. Soc. Volume: 150, Issue: 8, Pages: B374-379 Time of Publication: 2003
Remark	Disk samples of alloy, with gold contact outside one oxide layer.

ID=26

Proton and apparent hydride ion conductivity in Al-substituted SrTiO3

Authors
Source	Solid State Ionics Volume: 154-155, Pages: 669-677 Time of Publication: 2002
Remark	Disk samples, 2-electrodes, Au seal, AC conductivity and concentration cell/EMF measurements of transport numbers for hydrogen and oxygen ions

ID=22

Phase relations, chemical diffusion and electrical conductivity in pure and doped Sr4Fe6O13 mixed conductor materials

Authors	R. Bredesen, T. Norby, A. Bardal, V. Lynum
Source	Solid State Ionics Volume: 135, Pages: 687-697 Time of Publication: 200
Remark	Disk sample, 4-point van der Pauw conductivity measurements

ID=15

Proton and deuteron conductivity in CsHSO4 and CsDSO4 by in situ isotopic exchange

Authors	T. Norby, M. Friesel, B.-E. Mellander
Source	Solid State Ionics Volume: 77, Pages: 105--110 Time of Publication: 1995
Remark	Disk sample, 4-point van der Pauw measurements

ID=10

Electrical conductivity and ionic transport number of YSZ and Cr-doped YSZ single crystals at 200-1000°C

Authors
Source	Solid State Ionics Volume: 67, Pages: 57-64 Time of Publication: 1993
Remark	Small single crystals, Pt paint electrodes, placed over small hole in support plate to form concentration cell. Role of sample holder parasitic conductance evaluated.

ID=7

The electrode system O2/Pt//ZrO2:8Y2O3 investigated by impedance spectroscopy

Authors	O. J. Velle, T. Norby, P. Kofstad
Source	Solid State Ionics Volume: 47, Pages: 161-167 Time of Publication: 1991
Remark	Thin electrolyte disk with 3 Pt electrodes. NOTE: probable reference electrode problem with such a thin electrolyte.

ID=4

Electrical Conductivity and Defect Structure of Y2O3 as a Function of Water Vapor Pressure

Authors	T. Norby, P. Kofstad
Source	J. Am. Ceram. Soc. Volume: 67, Issue: 12, Pages: 786-792 Time of Publication: 1984
Remark	5 disk samples stacked and measured simultaneously (2-electrode AC conductivity)

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General characterization and potential use of Moroccan lizardite clay in ceramics: Technological and dielectric studies

The Role of Strain in Proton Conduction in Multi-Oriented BaZr0.9Y0.1O3−δ Thin Film

Low temperature ammonia synthesis by surface protonics over metal supported catalysts

Surface protonic conductivity in chemisorbed water in porous nanoscopic CeO2

Ultrafast Crystallization and Sintering of Li1.5Al0.5Ge1.5(PO4)3 Glass and Its Impact on Ion Conduction

Development and characterization of highly stable electrode inks for low-temperature ceramic fuel cells

Native point defects and polaron transport in zirconium pyrovanadate

Surface kinetics and bulk transport in La2Ni0.5Cu0.5O4+δ membranes from conductivity relaxation

Electrospun Ca3Co4−xO9+δ nanofibers and nanoribbons: Microstructure and thermoelectric properties

Effects of Ni-NCAL and Ni–Ag electrodes on the cell performances of low-temperature solid oxide fuel cells with Sm0.2Ce0·8O2-δ electrolyte at various temperatures

Tuning the Thermoelectric Performance of CaMnO3-Based Ceramics by Controlled Exsolution and Microstructuring

Magnetron sputtered LSC-GDC composite cathode interlayer for intermediate-temperature solid oxide fuel cells

Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3–Ce0.8Sm0.2O2 Heterointerfaces as All-Ceramic Functional Layers for Solid Oxide Fuel Cell Applications

Correlations between structure, microstructure and ionic conductivity in (Gd,Sm)-doped ceria†

