Dense Button Cells - BZY15, BZY15-Ni, and BZCY81-Ni

BZY is considered to be one of the candidate materials for proton ceramic fuel cells (PCFCs) and electrolyzer cells (PCECs) due to its high proton conductivity and chemical stability towards H₂O and CO₂ containing atmospheres.

Suitable for studies of proton conduction, impedance electroscopy of bulk, grain boundary, and electrodes.

Standard electrolyte for testing of electrodes for PCFCs and PCECs.

NORECS now offers BZY-based disk samples as described below.*

 *Other compositions and dimensions are upon request.

These articles refer to ProboStat or other NORECS products, filtered with keywords: 'BZY'  

ID=711

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

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

ID=608

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

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

ID=571

Electrochemical promotion of Ru nanoparticles deposited on a proton conductor electrolyte during CO2 hydrogenation

Authors	Dimitrios Zagoraiosa, Christopher Panaritis, Aikaterina Krassakopoulou, Elena A. Baranova, Alexandros Katsaounis, Constantinos G. Vayenas
Source	Applied Catalysis B: Environmental Volume: 276, Pages: 119148 Time of Publication: 2020
Abstract	Recycling CO2 into a carbon-neutral source is a beneficial approach in reducing non-renewable energy sources. Herein, the electrochemical promotion of catalysis (EPOC) has been exploited to enhance the catalytic activity of Ru nanoparticles (0.7−1 nm) deposited on the proton conductor yttria-doped barium zirconate (BZY), as free-standing nanoparticles and supported on Co3O4 semiconductor, for CO2 hydrogenation. Under 250−450 °C and atmospheric pressure, both methanation and reverse water-gas shift (RWGS) reaction take place simultaneously over the Ru nanoparticles with a superior selectivity to CO. Under anodic polarization, free-standing Ru nanoparticles displayed an increase in CH4 and a decrease in CO production, while the opposite effect was observed under cathodic polarization. Ru supported on Co3O4 displayed a superior catalytic activity mostly due to enhanced metal–support interactions. The electronic effects induced by the pairing of Co3O4 and BZY resulted in a new approach to EPOC applications that brings it closer to industrial application.
Remark	Link

ID=467

Electrochemical promotion of nanodispersed Ru-Co catalysts for the hydrogenation of CO2

Authors	A. Kotsirasa, I. Kalaitzidoua, D. Grigorioua, A. Symillidisa, M. Makria, A. Katsaounisa, C.G. Vayenas
Source	Applied Catalysis B: Environmental Volume: 232, Pages: 60-68 Time of Publication: 2018
Abstract	Electrochemical promotion of the CO2 hydrogenation to CH4 and CO on a nanodispersed Ru-Co catalyst has been achieved via slurry deposition of the nanodispersed catalyst on an interlayer Ru film deposited on a BZY (BaZr0.85Y0.15O3) proton conducting solid electrolyte disc. The effect of current is nonFaradaic, with Faradaic efficiency values as high as 60 and leads to a reversible variation of the selectivity to CH4 between 16% and 41%. Due to thermal spillover of protons on the Ru-Co catalyst surface, the open circuit selectivity to CO is quite high, i.e. up to 84% and similar values are obtained via negative potential application, i.e. proton supply to the Ru catalyst film deposited on BZY before the deposition of the nanodispersed catalyst. These results underline the similarity between electrochemical promotion and metal support interactions when using proton conducting supports. They also show the usefulness of electrochemical promotion for mechanistic investigations. The electrochemical promotion of nanodispersed catalysts is a promising step for the practical utilization of electrochemical promotion.
Keywords	Electrochemical promotion, EPOC, NEMCA effect, CO2 hydrogenation, Dispersed catalyst, BZY
Remark	https://doi.org/10.1016/j.apcatb.2018.03.031 Link

ID=434

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

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

ID=422

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

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

ID=414

Study of novel proton conductors for high temperature Solid Oxide Cells

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

ID=397

Development of novel metal-supported proton ceramic electrolyser cell with thin film BZY15–Ni electrode and BZY15 electrolyte

Authors
Source	International Journal of Hydrogen Energy Volume: 42, Issue: 19, Pages: 13454–13462 Time of Publication: 2017
Abstract	Metal supports for planar MS-PCEC were manufactured using tape-casting of low-cost ferritic stainless steel. A coating protecting the metal support against oxidation was applied by vacuum infiltration and a buffer layer of La0.5Sr0.5Ti0.75Ni0.25O3–δ (LSTN) was further deposited to smoothen the surface. The BaZr0.85Y0.15O3–δ–NiO (BZY15–NiO) cathode and the BaZr0.85Y0.15O3–δ (BZY15) electrolyte were applied by pulsed laser deposition (PLD) at elevated substrate temperatures (at 700 °C and 600 °C, respectively). The main challenges are related to the restrictions in sintering temperature and atmosphere induced by the metal support, as well as strict demands on the roughness of substrates used for PLD. Reduction treatment of the half cells confirmed that NiO in the BZY15–NiO layer was reduced to Ni, resulting in increased porosity of the BZY15–Ni cathode, while keeping the columnar and dense microstructure of the BZY15 electrolyte. Initial electrochemical testing with a Pt anode showed a total resistance of 40 Ω·cm2 at 600 °C. Through this work important advances in using metal supports and thin films in planar PCEC assemblies have been made.
Keywords	Proton ceramic electrolyser cell (PCEC); Tape casting; Thin film deposition; Metal supports
Remark	https://doi.org/10.1016/j.ijhydene.2017.03.028 Link

ID=354

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

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

ID=327

Electrochemical promotion of the hydrogenation of CO2 on Ru deposited on a BZY proton conductor

Authors	I. Kalaitzidou, A. Katsaounis, T. Norby, C.G. Vayenas
Source	Journal of Catalysis Volume: 331, Pages: 98–109 Time of Publication: 2015
Abstract	he kinetics and the electrochemical promotion of the hydrogenation of CO2 on polycrystalline Ru deposited on BZY (BaZr0.85Y0.15O3−α + 1 wt% NiO), a proton conductor in wet atmospheres, with α ≈ 0.075, was investigated at temperatures 300–450 °C and atmospheric pressure. Methane and CO were the only detectable products and the selectivity to CH4 could be reversibly controlled between 15% and 65% by varying the catalyst potential by less than 1.2 V. The rate and the selectivity to CH4 are very significantly enhanced by proton removal from the catalyst via electrochemically controlled spillover of atomic H from the catalyst surface to the proton-conducting support. The effect is strongly non-Faradaic and the apparent Faradaic efficiency of methanation takes values up to 500 and depends strongly on the porous Ru catalyst film thickness. The observed strong promotional effect, in conjunction with the observed reaction kinetics, is in good agreement with the rules of electrochemical and chemical promotion.
Keywords	Hydrogenation of CO2; CO2 methanation; Ru catalyst; RWGS reaction; BZY proton conducting support; Selectivity modification; Electrochemical promotion of catalysis (EPOC); Non-faradaic electrochemical modification of catalytic activity (NEMCA effect)
Remark	doi:10.1016/j.jcat.2015.08.023 Link

ID=116

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

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