"Roughly half of worlds primary energy consumption is lost as waste heat."
ProboStat accessory (ProboTEG) allows mounting four thermoelectric legs (5 x 5 mm area, 10 mm length, 2x p-type, 2x n-type) into a module that can be exposed to temperature gradients up to 600ºC with the hot side over 1000ºC, and under controlled atmospheres. The module can be characterized with any AC or DC method, and is especially suitable for studies of long term performance and degradation under (stable or dynamic) temperatures, gradients and atmospheres. |
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 |
Experimental application of a laser-based manufacturingprocess to develop a free customizable, scalablethermoelectric generator demonstrated on a hot shaft
Authors |
Marvin Abt, Katharina Kruppa, Mario Wolf, Armin Feldhoff, Ludger Overmeyer
|
Source |
Engineering Reports
Time of Publication: 2022
|
Abstract | Geometry, design, and processing in addition to the thermoelectric materialproperties have a significant influence on the economic efficiency and perfor-manceofthermoelectricgenerators(TEGs).WhileconventionalBULKTEGsareelaborate to manufacture and allow only limited variations in geometry, printedTEGs are often restricted in their application and processing temperature due totheuseoforganicmaterials.Inthiswork,aproof-of-conceptforfabricatingmod-ular, customizable, and temperature-stable TEGs is demonstrated by applyingan alternative laser process. For this purpose, low temperature cofired ceram-ics substrates were coated over a large area, freely structured and cut withoutmasks by a laser and sintered to a solid structure in a single optimized thermalpost-processing.Ascalabledesignwithcomplexgeometryandlargecoolingsur-face for application on a hot shaft was realized to prove feasibility. Investigationson sintering characteristics up to a peak temperature of 1173K, thermoelec-tric material properties and temperature distribution were carried out for aCa3Co4O9/Ag-based prototype and evaluated using profilometer, XRD, and IRmeasurements. For a combined post-processing, an optimal sintering profilecould be determined at 1073K peak temperature with a 20min holding time.Temperaturegradientsofupto100Kcouldbeachievedalongathermocouple.Asingle TEG module consisting of 12 thermocouples achieved a maximum powerof0.224μWandopen-circuitvoltageof134.41mVatanaveragehot-sidetemper-ature of 413.6 K and temperature difference of 106.7 K. Three of these modulescombined into a common TEG with a total of 36 thermocouples reached a maxi-mumpowerof0.58Kandopen-circuitvoltageof319.28mVwithalesseraveragehot-side temperature of 387.8 K and temperature difference of 83.4 K. |
Remark |
https://doi.org/10.1002/eng2.12590 Link |
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 |
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 |
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 properties─solid/gas reactivity and in-plane conductivity─are 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 |
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 |
La1-xSrxMO3 (M = Co, Mn, Cr) interconnects in a 4-leg all-oxide thermoelectric generator at high temperatures
Authors |
Reshma K. Madathil, Raphael Schuler, Truls Norby
|
Source |
Journal of Physics and Chemistry of Solids
Volume: 167,
Pages: 110739 Time of Publication: 2022 |
Abstract | We herein report tests at high temperatures of a 4-leg oxide thermoelectric generator consisting of two pairs of p-type Ni0.98Li0.02O (Li–NiO) and n-type Zn0.98Al0.02O (Al–ZnO), assembled with various conducting perovskite oxides as interconnects. Using a custom-built testing system, we evaluated performance and stability at a hot side (furnace) temperature of up to 1000 °C under temperature differences up to ΔT = 600 °C in air. With a La0.6Sr0.4CoO3 (LSC) interconnect, a maximum power output of 18 mW was achieved with TH = 940 and TC = 340 °C (ΔT = 600 °C). Power maxima with La0.8Sr0.2MnO3 (LSM) and La0.8Sr0.2CrO3 (LSCr) as interconnects were lower, 6 mW and 2 mW, respectively, under similar conditions, attributed to their lower thermal and electrical conductivities. This demonstrates the requirements and potential of oxide interconnects for stable use of all-oxide thermoelectric generators at high temperatures in ambient air. |
Keywords | Thermoelectric generator; Oxide; Interconnect; NiO; ZnO; La0.6Sr0.4CoO3 (LSC) |
Remark |
https://doi.org/10.1016/j.jpcs.2022.110739 Link |
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 |
NaMn0.2Fe0.2Co0.2Ni0.2Ti0.2O2 high-entropy layered oxide – experimental and theoretical evidence of high electrochemical performance in sodium batteries
Authors |
Katarzyna Walczak, Anna Plewa, Corneliu Ghica, Wojciech Zajac, Anita Trenczek-Zajac, Marcin Zajac, Janusz Tobota, Janina Molenda
|
Source |
Energy Storage Materials
Volume: 47,
Pages: 500-514 Time of Publication: 2022 |
Abstract | Li-ion batteries, widely used in portable electronics, electric vehicles, and energy storage systems, are an integral element of our daily life. However, the limitation of lithium sources, which leads to high prices, prompts the search for alternatives. Recently there has been noticed a rapid interest in Na-ion batteries technology. Especially, suitable cathode structures are investigated to accumulate larger sodium ions. In this paper, the high entropy layered oxide NaMn0.2Fe0.2Co0.2Ni0.2Ti0.2O2 is presented which achieves superior electrochemical properties with a stable capacity of ca. 180 mAh g−1. The understanding of its high performance is based on a complex study of the multiphase intercalation mechanism. The combination of advanced structural analysis by XAS, in situ XRD, TEM, and computational DFT modelling gives a new concept on the nature of O3-P3 structure reorganization. The presented experimental and theoretical evidence indicates that the P3 phase of layered oxides is energetically favourable for a lower sodium content for specific transition metal-oxide pair distance. Fundamental understanding of the nature of phase transformation is crucial for tailoring structural composition, where the desirable O3-P3 reorganization will occur, resulting in achieving high-performance cathodes. |
Remark |
https://doi.org/10.1016/j.ensm.2022.02.038 Link |
