Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Rowberg, Andrew J. E.; Slomski, Heather S.; Kim, Namhoon; Strange, Nicholas A.; Gorman, Brian P.; Shulda, Sarah; Ginley, David S.; Kweon, Kyoung E.; Wood, Brandon C.

doi:10.1021/acs.chemmater.4c00511

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Journal Article · Sat Jun 15 00:00:00 EDT 2024 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.4c00511· OSTI ID:2397031

^[1]; Slomski, Heather S. ^[2]; Kim, Namhoon ^[1]; ^[3]; Gorman, Brian P. ^[4]; Shulda, Sarah ^[5]; Ginley, David S. ^[5]; ^[1]; ^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO₂ (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO₃. Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO₃ also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO₃ to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO₃ forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO₃ on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-76SF00515; AC36-08GO28308; AC52-07NA27344

OSTI ID:: 2397031

Alternate ID(s):: OSTI ID: 2396648
OSTI ID: 2440284

Report Number(s):: LLNL--JRNL-860613; 1091726

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 13 Vol. 36; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (63)

Physical Chemistry of Ionic Materials: Ions and Electrons in Solids Maier, Joachim https://doi.org/10.1002/0470020229	book	April 2004
Kinetics of Materials Balluffi, Robert W.; Allen, Samuel M.; Carter, W. Craig https://doi.org/10.1002/0471749311	book	September 2005
High temperature and in situ study of SrO surface precipitation on perovskite ceramics Niania, Mathew; Podor, Renaud; Britton, Ben European Microscopy Congress 2016: Proceedings https://doi.org/10.1002/9783527808465.EMC2016.5758	other	December 2016
The Sluggish Diffusion of Cations in CeO₂ Probed through Molecular Dynamics and Metadynamics Simulations Körfer, Sylvia; Bonkowski, Alexander; Kler, Joe Advanced Engineering Materials, Vol. 25, Issue 18 https://doi.org/10.1002/adem.202201788	journal	February 2023
Strain Tuning and Strong Enhancement of Ionic Conductivity in SrZrO ₃ -RE ₂ O ₃ (RE = Sm, Eu, Gd, Dy, and Er) Nanocomposite Films Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia Advanced Functional Materials, Vol. 25, Issue 27 https://doi.org/10.1002/adfm.201404420	journal	June 2015
A Highly Efficient and Robust Nanofiber Cathode for Solid Oxide Fuel Cells Chen, Yu; Bu, Yunfei; Zhang, Yanxiang Advanced Energy Materials, Vol. 7, Issue 6 https://doi.org/10.1002/aenm.201601890	journal	November 2016
Electrostatic interactions between charged defects in supercells Freysoldt, Christoph; Neugebauer, Jörg; Van de Walle, Chris G. physica status solidi (b), Vol. 248, Issue 5 https://doi.org/10.1002/pssb.201046289	journal	December 2010
Thermochemical Stability, Electrical Conductivity, and Seebeck Coefficient of Sr-Doped LaCo0.2Fe0.8O3-δ Tai, L-W.; Nasrallah, M. M.; Anderson, H. U. Journal of Solid State Chemistry, Vol. 118, Issue 1 https://doi.org/10.1006/jssc.1995.1319	journal	August 1995
Protonic and oxygen-ion conduction in SrZrO3-based materials Labrincha, J. A.; Marques, F. M. B.; Frade, J. R. Journal of Materials Science, Vol. 30, Issue 11 https://doi.org/10.1007/BF00349644	journal	June 1995
Surface Segregation in Solid Oxide Cell Oxygen Electrodes: Phenomena, Mitigation Strategies and Electrochemical Properties Chen, Kongfa; Jiang, San Ping Electrochemical Energy Reviews, Vol. 3, Issue 4 https://doi.org/10.1007/s41918-020-00078-z	journal	August 2020