High-temperature electrical conductivity and electrochemical activity in oxygen redox reaction of La-doped Sr2FeCo0.5Mo0.5O6-δ

Effects of LiNi0.8Co0.15Al0.05O2 electrodes on the conduction mechanism of Sm0.2Ce0.8O2−δ electrolyte and performance of low-temperature solid oxide fuel cells

Efficiencies of cobalt- and copper-based coatings applied by different deposition processes for applications in intermediate-temperature solid oxide fuel cells

Synthesis of a Novel Nanoparticle BaCoO2.6 through Sol-Gel Method and Elucidation of Its Structure and Electrical Properties

Conduction mechanism of donor and acceptor doped sodium niobate-based ceramics

Characterization of Y and Mn co-substituted BaZrO3 ceramics: Material properties as a function of the substituent concentration

Performance of membranes based on novel Ce0.8Sm0.2O2-δ /Ag cermet and molten carbonates for CO2 and O2 separation

The effect of alkaline earth metal substitution on thermoelectric properties of A0.98La0.02MnO3-δ (A = Ca, Ba)

Tuning of the microstructural and electrical properties of undoped BaTiO3 by spark plasma sintering

Tailored and Improved Protonic Conductivity through Ba(ZxCe10−x)0.08Y0.2O3−δ Ceramics Perovskites Type Oxides for Electrochemical Devices

On the mechanism of Mn(II)-doping in Scandia stabilized zirconia electrolytes

Detailed characterization of oxide-ion and proton transport numbers in Sr–Ti layered perovskites using an improved electromotive force method

Impedance spectroscopy study of Au electrodes on Gd-doped CeO2 (GDC) – Molten Li2CO3+Na2CO3 (LNC) composite electrolytes

Oxide Ion and Proton Conductivity in a Family of Highly Oxygen-Deficient Perovskite Derivatives

Reaction Sintering of Ca3Co4O9 with BiCuSeO Nanosheets for High-Temperature Thermoelectric Composites

Synthesis, structure and ionic conductivity of nanocrystalline Ce1−xLaxO2−δ as an electrolyte for intermediate temperature solid oxide fuel cells

Unlocking bulk and surface oxygen transport properties of mixed oxide-ion and electron conducting membranes with combined oxygen permeation cell and oxygen probe method

Electrical properties of yttria-stabilised hafnia ceramics

Electrochemical Performance of SrWO4 Electrolyte for SOFC

Expanded Chemistry and Proton Conductivity in Vanadium-Substituted Variants of γ-Ba4Nb2O9

Electrical transport in a molten-solid V2O5–ZrV2O7 composite

Structural and Electrochemical Properties of Scandia Alumina Stabilized Zirconia Thin Films

Preparation of NdBaCo2O5+δ–Ce0.9Gd0.1O1.95 composite cathode by in situ sol-mixing method and its high-temperature electrochemical properties

Impedance spectroscopy studies of the chlorophosphate glasses

Optical properties and frequency-dependent conductivity of K2O-BaO-TiO2-P2O5 glasses

Synthesis and Triple Conductive Properties of Ba and Fe Co-Doped Sr2TiO4 Based Layered Perovskite: (BaxSr2-x) (Ti0.9Fe0.1)O4-δ (X= 0.05, 0.10)

Electrochemical, Thermal, and Structural Features of BaF2–SnF2 Fluoride-Ion Electrolytes

Enhanced activity of catalysts on substrates with surface protonic current in an electrical field – a review

Microstructure and electrochemical behavior of layered cathodes for molten carbonate fuel cell

Influence of Doping on the Transport Properties of Y1−xLnxMnO3+δ (Ln: Pr, Nd)

Ceramic composites based on Ca3Co4−xO9+δ and La2NiO4+δ with enhanced thermoelectric properties

Amorphous ZnO modified anatase TiO2 thin films templated by tripropylamine and their electrical properties