Lanthanum strontium cobaltite as interconnect in oxide thermoelectric generators
Authors |
Reshma K.Madathil, TrulsNorby
|
Source |
Solid State Sciences
Volume: 124,
Pages: 106801 Time of Publication: 2022 |
Abstract | Issues related to use of metallic interconnects in oxide thermoelectric generators (TEGs) need to be addressed to secure performance and durability. Metal interconnects suffer from high cost of noble metals or chemical instability and contact resistance of non-noble metals, arising from oxidation, evaporation, and delamination in the oxidising conditions of ambient air at high operating temperatures. This work introduces the use of a stable and highly conducting ceramic oxide, in our case p-type lanthanum strontium cobaltite (La0.6Sr0.4CoO3, LSC) as interconnect. We verified the thermochemical stability of LSC in contact with p-type Ni0.98Li0.02O (Li–NiO) and n-type Zn0.98Al0.02O (Al–ZnO) and examined the electrical characteristics. An area specific contact resistance (ASRc) of ∼1800 Ω cm2 for a direct p-n junction was reduced to ∼400 mΩ cm2 for a p-LSC-n junction at a temperature of 300 °C, validating the concept. The use of a screen-printed LSC/Al–ZnO composite as a thin interconnect layer was found to decrease the contact resistance of the junction further to ∼260 mΩ cm2 at 300 °C, attributed to increased effective area of the LSC/Al–ZnO p-n junction. |
Keywords | Thermoelectric generator; All-oxide; Thermoelectric materials; Oxides; Interconnect; Oxide; p-n-junction; Ohmic; LaCoO3; Sr-substituted; La0.6Sr0.4CoO3 |
Remark | Link |
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 |
Improved thermoelectric properties in ceramic composites based on Ca3Co4O9 and Na2Ca2Nb4O13
Authors |
R. Hinterding, M. Wolf, M. Jakob, O. Oeckler, A. Feldhoff
|
Source |
Open Ceramics
Volume: 8,
Pages: 100198 Time of Publication: 2021 |
Abstract | The oxide materials Ca3Co4O9 and Na2Ca2Nb4O13 were combined in a new ceramic composite with promising synergistic thermoelectric properties. Both compounds show a plate-like crystal shape and similar aspect ratios but the matrix material Ca3Co4O9 with lateral sizes of less than 500 nm is about two orders of magnitude smaller. Uniaxial pressing of the mixed compound powders was used to produce porous ceramics after conventional sintering. Reactions between both compounds and their compositions were thoroughly investigated. In comparison to pure Ca3Co4O9, mixing with low amounts of Na2Ca2Nb4O13 proved to be beneficial for the overall thermoelectric properties. A maximum figure-of-merit of zT = 0.32 at 1073 K and therefore an improvement of about 19% was achieved by the ceramic composites. |
Remark |
https://doi.org/10.1016/j.oceram.2021.100198 Link |
Glass-ceramic composites as insulation material for thermoelectric oxide multilayer generators
Authors |
Sophie Bresch, Björn Mieller, Paul Mrkwitschka, Ralf Moos, Torsten Rabe
|
Source |
Time of Publication: 2021
|
Abstract | Thermoelectric generators can be used as energy harvesters for sensor applications. Adapting the ceramic multilayer technology, their production can be highly automated. In such multilayer thermoelectric generators, the electrical insulation material, which separates the thermoelectric legs, is crucial for the performance of the device. The insulation material should be adapted to the thermoelectric regarding its averaged coefficient of thermal expansion α and its sintering temperature while maintaining a high resistivity. In this study, starting from theoretical calculations, a glass-ceramic composite material adapted for multilayer generators from calcium manganate and calcium cobaltite is developed. The material is optimized towards an α of 11 × 10−6 K−1 (20–500°C), a sintering temperature of 900°C, and a high resistivity up to 800°C. Calculated and measured α are in good agreement. The chosen glass-ceramic composite with 45 vol.% quartz has a resistivity of 1 × 107 Ωcm and an open porosity of <3%. Sintered multilayer samples from tape-cast thermoelectric oxides and screen-printed insulation show only small reaction layers. It can be concluded that glass-ceramic composites are a well-suited material class for insulation layers as their physical properties can be tuned by varying glass composition or dispersion phases. |
Remark |
https://doi.org/10.1111/jace.18235 Link |
Metal Supported Proton Conducting Ceramic Cell with Thin Film Electrolyte for Electrolysis Application
Authors |
Haoyu Zheng, Feng Han, Noriko Sata, Matthias Riegraf, Amir Masoud Dayaghi, Truls Norby and Rémi Costa
|
Source |
ECS Transactions
Volume: 103,
Issue: 1,
Pages: 693 Time of Publication: 2021 |
Abstract | Manufacturing of metal supported proton conducting ceramic cells is investigated in the present study. A low temperature fabrication route was chosen to avoid metal corrosion during the fabrication process, in which pulsed laser deposition (PLD) was employed to apply the thin-film BaZr0.7Ce0.2Y0.1O3-δ electrolyte layer. The surface condition of the support layer is a critical aspect to produce a dense and gas-tight electrolyte layer by PLD. In order to decrease the average size of the 10-30 µm large pores in metal substrate down to the nano-scale, different powders with different particles size were successfully fabricated and integrated into a pore-size graded structure to form a homogeneous porous surface whose size distribution meets the requirements for making a dense PLD coating layer. An electrolyte layer with the intended phase is achieved with a thickness of around 1 µm. Initial electrochemical investigation with a Pt oxygen electrode showed a total resistance of 4.92 Ω cm2 at 600°C at OCV. |
Remark | Link |
The Electrochemical Society, find out more The Electrochemical Society, find out more Metal Supported Proton Conducting Ceramic Cell with Thin Film Electrolyte for Electrolysis Application
Authors |
Haoyu Zheng, Feng Han, Noriko Sata, Matthias Riegraf, Amir Masoud Dayaghi, Truls Norby and Rémi Costa
|
Source |
ECS Transactions
Volume: 103,
Pages: 693 Time of Publication: 2021 |