Frequency factors and isotope effects in solid state rate processes Vineyard, George H. Journal of Physics and Chemistry of Solids, Vol. 3, Issue 1-2 https://doi.org/10.1016/0022-3697(57)90059-8	journal	January 1957
Chemical reactivity and interdiffusion of (La, Sr)MnO3 and (Zr, Y)O2, solid oxide fuel cell cathode and electrolyte materials van Roosmalen, J. Solid State Ionics, Vol. 52, Issue 4 https://doi.org/10.1016/0167-2738(92)90177-Q	journal	June 1992
Phase relations and conductivity of Sr- and La-zirconates Willy Poulsen, Finn; van der Puil, Nelleke Solid State Ionics, Vol. 53-56 https://doi.org/10.1016/0167-2738(92)90254-m	journal	July 1992
Defect structure of SrZrO3 Labrincha, J.; Frade, J.; Marques, F. Solid State Ionics, Vol. 61, Issue 1-3 https://doi.org/10.1016/0167-2738(93)90336-2	journal	May 1993
Properties of A-site-deficient La0.6Sr0.4Co0.2Fe0.8O3−δ-based perovskite oxides Kostogloudis, G. Ch; Ftikos, Ch Solid State Ionics, Vol. 126, Issue 1-2 https://doi.org/10.1016/S0167-2738(99)00230-1	journal	November 1999
A review of solid oxide steam-electrolysis cell systems: Thermodynamics and thermal integration Min, Gyubin; Choi, Saeyoung; Hong, Jongsup Applied Energy, Vol. 328 https://doi.org/10.1016/j.apenergy.2022.120145	journal	December 2022
Degradation mechanism of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ /Gd 0.1 Ce 0.9 O 2-δ composite electrode operated under solid oxide electrolysis and fuel cell conditions Laurencin, J.; Hubert, M.; Sanchez, D. Ferreira Electrochimica Acta, Vol. 241 https://doi.org/10.1016/j.electacta.2017.05.011	journal	July 2017
Technological development of hydrogen production by solid oxide electrolyzer cell (SOEC) Ni, M.; Leung, M.; Leung, D. International Journal of Hydrogen Energy, Vol. 33, Issue 9 https://doi.org/10.1016/j.ijhydene.2008.02.048	journal	May 2008
Preparation of NiO–YSZ composite powder by a combustion method and its application for cathode of SOEC Liang, Mingde; Yu, Bo; Wen, Mingfen International Journal of Hydrogen Energy, Vol. 35, Issue 7 https://doi.org/10.1016/j.ijhydene.2009.05.006	journal	April 2010
Activation and failure mechanism of La0.6Sr0.4Co0.2Fe0.8O3−δ air electrode in solid oxide electrolyzer cells under high-current electrolysis Pan, Zehua; Liu, Qinglin; Ni, Meng International Journal of Hydrogen Energy, Vol. 43, Issue 11 https://doi.org/10.1016/j.ijhydene.2018.01.181	journal	March 2018
Activation of LSCF–YSZ interface by cobalt migration during electrolysis operation in solid oxide electrolysis cells Shen, Jian; Miao, Bin; Liu, Qinglin International Journal of Hydrogen Energy, Vol. 47, Issue 90 https://doi.org/10.1016/j.ijhydene.2022.09.008	journal	November 2022
A critical review on cathode materials for steam electrolysis in solid oxide electrolysis Biswas, Saheli; Kaur, Gurpreet; Paul, Gary International Journal of Hydrogen Energy, Vol. 48, Issue 34 https://doi.org/10.1016/j.ijhydene.2022.11.307	journal	April 2023
Degradation phenomena in a solid oxide electrolysis cell after 9000 h of operation Tietz, F.; Sebold, D.; Brisse, A. Journal of Power Sources, Vol. 223 https://doi.org/10.1016/j.jpowsour.2012.09.061	journal	February 2013
Degradation study by 3D reconstruction of a nickel–yttria stabilized zirconia cathode after high temperature steam electrolysis operation Lay-Grindler, E.; Laurencin, J.; Villanova, J. Journal of Power Sources, Vol. 269 https://doi.org/10.1016/j.jpowsour.2014.07.066	journal	December 2014
Microstructural comparison of solid oxide electrolyser cells operated for 6100 h and 9000 h The, D.; Grieshammer, S.; Schroeder, M. Journal of Power Sources, Vol. 275 https://doi.org/10.1016/j.jpowsour.2014.10.188	journal	February 2015
