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

Rowberg, Andrew J. E.; Van Winkle, Madeline; Slomski, Heather S.; Chatterjee, Sourav; Kane, Nicholas J.; Yu, Henry; Kim, Namhoon; Ginley, David S.; Gorman, Brian P.; Shulda, Sarah; Heo, Tae Wook; Kweon, Kyoung Eun; Wood, Brandon C.

doi:10.1021/acsami.5c12101

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

Journal Article · Tue Sep 16 00:00:00 EDT 2025 · ACS Applied Materials & Interfaces

DOI:https://doi.org/10.1021/acsami.5c12101· OSTI ID:2997204

^[1]; Van Winkle, Madeline ^[2]; ^[3]; Chatterjee, Sourav ^[1]; Kane, Nicholas J. ^[4]; Yu, Henry ^[1]; Kim, Namhoon ^[1]; Ginley, David S. ^[2]; Gorman, Brian P. ^[5]; Shulda, Sarah ^[2]; ^[1]; ^[1]; ^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Colorado School of Mines, Golden, CO (United States)

Solid-oxide electrolyzer cells (SOECs) convert steam to hydrogen efficiently at high temperatures. However, during operation, the diffusion of cations or impurities through the cells due to electrode degradation can cause unwanted secondary phases to form, which may degrade device performance. Here, in this study, we use atomistic and mesoscale simulations coupled with experimental analysis to study the diffusion of Sr through the Gd-doped CeO₂ (GDC) barrier layer used to protect the yttria-stabilized zirconia (YSZ) electrolyte in SOECs. From our atomistic calculations, we find Sr diffusion to be negligibly slow in bulk GDC; however, surface diffusion is much more favorable. Subsequent mesoscale simulations show that Sr diffusion is activated when the porosity of GDC exceeds ∼10% and significantly exceeds diffusion in bulk and grain boundary regions. We also find that SrO-based species can accumulate at GDC surfaces; however, SrO aggregation and coarsening will be limited by the large lattice mismatch between GDC and SrO. Energy-dispersive X-ray spectroscopy (EDS) and electron diffraction confirm that Sr can accumulate within GDC pores and form disperse Sr-containing secondary phases. Altogether, Sr diffusion in dense GDC is unlikely to give rise to thick SrO layers, which would severely limit device performance. The formation of Sr-containing secondary phases can largely be avoided by restricting the porosity of the GDC layer as much as possible.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, 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 Nuclear Energy (NE)

Grant/Contract Number:: AC07-05ID14517; AC36-08GO28308; AC52-07NA27344

OSTI ID:: 2997204

Report Number(s):: LLNL--JRNL-2007077

Journal Information:: ACS Applied Materials & Interfaces, Journal Name: ACS Applied Materials & Interfaces Journal Issue: 39 Vol. 17; ISSN 1944-8244; ISSN 1944-8252