Abstract | Manufacturing of metal supported proton conducting ceramic cells is investigated in the present study. A low temperature fabrication route was chosen to avoid metal corrosion during the fabrication process, in which pulsed laser deposition (PLD) was employed to apply the thin-film BaZr0.7Ce0.2Y0.1O3-δ electrolyte layer. The surface condition of the support layer is a critical aspect to produce a dense and gas-tight electrolyte layer by PLD. In order to decrease the average size of the 10-30 µm large pores in metal substrate down to the nano-scale, different powders with different particles size were successfully fabricated and integrated into a pore-size graded structure to form a homogeneous porous surface whose size distribution meets the requirements for making a dense PLD coating layer. An electrolyte layer with the intended phase is achieved with a thickness of around 1 µm. Initial electrochemical investigation with a Pt oxygen electrode showed a total resistance of 4.92 Ω cm2 at 600°C at OCV. |
Remark | Link |
Effect of ball-milling on the phase formation and enhanced thermoelectric properties in zinc antimonides
Authors |
Priyadarshini Balasubramaniana, Manjusha Battabyal, Arumugam Chandra Bose, Raghavan Gopalan
|
Source |
Materials Science and Engineering: B
Volume: 271,
Pages: 115274 Time of Publication: 2021 |
Abstract | We report the phase formation mechanism and the enhanced thermoelectric properties of zinc antimonide (ZnSb) thermoelectric material. The phase pure ZnSb thermoelectric material is achieved using high-energy ball milling of Zn and Sb in a shorter span of time. The ZnSb phase formation is explained by the kinetic energy transferred to the powders during milling for the solid-state reaction between Zn and Sb to form the desired ZnSb phase. The repeatability in transport properties up to three thermal cycles corroborates the thermal stability of the processed samples. The thermoelectric figure of merit obtained at 600 K is ~ 0.76 for the processed phase pure ZnSb sample, the highest value in binary ZnSb reported so far. Our results address the ZnSb phase evolution in a shorter milling time and the enhanced thermoelectric properties of the ZnSb materials. The observations will help to scale up the processing of high-performance ZnSb thermoelectric materials. |
Keywords | Zinc antimonide; Thermoelectric materials; Ball milling; Phase formation kinetics; X-ray diffraction; Figure of merit |
Remark |
https://doi.org/10.1016/j.mseb.2021.115274 Link |
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 ◦C in air or O2. Improvement for samples maintaining the same P63cm crystal structure can exceed 3 orders of magnitude below 200 ◦C 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 ◦C) 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 |
Fabrication of a Silicide Thermoelectric Module Employing Fractional Factorial Design Principles
Authors |
Joachim S. Graff, Raphael Schuler, Xin Song, Gustavo Castillo-Hernandez, Gunstein Skomedal, Erik Enebakk, Daniel Nilsen Wright, Marit Stange, Johannes de Boor, Ole Martin Løvvik & Matthias Schrade
|
Source |
Journal of Electronic Materials volume
Volume: 50,
Pages: 4041–4049 Time of Publication: 2021 |
Abstract | Thermoelectric modules can be used in waste heat harvesting, sensing, and cooling applications. Here, we report on the fabrication and performance of a four-leg module based on abundant silicide materials. While previously optimized Mg2Si0.3Sn0.675Bi0.025 is used as the n-type leg, we employ a fractional factorial design based on the Taguchi methods mapping out a four-dimensional parameter space among Mnx-εMoεSi1.75−δGeδ higher manganese silicide compositions for the p-type material. The module is assembled using a scalable fabrication process, using a Cu metallization layer and a Pb-based soldering paste. The maximum power output density of 53 μW cm–2 is achieved at a hot-side temperature of 250 °C and a temperature difference of 100 °C. This low thermoelectric output is related to the high contact resistance between the thermoelectric materials and the metallic contacts, underlining the importance of improved metallization schemes for thermoelectric module assembly. |
Remark | Link |
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 K was 0.27 for the pure Ca3Co4−xO9+δ as well as for the sample containing 5 wt% 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 |
Versatile four-leg thermoelectric module test setup adapted to a commercial sample holder system for high temperatures and controlled atmospheres
Authors |
Raphael Schuler, Reshma K. Madathil, and Truls Norby
|
Source |
Review of Scientific Instruments
Volume: 92,
Pages: 043902 Time of Publication: 2021 |
Abstract | A high temperature thermoelectric test setup for the NORECS ProboStat™ sample holder cell has been designed, constructed, and tested. It holds four thermoelectric legs of up to 5 × 5 mm2 area each and flexible height, allows various interconnects to be tested, and utilizes the spring-load system of the ProboStat for fixation and contact. A custom stainless steel support tube flushed with water provides the cold sink, enabling large temperature gradients. Thermocouples and electrodes as well as the gas supply and outer tube use standard ProboStat base unit feedthroughs and dimensions. The setup allows for testing in controlled atmospheres with the hot side temperature of up to around 1000 °C and a temperature gradient of up to 600 °C. We demonstrate the test setup on a four-leg Li–NiO/Al–ZnO module with gold interconnects. The comparison between the predicted performance based on individual material parameters and the experimentally obtained module performance underlines the necessity for testing materials in combination, including interconnects. The four-leg setup allows versatile match-screening, performance evaluation, and long-term stability studies of thermoelectric materials in combination with hot and cold side interconnects under realistic operational conditions. |
Remark | Link |
Crystal structure, dielectric and optical properties of β-Ca3(PO4)2-type phosphates Ca9-xZnxLa(PO4)7:Ho3+
Authors |
Yu.Yu. Dikhtyar, D.V. Deyneko, K.N. Boldyrev, O.V. Baryshnikova, А.А. Belik, V.А. Morozov, B.I. Lazoryak
|
Source |
Journal of Luminescence
Volume: 236,
Pages: 118083 Time of Publication: 2021 |