Stability of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 /Ce 0.9 Gd 0.1 O 2 cathodes during sintering and solid oxide fuel cell operation Kiebach, Ragnar; Zhang, Wei-Wei; Zhang, Wei Journal of Power Sources, Vol. 283 https://doi.org/10.1016/j.jpowsour.2015.02.064	journal	June 2015
Correlative tomography at the cathode/electrolyte interfaces of solid oxide fuel cells Wankmüller, Florian; Szász, Julian; Joos, Jochen Journal of Power Sources, Vol. 360 https://doi.org/10.1016/j.jpowsour.2017.06.008	journal	August 2017
An insight into the effects of B-site transition metals on the activity, activation effect and stability of perovskite oxygen electrodes for solid oxide electrolysis cells Bi, Jiaxin; Yang, Shengbing; Zhong, Shaohua Journal of Power Sources, Vol. 363 https://doi.org/10.1016/j.jpowsour.2017.07.118	journal	September 2017
Alternative and innovative solid oxide electrolysis cell materials: A short review Nechache, Aziz; Hody, Stéphane Renewable and Sustainable Energy Reviews, Vol. 149 https://doi.org/10.1016/j.rser.2021.111322	journal	October 2021
Effect of Gd-doped ceria interlayer on the stability of solid oxide electrolysis cell Kim, Sun Jae; Kim, Sun Woong; Park, Young Min Solid State Ionics, Vol. 295 https://doi.org/10.1016/j.ssi.2016.07.007	journal	November 2016
Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions Feng, Zhenxing; Hong, Wesley T.; Fong, Dillon D. Accounts of Chemical Research, Vol. 49, Issue 5 https://doi.org/10.1021/acs.accounts.5b00555	journal	April 2016
Computational Study of Cation Diffusion in Ceria Beschnitt, Stefan; Zacherle, Tobias; De Souza, Roger A. The Journal of Physical Chemistry C, Vol. 119, Issue 49 https://doi.org/10.1021/acs.jpcc.5b09499	journal	November 2015
Optimizing Proton Conductivity in Zirconates through Defect Engineering Rowberg, Andrew J. E.; Weston, Leigh; Van de Walle, Chris G. ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.8b02222	journal	March 2019
Oxide-ion conductors by design Goodenough, John B. Nature, Vol. 404, Issue 6780 https://doi.org/10.1038/35009177	journal	April 2000
Influence of surface atomic structure demonstrated on oxygen incorporation mechanism at a model perovskite oxide Riva, Michele; Kubicek, Markus; Hao, Xianfeng Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05685-5	journal	September 2018
Surface chemistry of La _0.6 Sr _0.4 CoO _3−δ thin films and its impact on the oxygen surface exchange resistance Rupp, Ghislain M.; Téllez, Helena; Druce, John Journal of Materials Chemistry A, Vol. 3, Issue 45 https://doi.org/10.1039/C5TA05279C	journal	January 2015
Design principles of tuning oxygen vacancy diffusion in SrZrO₃ for resistance random access memory Guo, Zhonglu; Zhu, Linggang; Zhou, Jian Journal of Materials Chemistry C, Vol. 3, Issue 16 https://doi.org/10.1039/C5TC00302D	journal	January 2015
A DFT+U study on the contribution of 4f electrons to oxygen vacancy formation and migration in Ln-doped CeO ₂ Alaydrus, M.; Sakaue, M.; Kasai, H. Physical Chemistry Chemical Physics, Vol. 18, Issue 18 https://doi.org/10.1039/C6CP00637J	journal	January 2016
Acceptor doping in the proton conductor SrZrO ₃ Weston, Leigh; Janotti, A.; Cui, X. Y. Physical Chemistry Chemical Physics, Vol. 19, Issue 18 https://doi.org/10.1039/C7CP01471F	journal	January 2017
Elucidating the origin of oxide ion blocking effects at GDC/SrZr(Y)O₃/YSZ interfaces Develos-Bagarinao, Katherine; Yokokawa, Harumi; Kishimoto, Haruo Journal of Materials Chemistry A, Vol. 5, Issue 18 https://doi.org/10.1039/C7TA01589E	journal	January 2017