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Operando and In situ X-ray Spectroscopies of Degradation in La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _{3− δ} Thin Film Cathodes in Fuel Cells Lai, Samson Y.; Ding, Dong; Liu, Mingfei ChemSusChem, Vol. 7, Issue 11 https://doi.org/10.1002/cssc.201402670	journal	September 2014
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
Computer simulation of 3-D grain growth using a phase-field model Krill III, C. E.; Chen, L. -Q. Acta Materialia, Vol. 50, Issue 12 https://doi.org/10.1016/S1359-6454(02)00084-8	journal	July 2002
A quantitative and thermodynamically consistent phase-field interpolation function for multi-phase systems Moelans, Nele Acta Materialia, Vol. 59, Issue 3 https://doi.org/10.1016/j.actamat.2010.10.038	journal	February 2011
A high-performance intermediate temperature reversible solid oxide cell with a new barrier layer free oxygen electrode Zhao, Kai; Lu, Jiaxin; Le, Long Applied Energy, Vol. 361 https://doi.org/10.1016/j.apenergy.2024.122962	journal	May 2024
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
Influence of boundary conditions on computation of the effective thermal conductivity of foams Low, Z. K.; Blal, N.; Naouar, N. International Journal of Heat and Mass Transfer, Vol. 155 https://doi.org/10.1016/j.ijheatmasstransfer.2020.119781	journal	July 2020
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
Current status, research trends, and challenges in water electrolysis science and technology Grigoriev, S. A.; Fateev, V. N.; Bessarabov, D. G. International Journal of Hydrogen Energy, Vol. 45, Issue 49 https://doi.org/10.1016/j.ijhydene.2020.03.109	journal	October 2020
The optical band gap of Gd-doped CeO2 thin films as function of temperature and composition Ruiz-Trejo, Enrique Journal of Physics and Chemistry of Solids, Vol. 74, Issue 4 https://doi.org/10.1016/j.jpcs.2012.12.014	journal	April 2013
Quantifying tortuosity in porous Li-ion battery materials Thorat, Indrajeet V.; Stephenson, David E.; Zacharias, Nathan A. Journal of Power Sources, Vol. 188, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.12.032	journal	March 2009
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
Role of phosphorus impurities in decomposition of La2NiO4–La0.5Ce0.5O2-δ oxygen electrode in a solid oxide electrolysis cell Liu, Tian; Escobar, Julian D.; Olszta, Matthew J. Journal of Power Sources, Vol. 589 https://doi.org/10.1016/j.jpowsour.2023.233748	journal	January 2024
Microstructure-based modeling of inner oxygen pressure in solid oxide electrolysis cells: Analysis of electrode delamination and mitigation Xue, Fei; Lei, Yinkai; Cheng, Tian-Le Journal of Power Sources, Vol. 631 https://doi.org/10.1016/j.jpowsour.2025.236199	journal	March 2025
Voltage cycling as a dynamic operation mode for high temperature electrolysis solid oxide cells Zhu, Zhikuan; Slomski, Heather S.; Dzara, Michael J. Journal of Power Sources, Vol. 642 https://doi.org/10.1016/j.jpowsour.2025.236958	journal	June 2025
MOOSE: A parallel computational framework for coupled systems of nonlinear equations Gaston, Derek; Newman, Chris; Hansen, Glen Nuclear Engineering and Design, Vol. 239, Issue 10 https://doi.org/10.1016/j.nucengdes.2009.05.021	journal	October 2009
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
The surface chemistry of cerium oxide Mullins, David R. Surface Science Reports, Vol. 70, Issue 1 https://doi.org/10.1016/j.surfrep.2014.12.001	journal	March 2015
py4DSTEM: A Software Package for Four-Dimensional Scanning Transmission Electron Microscopy Data Analysis Savitzky, Benjamin H.; Zeltmann, Steven E.; Hughes, Lauren A. Microscopy and Microanalysis https://doi.org/10.1017/S1431927621000477	journal	May 2021
Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells Rowberg, Andrew J. E.; Slomski, Heather S.; Kim, Namhoon Chemistry of Materials, Vol. 36, Issue 13 https://doi.org/10.1021/acs.chemmater.4c00511	journal	June 2024
Understanding (La,Sr)(Co,Fe)O_3−δ Phase Instability within SOECs Using a Combined Experimental and Atomistic Modeling Approach Slomski, Heather S.; Kaufman, Jonas L.; Dzara, Michael J. ACS Physical Chemistry Au, Vol. 5, Issue 2 https://doi.org/10.1021/acsphyschemau.4c00095	journal	January 2025
Chemical Potential Analysis as an Alternative to the van’t Hoff Method: Hypothetical Limits of Solar Thermochemical Hydrogen Lany, Stephan Journal of the American Chemical Society, Vol. 146, Issue 20 https://doi.org/10.1021/jacs.4c02688	journal	May 2024
Electrochemical Polarization Dependence of the Elastic and Electrostatic Driving Forces to Aliovalent Dopant Segregation on LaMnO ₃ Kim, Dongha; Bliem, Roland; Hess, Franziska Journal of the American Chemical Society, Vol. 142, Issue 7 https://doi.org/10.1021/jacs.9b13040	journal	January 2020
Computational engineering of the oxygen electrode-electrolyte interface in solid oxide fuel cells Cheng, Kaiming; Xu, Huixia; Zhang, Lijun npj Computational Materials, Vol. 7, Issue 1 https://doi.org/10.1038/s41524-021-00584-8	journal	July 2021