Abstract | A series of new phosphates Ca9-xZnxLa(PO4)7:Ho3+ with the β-Ca3(PO4)2-type structure was synthesized by the solid state route. An intense near infra-red (NIR) emission according to intraconfigural 4f-4f transitions of Ho3+ ions 5I7 – 5I8 (~2 μm) and 5I6 – 5I8 (~1.156 μm) was observed. The obtained phases were studied by a combination of methods including synchrotron powder X-ray diffraction, dielectric spectroscopy, second harmonic generation, differential scanning calorimetry, luminescence spectroscopy. The structure of Ca8ZnLa(PO4)7 was refined by the Rietveld method in centrosymmetric space group Rc. The Ca2+ → Zn2+ substitution in the M5 site leads to a transformation from polar R3c space group (x = 0 – 0.5) to centrosymmetric Rc space group (x = 0.6–1) and to the increased integral intensity of luminescence with maxima at x = 1. It was concluded that the crystal site engineering in the Ho3+-containing β-Ca3(PO4)2-type hosts offers a promising way to obtain new NIR phosphors for use in the creation of biocompatible bone tissue fillers. |
Remark | Link |
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 |
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 |
Improved environmental stability of thermoelectric ceramics based on intergrowths of Ca3Co4O9–Na0.75CoO2
Authors |
Damjan Vengust, Bostjan Jancar, Tilen Sever, Andreja Šestan, Vid Bobnar, Zdravko Kutnjak, Nina Daneu, Danilo Suvorov, Matjaz Spreitzer
|
Source |
Ceramics International
Volume: 47,
Issue: 8,
Pages: 11687-11693 Time of Publication: 2021 |
Abstract | Ceramics based on calcium and sodium cobaltates are promising high-temperature thermoelectric oxide materials with complementary advantages. Ca3Co4O9 is stable at high temperatures, whereas Na0.75CoO2 can be easily processed as a textured ceramic with excellent thermoelectric properties. Na0.75CoO2, however, lacks long-term stability and degrades in even a relatively mild humid environment. In this work, we present a novel approach to the synthesis of complex composite materials based on intergrowths of sodium and calcium cobaltates that have excellent thermoelectric performance and improved stability. We synthesized samples with the mixed composition (3-x)Ca3Co4O9–4x(Na0.75CoO2) in an over-pressured oxygen atmosphere. Samples with the mixed Ca–Na composition developed textured microstructures composed of intergrowths of both end-members, as revealed by transmission electron microscopy. We also examined the thermoelectric performance of the investigated materials after exposure to high humidity and found that the composition with x = 0.8 (Ca:Na = 2.75) has long-term stability. |
Keywords | Composite materials; Microstructure; Transmission electron microscopy; Thermoelectric |
Remark | Link |
Time-Enhanced Performance of Oxide Thermoelectric Modules Based on a Hybrid p–n Junction
Authors |
Nikola Kanas, Rasmus Bjørk, Kristin Høydalsvik Wells, Raphael Schuler, Mari-Ann Einarsrud, Nini Pryds, and Kjell Wiik
|
Source |
ACS Omega
Volume: 6,
Issue: 1,
Pages: 197–205 Time of Publication: 2020 |
Abstract | The present challenge with all-oxide thermoelectric modules is their poor durability at high temperatures caused by the instability of the metal-oxide interfaces at the hot side. This work explains a new module concept based on a hybrid p–n junction, fabricated in one step by spark plasma co-sintering of Ca3Co4–xO9+δ (CCO, p-type) and CaMnO3−δ/CaMn2O4 (CMO, n-type). Different module (unicouple) designs were studied to obtain a thorough understanding of the role of the in situ formed hybrid p–n junction of Ca3CoMnO6 (CCMO, p-type) and Co-oxide rich phases (p-type) at the p–n junction (>700 °C) in the module performance. A time-enhanced performance of the modules attributed to this p–n junction formation was observed due to the unique electrical properties of the hybrid p–n junction being sufficiently conductive at high temperatures (>700 °C) and nonconductive at moderate and low temperatures. The alteration of module design resulted in a variation of the power density from 12.4 (3.1) to 28.9 mW/cm2 (7.2 mW) at ΔT ∼ 650 °C after 2 days of isothermal hold (900 °C hot side). This new concept provides a facile method for the fabrication of easily processable, cheap, and high-performance high-temperature modules. |
Remark | Link |
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 |
Thermally stable, low resistance Mg2Si0.4Sn0.6/Cu thermoelectric contacts using SS 304 interlayer by one step sintering
Authors |
B.Jayachandran, B. Prasanth, R. Gopalana, T.Dasgupt°, D. Sivaprahasam
|
Source |
Materials Research Bulletin
Volume: 136,
Pages: 111147 Time of Publication: 2021 |
Abstract | Device fabrication using Mg2Si1-xSnx thermoelectric (TE) material for 600–800 K application requires stable and low resistance electrical contacts between TE legs and the electrodes. In this study, n-type Mg2Si0.38Sn0.6Bi0.02 was hot-pressed with Cu electrodes in a single step, resulting in Cu3Mg2Si and Cu4MgSn phases at the interface. Although the specific contact resistance (rc) across the interface was 4.4 ± 0.9 μΩ.cm2, the electrical resistivity of the TE leg increased by approximately 60 % due to Cu diffusion through the interface. Incorporating the SS304 interlayer to prevent Cu diffusion increased rc to 6.1 ± 2 μΩ.cm2. Upon annealing at 723 K for 3–15 days, rc remained at <10 μΩ.cm2 with an approximately 15 % decrease in the power factor. However, without SS304, rc increased to 41.5 ± 18 μΩ.cm2, with 65 % reduction in the power factor. Thus, this work demonstrates the fabrication of thermally stable Cu/Mg2Si0.4Sn0.6 joints by using the SS304 interlayer in a single-step process. |
Remark | Link |
Strategies to Mitigate the Degradation of Stainless-SteelInterconnects Used in Solid Oxide Fuel Cells
Author |
Claudia Gоbel
|
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 |
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 |
Ceramic-based thermoelectric generator processed via spray-coating and laser structuring
Authors |
Mario Wolf, Marvin Abt, Gerd Hoffmann, Ludger Overmeyer, Armin Feldhoff
|
Source |
Open Ceramics
Volume: 1,
Pages: 100002 Time of Publication: 2020 |