Stable high current density operation of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ oxygen electrodes Lu, Matthew Y.; Railsback, Justin G.; Wang, Hongqian Journal of Materials Chemistry A, Vol. 7, Issue 22 https://doi.org/10.1039/C9TA04020J	journal	January 2019
Understanding carbon contamination in the proton-conducting zirconates and cerates Rowberg, Andrew J. E.; Swift, Michael W.; Van de Walle, Chris G. Physical Chemistry Chemical Physics, Vol. 23, Issue 26 https://doi.org/10.1039/D1CP01902C	journal	January 2021
Chromium deposition and poisoning of La _0.8 Sr _0.2 MnO ₃ oxygen electrodes of solid oxide electrolysis cells Chen, Kongfa; Hyodo, Junji; Dodd, Aaron Faraday Discussions, Vol. 182 https://doi.org/10.1039/c5fd00010f	journal	January 2015
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 124, Issue 21 https://doi.org/10.1063/1.2204597	journal	June 2006
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Structural and electronic properties of SrZrO 3 and Sr(Ti,Zr) O 3 alloys Weston, L.; Janotti, A.; Cui, X. Y. Physical Review B, Vol. 92, Issue 8 https://doi.org/10.1103/PhysRevB.92.085201	journal	August 2015
Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations Freysoldt, Christoph; Neugebauer, Jörg; Van de Walle, Chris G. Physical Review Letters, Vol. 102, Issue 1 https://doi.org/10.1103/PhysRevLett.102.016402	journal	January 2009
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
First-principles calculations for point defects in solids Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann Reviews of Modern Physics, Vol. 86, Issue 1 https://doi.org/10.1103/RevModPhys.86.253	journal	March 2014
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Proton-Conducting Oxides Kreuer, K. D. Annual Review of Materials Research, Vol. 33, Issue 1, p. 333-359 https://doi.org/10.1146/annurev.matsci.33.022802.091825	journal	August 2003
Strontium Migration at the GDC-YSZ Interface of Solid Oxide Cells in SOFC and SOEC Modes Rinaldi, Giorgio; Nakajo, Arata; Van herle, Jan ECS Transactions, Vol. 78, Issue 1 https://doi.org/10.1149/07801.3297ecst	journal	May 2017
Degradation Mechanisms of La–Sr–Co–Fe–O[sub 3] SOFC Cathodes Simner, S. P.; Anderson, M. D.; Engelhard, M. H. Electrochemical and Solid-State Letters, Vol. 9, Issue 10 https://doi.org/10.1149/1.2266160	journal	January 2006
SrZrO ₃ Formation at the Interlayer/Electrolyte Interface during (La _1-x Sr _x ) _1-δ Co _1-y Fe _y O ₃ Cathode Sintering Lu, Zigui; Darvish, Shadi; Hardy, John Journal of The Electrochemical Society, Vol. 164, Issue 10 https://doi.org/10.1149/2.0141710jes	journal	January 2017
Revisiting the Temperature Dependent Ionic Conductivity of Yttria Stabilized Zirconia (YSZ) Ahamer, C.; Opitz, A. K.; Rupp, G. M. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.0641707jes	journal	January 2017
Nine Thousand Hours of Operation of a Solid Oxide Cell in Steam Electrolysis Mode Schefold, J.; Brisse, A.; Tietz, F. Journal of The Electrochemical Society, Vol. 159, Issue 2 https://doi.org/10.1149/2.076202jes	journal	January 2011

Similar Records

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Journal Article · Sat Jun 15 00:00:00 EDT 2024 · Chemistry of Materials · OSTI ID:2396648

Kinetics and Thermodynamics of Sr Permeation in CeO₂-Based Barrier Layers for Solid-Oxide Electrolyzer Cells

Journal Article · Mon Sep 15 20:00:00 EDT 2025 · ACS Applied Materials & Interfaces · OSTI ID:2997204

Related Subjects

08 HYDROGEN
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Citation Formats

References (63)

Similar Records

Related Subjects