Realistic roles for hydrogen in the future energy transition Johnson, Nathan; Liebreich, Michael; Kammen, Daniel M. Nature Reviews Clean Technology, Vol. 1, Issue 5 https://doi.org/10.1038/s44359-025-00050-4	journal	April 2025
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
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
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
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
Evaluation of cation migration in lanthanum strontium cobalt ferrite solid oxide fuel cell cathodes via in-operando X-ray diffraction Hardy, J. S.; Coyle, C. A.; Bonnett, J. F. Journal of Materials Chemistry A, Vol. 6, Issue 4 https://doi.org/10.1039/C7TA06856E	journal	January 2018
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
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
In situ characterization of strontium surface segregation in epitaxial La0.7Sr0.3MnO3 thin films as a function of oxygen partial pressure Fister, Tim T.; Fong, Dillon D.; Eastman, Jeffrey A. Applied Physics Letters, Vol. 93, Issue 15 https://doi.org/10.1063/1.2987731	journal	October 2008
Precipitation of dopants on acceptor-doped LaMnO_3±δ revealed by defect chemistry from first principles Hess, Franziska; Yildiz, Bilge The Journal of Chemical Physics, Vol. 154, Issue 6 https://doi.org/10.1063/5.0035691	journal	February 2021
Graphene-like monolayer monoxides and monochlorides Luo, Bingcheng; Yao, Yuan; Tian, Enke Proceedings of the National Academy of Sciences, Vol. 116, Issue 35 https://doi.org/10.1073/pnas.1906510116	journal	August 2019
Tortuosity in electrochemical devices: a review of calculation approaches Tjaden, Bernhard; Brett, Dan J. L.; Shearing, Paul R. International Materials Reviews, Vol. 63, Issue 2 https://doi.org/10.1080/09506608.2016.1249995	journal	November 2016
Native defects, hydrogen impurities, and metal dopants in CeO2 Hoang, Khang; Johannes, Michelle D. Physical Review Materials, Vol. 9, Issue 9 https://doi.org/10.1103/8qzc-t7dy	journal	September 2025
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
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
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
Mean-Value Point in the Brillouin Zone Baldereschi, A. Physical Review B, Vol. 7, Issue 12 https://doi.org/10.1103/PhysRevB.7.5212	journal	June 1973
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies Stevanović, Vladan; Lany, Stephan; Zhang, Xiuwen Physical Review B, Vol. 85, Issue 11 https://doi.org/10.1103/PhysRevB.85.115104	journal	March 2012
Ab initio analysis of the defect structure of ceria Zacherle, T.; Schriever, A.; De Souza, R. A. Physical Review B, Vol. 87, Issue 13 https://doi.org/10.1103/PhysRevB.87.134104	journal	April 2013
First-principles DFT+ U investigation of charged states of defects and fission gas atoms in CeO 2 Shi, Lei; Vathonne, Emerson; Oison, Vincent Physical Review B, Vol. 94, Issue 11 https://doi.org/10.1103/PhysRevB.94.115132	journal	September 2016
First-principles calculations for charged defects at surfaces, interfaces, and two-dimensional materials in the presence of electric fields Freysoldt, Christoph; Neugebauer, Jörg Physical Review B, Vol. 97, Issue 20 https://doi.org/10.1103/PhysRevB.97.205425	journal	May 2018
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
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
Evidence of Subsurface Oxygen Vacancy Ordering on Reduced CeO 2 ( 111 ) Torbrügge, Stefan; Reichling, Michael; Ishiyama, Atsushi Physical Review Letters, Vol. 99, Issue 5 https://doi.org/10.1103/PhysRevLett.99.056101	journal	August 2007
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
Baseload Hydrogen Production Using Nuclear and Renewable Energy: A Comparative Analysis Poudel, Bikash; Wendt, Daniel; McJunkin, Timothy 2024 IEEE Green Technologies Conference (GreenTech) https://doi.org/10.1109/GreenTech58819.2024.10520502	conference	April 2024
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
Resolving the Discrepancy in Tortuosity Factor Estimation for Li-Ion Battery Electrodes through Micro-Macro Modeling and Experiment Usseglio-Viretta, Francois L. E.; Colclasure, Andrew; Mistry, Aashutosh N. Journal of The Electrochemical Society, Vol. 165, Issue 14 https://doi.org/10.1149/2.0731814jes	journal	January 2018
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
State of the art in low-temperature and high-temperature electrolysis Ayers, Katherine E.; Marina, Olga A. MRS Bulletin, Vol. 49, Issue 12 https://doi.org/10.1557/s43577-024-00806-6	journal	November 2024
Challenges in practical button cell testing for hydrogen production from high temperature electrolysis of water Priest, Cameron M.; Gomez, Joshua Y.; Kane, Nicholas J. Frontiers in Energy Research, Vol. 11 https://doi.org/10.3389/fenrg.2023.1278203	journal	September 2023

Similar Records

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:3014869

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

Related Subjects

Gd-doped CeO2
Sr diffusion
microstructure-aware diffusivity
porosity
secondary phase formation
solid oxide electrolysis

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

Citation Formats

References (68)

Similar Records

Related Subjects

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