Abstract | Processing technology to improve the manufacturing of thermoelectric generators (TEGs) is a growing field of research. In this paper, an adaptable and scalable process comprising spray-coating and laser structuring for fast and easy TEG manufacturing is presented. The developed process combines additive and subtractive processing technology towards an adaptable ceramic-based TEG, which is applicable at high temperatures and shows a high optimization potential. As a prototype, a TEG based on Ca3Co4O9 (CCO) and Ag on a ceramic substrate was prepared. Microstructural and thermoelectric characterization is shown, reaching up to 1.65 μW cm−2 at 673 K and a ΔT of 100 K. The high controllability of the developed process also enables adaptation for different kinds of thermoelectric materials. |
Remark | Link |
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 |
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 |
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 |
Metal oxides for thermoelectrics
Author |
Johannes Gutenberg
|
Source |
Time of Publication: 2019
|
Remark |
Dissertation Link |
Mixed proton and electron conducting double perovskite anodes for stable and efficient tubular proton ceramic electrolysers
Authors | |
Source |
Nature Materials
Volume: 18,
Pages: 752–759 Time of Publication: 2019 |
Abstract | Hydrogen production from water electrolysis is a key enabling energy storage technology for the large-scale deployment of intermittent renewable energy sources. Proton ceramic electrolysers (PCEs) can produce dry pressurized hydrogen directly from steam, avoiding major parts of cost-driving downstream separation and compression. However, the development of PCEs has suffered from limited electrical efficiency due to electronic leakage and poor electrode kinetics. Here, we present the first fully operational BaZrO3-based tubular PCE, with 10 cm2 active area and a hydrogen production rate above 15 Nml min−1. The novel steam anode Ba1−xGd0.8La0.2+xCo2O6−δ exhibits mixed p-type electronic and protonic conduction and low activation energy for water splitting, enabling total polarization resistances below 1 Ω cm2 at 600 °C and Faradaic efficiencies close to 100% at high steam pressures. These tubular PCEs are mechanically robust, tolerate high pressures, allow improved process integration and offer scale-up modularity. |
Remark | Link |
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 |
SOFC cathodic layers using wet powder spraying technique with self synthesized nanopowders
Authors | |
Source |
International Journal of Hydrogen Energy
Volume: 44,
Issue: 14,
Pages: 7555-7563 Time of Publication: 2019 |
Abstract | In this work, a wet powder spraying method has been investigated as a facile low cost route to deposit electrode layer on SOFC electrolyte support. A particular focus has been examining the interfacial stability of the deposited layers, and determining the influence of the thickness of the different layers, as well as the ball milling regime used to produce the electrode inks. The developed system consist of an yttria stabilized zirconia electrolyte support, a La0.6Sr0.4FeO3 (LSF) cathode, a Sm0.2Ce0.8O1.9 (SDC) barrier layer between the electrolyte and the cathode, and LaNi0.6Fe0.4O3 (LNF) as a contact layer, for a future integration with the SOFC interconnector. The electrolyte supports (300 μm thickness and 9 mm diameter) supports were prepared by uniaxial pressing, while the deposition of thin barrier layers, cathode and contact layer were carried out by manual spray coating. |
Remark |
https://doi.org/10.1016/j.ijhydene.2019.01.220 Link |
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 |
Template-free mesoporous La0.3Sr0.7Ti1-xFexO3±δ for CH4 and CO oxidation catalysis
Authors |
Buğra Kayaalp, Siwon Lee, Kurt Klauke, Jongsu Seo, Luca Nodaric, Andreas Kornowski, WooChul Jung, Simone Mascotto
|
Source |
Applied catalysis B: Enviromental
Volume: 245,
Pages: 536-545 Time of Publication: 2019 |
Abstract | The design of perovskite oxides with improved textural properties in combination with tunable composition variations is a forward-looking strategy for the preparation of next generation catalytic converter. In the present work we report the template-free synthesis of mesoporous solid solutions of La0.3Sr0.7Ti1-xFexO3±δ (0 ≤ x ≤ 0.5) and the study of their catalytic performance towards CH4 and CO oxidation. Using an innovative polymer complex route, phase pure perovskite solid solutions with specific surface area of 65 m2 g−1 and average pore size of 15 nm were prepared. The iron concentration increase led to a progressive enhancement of not only both concentration and transport of the charge carriers but also reducibility and oxygen desorption capability on the catalyst. As a result, we observed almost complete conversion of CH4 and CO at 600 °C and 300 °C, respectively. Kinetic studies on methane oxidation showed that competing suprafacial and intrafacial reaction mechanisms coexist, and that the concentration of 30% of Fe maximizes the suprafacial contribution. Under reducing conditions at 600 °C the materials retained their structural and morphological integrity, showing superior stability. Finally, the reaction rate of CH4 and CO conversion evidenced that our systems are by a maximum of 90 times more performing than other bulk and nanoporous Fe-based perovskites in literature (e.g. La0.66Sr0.34Co0.2Fe0.8O3-δ), as a result their large surface area, intimate gas-solid contact and short intragrain oxygen diffusion pathways induced by the mesoporous structure. |
Remark | Link |
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 |
Large-area and adaptable electrospun silicon-based thermoelectric nanomaterials with high energy conversion efficiencies
Authors | |
Source |
Nature Communications
Volume: 9
Time of Publication: 2018
|
Abstract | Large amounts of waste heat generated in our fossil-fuel based economy can be converted into useful electric power by using thermoelectric generators. However, the low-efficiency, scarcity, high-cost and poor production scalability of conventional thermoelectric materials are hindering their mass deployment. Nanoengineering has proven to be an excellent approach for enhancing thermoelectric properties of abundant and cheap materials such as silicon. Nevertheless, the implementation of these nanostructures is still a major challenge especially for covering the large areas required for massive waste heat recovery. Here we present a family of nano-enabled materials in the form of large-area paper-like fabrics made of nanotubes as a cost-effective and scalable solution for thermoelectric generation. A case study of a fabric of p-type silicon nanotubes was developed showing a five-fold improvement of the thermoelectric figure of merit. Outstanding power densities above 100 W/m2 at 700 °C are therefore demonstrated opening a market for waste heat recovery. |