Impedance spectroscopy of manganese-doped mixed alkali phosphate glasses

Thermal Conductivity and Thermoelectric Power of Compounds in the Cu–Ge–As–Se System

Mixed ionic-electronic transport in the high-entropy (Co,Cu,Mg,Ni,Zn)1-xLixO oxides

The performance of intermediate temperature solid oxide fuel cells with sputter deposited La1-xSrxCoO3 interlayer

Near-Broken-Gap Alignment between FeWO4 and Fe2WO6 for Ohmic Direct p–n Junction Thermoelectrics

Effect of the Ba/K ratio on structural, dielectric and energy storage properties of BaO–K2O–TiO2–P2O5 glass-ceramics

Modification of Ruddlesden-Popper-type Nd2-xNi0.75Cu0.2M0.05O4±δ by the Nd-site cationic deficiency and doping with Sc, Ga or In: Crystal structure, oxygen content, transport properties and oxygen permeability

Comparative investigation on the functional properties of alkaline earth metal (Ca, Ba, Sr) doped Nd2NiO4+δ oxygen electrode material for SOFC applications

Synthesis and processing of SOFC components for the fabrication and characterization of anode supported cells

Increasing the thermal expansion of proton conducting Y-doped BaZrO3 by Sr and Ce substitution

Properties of Barium Cerate Thin Films Formed Using E-Beam Deposition

From insulator to oxide-ion conductor by a synergistic effect from defect chemistry and microstructure: acceptor-doped Bi-excess sodium bismuth titanate Na0.5Bi0.51TiO3.015

NiO–ZnO based junction interface as high-temperature contact materials

Cation-driven electrical conductivity in Ta-doped orthorhombic zirconia ceramics

Direct Solid Oxide Electrolysis of Carbon Dioxide:Analysis of Performance and Processes

Structural, optical, and dielectric properties of Bi2O3-K2O-TiO2-P2O5 glasses and related glass-ceramics

Strategies to Mitigate the Degradation of Stainless-SteelInterconnects Used in Solid Oxide Fuel Cells

Mitigation of grain boundary resistance inLa2/3-xLi3xTiO3perovskite as an electrolyte forsolid-state Li-ion batteries

Crystal structures and proton transport properties of Sr2(Ti1-xMx)O4-δ (M = Fe, Al)

Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li2OHCl

Conduction properties of acceptor-doped BaTiO3–Bi(Zn1/2Ti1/2)O3-based ceramics

Ionic conductivity in LixTaOy thin films grown by atomic layer deposition

Structural and Electrochemical Properties of Tysonite Ce0.95A0.05F2.95 (A = Mg, Ca, Sr, and Ba): Fast-Fluoride-Ion-Conducting Solid Electrolytes

Structural and Electrochemical Properties of Tysonite Ce0.95A0.05F2.95 (A = Mg, Ca, Sr, and Ba): Fast-Fluoride-Ion-Conducting Solid Electrolytes

Structural characterization and electrical/electrochemical studies of Nd1-xBaxCo1-y(Fe, Ti)y O3-δ (0 ≤ x ≤ 0.3, y = 0, 0.2) materials as cathode for SOFCs application

Effect of the Complexing Agent in the Pechini Method on the Structural and Electrical Properties of an Ionic Conductor of Formula La1−xSrxAlO3−δ (x = 0, 0.05, 0.1, 0.15)

High Cu content LaNi1-xCuxO3-δ perovskites as candidate air electrode materials for Reversible Solid Oxide Cells

Activation of C−H Bond of Propane by Strong Basic Sites Generated by Bulk Proton Conduction on VâModified Hydroxyapatites for the Formation of Propene

Thermoelectric properties of A-site deficient La-doped SrTiO3 at 100–900 °C under reducing conditions

Thermoelectric Properties of (1-x)LaCoO₃.(x)La_0.95Sr_0.05CoO₃ composite

p-Type/n-type behaviour and functional properties of KxNa(1-x)NbO3 (0.49 ≤ x ≤ 0.51) sintered in air and N2