Remark |
Article number: 4759 (2018) |
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 |
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 |
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 |
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 |
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 |
Thermoelectric Properties of (1-x)LaCoO3.(x)La0.95Sr0.05CoO3 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 |
All-Oxide Thermoelectric Module with in Situ Formed Non-Rectifying Complex p–p–n Junction and Transverse Thermoelectric Effect
Authors |
Nikola Kanas, Michael Bittner, Temesgen Debelo Desissa, Sathya Prakash Singh, Truls Norby, Armin Feldhoff, Tor Grande, Kjell Wiik, and Mari-Ann Einarsrud
|
Source |
ACS Omega
Volume: 3,
Issue: 8,
Pages: 9899–9906 Time of Publication: 2018 |
Abstract | All-oxide thermoelectric modules for energy harvesting are attractive because of high-temperature stability, low cost, and the potential to use nonscarce and nontoxic elements. Thermoelectric modules are mostly fabricated in the conventional π-design, associated with the challenge of unstable metallic interconnects at high temperature. Here, we report on a novel approach for fabrication of a thermoelectric module with an in situ formed p–p–n junction made of state-of-the-art oxides Ca3Co4–xO9+δ (p-type) and CaMnO3–CaMn2O4 composite (n-type). The module was fabricated by spark plasma co-sintering of p- and n-type powders partly separated by insulating LaAlO3. Where the n- and p-type materials originally were in contact, a layer of p-type Ca3CoMnO6 was formed in situ. The hence formed p–p–n junction exhibited Ohmic behavior and a transverse thermoelectric effect, boosting the open-circuit voltage of the module. The performance of the module was characterized at 700–900 °C, with the highest power output of 5.7 mW (around 23 mW/cm2) at 900 °C and a temperature difference of 160 K. The thermoelectric properties of the p- and n-type materials were measured in the temperature range 100–900 °C, where the highest zT of 0.39 and 0.05 were obtained at 700 and 800 °C, respectively, for Ca3Co4–xO9+δ and the CaMnO3–CaMn2O4 composite. |
Remark |
DOI: 10.1021/acsomega.8b01357 |
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 |
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 |
Inter-diffusion across a direct p-n heterojunction of Li-doped NiO and Al-doped ZnO
Authors |
Temesgen D. Desissa, Reidar Haugsrud, Kjell Wiik, Truls Norby
|
Source |
Solid State Ionics
Volume: 320,
Pages: 215-220 Time of Publication: 2018 |
Abstract | We herein report inter-diffusion across the interface between p-type Ni0.98Li0.02O and n-type Zn0.98Al0.02O for various applications including p-n-heterojunction diodes and oxide thermoelectrics. Diffusion couples were made of polished surfaces of ceramic samples pre-sintered at 1250 and 1350 °C for Ni0.98Li0.02O and Zn0.98Al0.02O, respectively. The inter-diffusion couples were annealed at 900–1200 °C for 160 h in ambient air. Electron Probe Micro Analysis (EPMA) was used to acquire diffusion profiles, followed by fitting to Ficks second law and Whipple–Le Claires models for bulk and grain-boundary diffusion calculation, respectively. Zn2+ diffused into Ni0.98Li0.02O mainly by bulk diffusion with an activation energy of 250 ± 10 kJ/mol, whereas Ni2+ diffused into Zn0.98Al0.02O by both bulk and enhanced grain boundary diffusion with activation energies of 320 ± 120 kJ/mol and 245 ± 50 kJ/mol, respectively. The amount of Al3+ diffused from the Al-doped ZnO into the NiO phase was too small for a corresponding diffusion coefficient to be calculated. Li-ion distribution and diffusivity were not determined due to lack of analyzer sensitivity for Li. The bulk and effective diffusivities of Zn2+ and Ni2+ into NiO and ZnO enable prediction of inter-diffusion lengths as a function of time and temperature, allowing estimates of device performance, stability, and lifetimes at different operation temperatures. |
Keywords | NiO, ZnO, Cation diffusion, Grain-boundary diffusion, p-n junction |
Remark |
https://doi.org/10.1016/j.ssi.2018.03.011 Link |
Solid oxide fuel cells with apatite-type lanthanum silicate-based electrolyte films deposited by radio frequency magnetron sputtering
Authors |
Yi-Xin Liu, Sea-Fue Wang, Yung-Fu Hsu, Chi-Hua Wang
|
Source |
Journal of Power Sources
Volume: 381,
Pages: 101-106 Time of Publication: 2018 |
Abstract | In this study, solid oxide fuel cells (SOFCs) containing high-quality apatite-type magnesium doped lanthanum silicate-based electrolyte films (LSMO) deposited by RF magnetron sputtering are successfully fabricated. The LSMO film deposited at an Ar:O2 ratio of 6:4 on an anode supported NiO/Sm0.2Ce0·8O2-δ (SDC) substrate followed by post-annealing at 1000 °C reveals a uniform and dense c-axis oriented polycrystalline structure, which is well adhered to the anode substrate. A composite SDC/La0·6Sr0·4Co0·2Fe0·8O3-δ cathode layer is subsequently screen-printed on the LSMO deposited anode substrate and fired. The SOFC fabricated with the LSMO film exhibits good mechanical integrity. The single cell with the LSMO layer of ≈2.8 μm thickness reports a total cell resistance of 1.156 and 0.163 Ωcm2, open circuit voltage of 1.051 and 0.982 V, and maximum power densities of 0.212 and 1.490 Wcm−2 at measurement temperatures of 700 and 850 °C, respectively, which are comparable or superior to those of previously reported SOFCs with yttria stabilized zirconia electrolyte films. The results of the present study demonstrate the feasibility of deposition of high-quality LSMO films by RF magnetron sputtering on NiO-SDC anode substrates for the fabrication of SOFCs with good cell performance. |
Keywords | Solid oxide fuel cell, Sputtering, Electrolyte Doped lanthanum silicate |
Remark |
https://doi.org/10.1016/j.jpowsour.2018.02.007 Link |
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 |
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 |
Microstructural design of CaMnO3 and its thermoelectric proprieties.
Author |
Natalia Maria Mazur
|
Source |
dissertation
Time of Publication: 2015
|
Remark |
Norwegian University of Science and Technology, Department of Materials Science and Engineering Link |
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 |
Influence of processing on stability, microstructure and thermoelectric properties of Ca3Co4 − xO9 + δ
Authors |
Nikola Kanasac Sathy, Prakash Singh, Magnus Rotan, Mohsin Saleemi, Michael Bittner, Armin Feldhoff, Truls Norby, Kjell Wiika, Tor Grande, Mari-Ann Einarsrud
|
Source |
Journal of the European Ceramic Society
Time of Publication: 2017
|
Abstract | Due to high figure of merit, Ca3Co4 − xO9 + δ (CCO) has potential as p-type material for high-temperature thermoelectrics. Here, the influence of processing including solid state sintering, spark plasma sintering and post-calcination on stability, microstructure and thermoelectric properties is reported. By a new post-calcination approach, single-phase materials were obtained from precursors to final dense ceramics in one step. The highest zT of 0.11 was recorded at 800 °C for CCO with 98 and 72% relative densities. In situ high-temperature X-ray diffraction in air and oxygen revealed a higher stability of CCO in oxygen (∼970 °C) than in air (∼930 °C), with formation of Ca3Co2O6 which also showed high stability in oxygen, even at 1125 °C. Since achievement of phase pure high density CCO by post-calcination method in air is challenging, the phase stability of CCO in oxygen is important for understanding and further improvement of the method. |
Keywords | Ca3Co4 − xO9 + δ, Post calcination, Phase stability, Microstructure, Thermoelectric performance |
Remark |
Available online 6 November 2017, https://doi.org/10.1016/j.jeurceramsoc.2017.11.011 Link |
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 |
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 |
Fabrication and testing of unileg oxide thermoelectric device
Authors |
Jyothi Sharma, R. D. Purohit, Deep Prakash, and P. K. Sinha
|
Source |
API Conference Proceedings
Time of Publication: 2017
|
Abstract | A prototype of oxide thermoelectric unileg device was fabricated. This device was based on only n-legs made of La doped calcium manganate. The powder was synthesized, characterised and consolidated in rectangular thermoelements. A 3×3 device was fabricated by fitting 9 rectangular bars in alumina housing and connected by silver strips. The device has been tested under large temperature difference (ΔT=480°C) using an indegenous system. An open circuit voltage of 468 mV was obtained for a nine leg unileg device. The device exhibits a internal resistance of ∼1Ω. The maximum power output for this nine leg device reached upto 50 mW in these working condition |
Keywords | Seebsys |
Remark | Link |
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 |
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 |
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 |
Relating defect chemistry and electronic transport in the double perovskite Ba1−xGd0.8La0.2+xCo2O6−δ (BGLC)
Authors | |
Source |
Journal of Materials Chemistry A
Volume: 5,
Pages: 15743-15751 Time of Publication: 2017 |
Abstract | Rare earth double perovskites comprise a class of functional oxides with interesting physiochemical properties both for low- and high-temperature applications. However, little can be found relating electrical properties with equilibrium thermodynamics of non-stoichiometry and defects. In the present work, a comprehensive and generally applicable defect chemical model is developed to form the link between the defect chemistry and electronic structure of partially substituted BGLC (Ba1−xGd0.8La0.2+xCo2O6−δ, 0 ≤ x ≤ 0.5). The equilibrium oxygen content of 4 different compositions is determined as a function of pO2 and temperature by thermogravimetric analysis, and combined with defect chemical modelling to obtain defect concentrations and thermodynamic parameters. Oxidation enthalpies determined by TG-DSC become increasingly exothermic (−50 to −120 kJ mol−1) with increased temperature and oxygen non-stoichiometry for all compositions, in excellent agreement with the thermodynamic parameters obtained from the defect chemical model. All compositions display high electrical conductivities (500 to 1000 S cm−1) with shallow pO2-dependencies and small and positive Seebeck coefficients (3 to 15 μV K−1), indicating high degree of degeneracy of the electronic charge carriers. The complex electrical properties of BGLC at elevated temperatures is rationalized by a two-band conduction model where highly mobile p-type charge carriers are transported within the valence band, whereas less mobile “n-type” charge carriers are located in narrow Co 3d band. |
Remark |
DOI: 10.1039/C7TA02659E Link |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
Solid oxide fuel cells with (La,Sr)(Ga,Mg)O3-δ electrolyte film deposited by radio-frequency magnetron sputtering
Authors |
Sea-Fue Wang, His-Chuan Lu, Yung-Fu Hsu, Yi-Xuan Hu
|
Source |
Journal of Power Sources
Volume: 281,
Pages: 258–264 Time of Publication: 2015 |
Abstract | In this study, solid oxide fuel cells (SOFCs) containing a high quality La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) film deposited on anode supported substrate using RF magnetron sputtering are successfully prepared. The anode substrate is composed of two functional NiO/Sm0.2Ce0.8O2-δ (SDC) composite layers with ratios of 60/40 wt% and 50/50 wt% and a current collector layer of pure NiO. The as-deposited LSGM film appears to be amorphous in nature. After post-annealing at 1000 °C, a uniform and dense polycrystalline film with a composition of La0.87Sr0.13Ga0.85Mg0.15O3-δ and a thickness of 3.8 μm is obtained, which was well adhered to the anode substrate. A composite LSGM/La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) layer, with a ratio of 30/70 wt%, is used as the cathode. The SOFC prepared reveals a good mechanical integrity with no sign of cracking, delamination, or discontinuity among the interfaces. The total cell resistance of a single cell with LSGM electrolyte film declines from 0.60 to 0.10 Ω cm2 as the temperature escalates from 600 to 800 °C and the open circuit voltage (OCV) ranges from 0.85 to 0.95 V. The maximum power density (MPD) of the single cell is reported as 0.65, 1.02, 1.30, 1.42, and 1.38 W cm−2 at 600, 650, 700, 750, and 800 °C, respectively. The good cell performance leads to the conclusion that RF magnetron sputtering is a feasible deposition method for preparing good quality LSGM films in SOFCs. |
Keywords | Solid oxide fuel cell; Sputtering; Electrolyte; Doped lanthanum gallate |
Remark |
doi:10.1016/j.jpowsour.2015.01.185 Link |
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 |
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 |
Thermoelectric Properties of A-site Deficient Lanthanum Substituted Strontium Titanate
Author |
Thomas Emdal Loland
|
Source |
Time of Publication: 2014
|
Remark | Link |
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 |
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 |
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 |
Multilayered thin films for oxidation protection of Mg2Si thermoelectric material at middle–high temperatures
Authors |
S. Battiston, S. Boldrini, S. Fiameni, A. Famengo, M. Fabrizio, S. Barison
|
Source |
Thin Solid Films
Volume: 526,
Pages: 150–154 Time of Publication: 2012-12 |
Abstract | Multilayered molybdenum silicide-based thin films were deposited via radio frequency magnetron sputtering in order to obtain efficient barrier against oxidation process which affected Mg2Si thermoelectric materials at middle–high temperatures. X ray diffraction, energy dispersive spectroscopy, secondary ion mass spectroscopy, field emission scanning electron microscopy (FE-SEM) and electrical measurements at high temperature were carried out in order to obtain, respectively, the structural, compositional, morphological and electrical characterization of coatings. Furthermore, the mechanical behavior of the thin film/Mg2Si-pellet system was observed in situ as a function of temperature by FE-SEM employing a heating module. Moreover, the barrier properties for oxygen protection after thermal treatment in air at high temperature were qualitatively evaluated. |
Keywords | Thin film; Thermoelectric material; Magnesium silicide; Molybdenum silicide; Middle–high temperature |
Remark | Link |
CO2 decomposition via oxygen deficient ferrite electrodes using solid oxide electrolyser cell
Source |
Time of Publication: 2012-09
|
Abstract | Oxygen Deficient Ferrites (ODF) electrodes integrated with Yttria Stabilized Zirconia (YSZ) electrolyte, electrochemically decompose carbon dioxide (CO2) into carbon (C)/carbon monoxide (CO) and oxygen (O2) in a continuous process. The ODF electrodes can be kept active by applying a small potential bias across the electrodes. CO2 and water (H2O) can also be electrolyzed simultaneously to produce syngas (H2+CO) and O2 continuously that can be fed back to the oxy-fuel combustion. With this approach, CO2 can be transformed into a valuable fuel source allowing CO2 neutral use of the hydrocarbon fuels. |
Remark |
United States Patent Application 20120228150 Link |
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. |
Impact of Parylene-A Encapsulation on ZnO Nanobridge Sensors and Sensitivity Enhancement via Continuous Ultraviolet Illumination
Authors |
C.-C. Huang, A.D. Mason, J.F. Conley, C. Heist, M.T. Koesdjojo, V.T. Remcho and T. Afentakis
|
Source |
Journal of Electronic Materials
Volume: 41,
Issue: 5,
Pages: 873-880 Time of Publication: 2012-05 |
Abstract | The impact of parylene-A encapsulation and the effect of continuous ultraviolet (UV) exposure on ZnO nanobridge sensor response are investigated. ZnO nanowire (NW) devices are fabricated using a novel method that involves selective growth of ZnO nanobridges between lithographically defined pads of carbonized photoresist (C-PR). We find that a thin coating of parylene-A effectively attenuates the response of NW devices to O2, H2O vapor, and UV illumination. The accessibility of the amine group on parylene-A for chemical functionalization is verified by transforming the amine groups on the surface of the parylene-A coating into aromatic imine groups, followed by UV–Vis absorption. Our results suggest that, in addition to modulating environmental sensitivity and providing protection of the ZnO NWs for liquid- and vapor-phase sensing, the parylene-A encapsulation may also serve as an activation layer for further specific functionalization targeting selective sensing. We also found that the sensitivity and response time of ZnO nanobridge devices to O2 are dramatically improved by continuously exposing the nanobridge devices to UV illumination. Finally, we show that the C-PR directed growth method can also be used to isolate free-standing NW carpet. |
Keywords | ZnO – nanowire – parylene – CVD – nanobridge – sensor – functionalization – directed integration |
Remark | Link |
Characterization of individual barium titanate nanorods and their assessment as building blocks of new circuit architectures
Authors |
K. Zagar, F. Hernandez-Ramirez, J. D. Prades, J. R. Morante, A. Rečnik and M. Čeh
|
Source |
Nanotechnology
Volume: 22,
Issue: 38,
Pages: 385501 Time of Publication: 2011-09 |
Abstract | In this work, we report on the integration of individual BaTiO3 nanorods into simple circuit architectures. Polycrystalline BaTiO3 nanorods were synthesized by electrophoretic deposition (EPD) of barium titanate sol into aluminium oxide (AAO) templates and subsequent annealing. Transmission electron microscopy (TEM) observations revealed the presence of slabs of hexagonal polymorphs intergrown within cubic grains, resulting from the local reducing atmosphere during the thermal treatment. Electrical measurements performed on individual BaTiO3 nanorods revealed resistivity values between 10 and 100 Ω cm, which is in good agreement with typical values reported in the past for oxygen-deficient barium titanate films. Consequently the presence of oxygen vacancies in their structure was indirectly validated. Some of these nanorods were tested as proof-of-concept humidity sensors. They showed reproducible responses towards different moisture concentrations, demonstrating that individual BaTiO3 nanorods may be integrated in complex circuit architectures with functional capacities. |
Remark |
doi: 10.1088/0957-4484/22/38/385501 Link |
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. |
Development of an In Situ Surface Deformation and Temperature Measurement Technique for a Solid Oxide Fuel Cell Button Cell
Authors |
Huang Guo, Gulfam Iqbal, Bruce S. Kang
|
Source |
International Journal of Applied Ceramic Technology
Volume: 7,
Issue: 1, January/February,
Pages: 55-62 Time of Publication: 2010-01 |
Abstract | A novel experimental technique is developed to measure the in situ surface deformation and temperature of a solid oxide fuel cell (SOFC) anode surface along with the cell electrochemical performance. The experimental setup consists of a NexTech ProboStat™ SOFC button cell test apparatus integrated with a Sagnac interferometric optical method and an infrared sensor for in situ surface deformation and temperature measurements, respectively. The button cell is fed with hydrogen or simulated coal syngas under SOFC operating conditions. The surface deformation is measured over time to estimate the anode structural degradation. The cell surface transient temperature is also monitored with different applied current densities under hydrogen and simulated coal syngas. The experimental results are useful to validate and develop SOFC structural durability and electrochemical models. |
Comperative Seebeck Coefficient Measurements on Ceramic and Compacted Powder Column Samples; Case of ZnO
Authors | |
Source |
Proceeding of the 1st Nordic School and Symposium on Functional Energy Related Materials
NorFERM-2008, 3-7 October 2008, Gol, Norway Volume: R, Pages: 36 Time of Publication: 2008 |
Thermoelectric power of the mixed ionic-electronic conductor SrTi0.8Fe0.2O3-d in various atmospheres
Authors |
T. Norby, S. Steinsvik
|
Source |
proc. Nordic Energy Research Workshop on "Hydrogen in Electrochemical Energy Conversion", Geilo
Volume: March 1999
Time of Publication: 1999
|
thermoelectric | |
Editors |
F.W. Poulsen, R.J. Aaberg
|
Remark |
Bar sample, thermoelectric power (Seebeck coefficient) measurements |