Effects of surface chemical potentials on cation segregation

Ostrovskiy, Eugene; Huang, Yi-Lin; Wachsman, Eric D.

doi:10.1039/d0ta08850a

Effects of surface chemical potentials on cation segregation

Journal Article · Mon Dec 14 00:00:00 EST 2020 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d0ta08850a· OSTI ID:1849290

^[1]; ^[2]; ^[2]

Univ. of Maryland, College Park, MD (United States); OSTI
Univ. of Maryland, College Park, MD (United States)

Surface cation segregation on perovskite-type electrodes is one of the major issues limiting the durability of high-temperature solid-oxide electrochemical cells, and this process is strongly dependent on temperature, the external gas-environment, and impurities in air, such as CO₂. Here cation segregation on La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) is systematically evaluated under a set of chemical potentials to determine the origin of surface segregation and the dominant factors that govern the segregation process. Temperature is the main driving force for surface strontium segregation as the thermodynamic stability of each phase varies, and the SrO particles appear primarily in a specific operating window. In addition to the required thermal energy, the presence of gaseous oxygen-containing molecules as reactants help drive the precipitation of SrO. Oxygen partial pressure (pO₂) controls the defect chemistry of LSCF, leading to promotion or suppression of surface segregation. The presence of CO₂ promotes the nucleation process and suppresses the surface migration step, significantly altering the surface morphology. We also show that A-site deficiency can limit the SrO segregation in certain conditions but shows no effect in others. This study reveals the impact of gas–solid interactions on surface segregation and highlights the subtle relationship between multiple segregation driving forces.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Maryland, College Park, MD (United States)

Sponsoring Organization:: USDOE; USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: FE0031662

OSTI ID:: 1849290

Alternate ID(s):: OSTI ID: 1755452

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 3 Vol. 9; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

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
Sm0.5Sr0.5CoO3 cathodes for low-temperature SOFCs Xia, C. Solid State Ionics, Vol. 149, Issue 1-2 https://doi.org/10.1016/S0167-2738(02)00131-5	journal	July 2002
Perovskite-type oxides for high-temperature oxygen separation membranes Kharton, V. V.; Yaremchenko, A. A.; Kovalevsky, A. V. Journal of Membrane Science, Vol. 163, Issue 2 https://doi.org/10.1016/S0376-7388(99)00172-6	journal	November 1999
Investigation of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ based cathode SOFC Yan, Aiyu; Maragou, Vasiliki; Arico, Antonino Applied Catalysis B: Environmental, Vol. 76, Issue 3-4 https://doi.org/10.1016/j.apcatb.2007.06.010	journal	November 2007
Effect of atmospheric CO2 on surface segregation and phase formation in La0.6Sr0.4Co0.2Fe0.8O3− thin films Yu, Yang; Luo, Heng; Cetin, Deniz Applied Surface Science, Vol. 323 https://doi.org/10.1016/j.apsusc.2014.09.019	journal	December 2014
A variational approach to surface cation segregation in mixed conducting perovskites Mebane, David S. Computational Materials Science, Vol. 103 https://doi.org/10.1016/j.commatsci.2014.11.025	journal	June 2015
High- and low- temperature behaviors of La0.6Sr0.4Co0.2Fe0.8O3−δ cathode operating under CO2/H2O-containing atmosphere Zhao, Zhe; Liu, Li; Zhang, Xiaomin International Journal of Hydrogen Energy, Vol. 38, Issue 35 https://doi.org/10.1016/j.ijhydene.2013.09.089	journal	November 2013
Performance stability and degradation mechanism of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ cathodes under solid oxide fuel cells operation conditions Liu, Yihui; Chen, Kongfa; Zhao, Ling International Journal of Hydrogen Energy, Vol. 39, Issue 28 https://doi.org/10.1016/j.ijhydene.2014.03.077	journal	September 2014
Phase stability of Sm0.5Sr0.5CoO3 cathodes for on-planar type, single-chamber, solid oxide fuel cells Song, Hwa Seob; Min, Ji-Hyun; Kim, Joosun Journal of Power Sources, Vol. 191, Issue 2 https://doi.org/10.1016/j.jpowsour.2009.02.028	journal	June 2009
Lattice expansion of LSCF-6428 cathodes measured by in situ XRD during SOFC operation Hardy, John S.; Templeton, Jared W.; Edwards, Dan J. Journal of Power Sources, Vol. 198 https://doi.org/10.1016/j.jpowsour.2011.09.099	journal	January 2012
Effect of CO2 on the stability of strontium doped lanthanum manganite cathode Hu, Boxun; Mahapatra, Manoj K.; Keane, Michael Journal of Power Sources, Vol. 268 https://doi.org/10.1016/j.jpowsour.2014.06.044	journal	December 2014
Thermodynamic stability maps for the La0.6Sr0.4Co0.2Fe0.8O3±δ–CO2–O2 system for application in solid oxide fuel cells Darvish, Shadi; Gopalan, Srikanth; Zhong, Yu Journal of Power Sources, Vol. 336 https://doi.org/10.1016/j.jpowsour.2016.10.004	journal	December 2016
Degradation of oxygen reduction reaction kinetics in porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathodes due to aging-induced changes in surface chemistry Baqué, Laura C.; Soldati, Analía L.; Teixeira-Neto, Erico Journal of Power Sources, Vol. 337 https://doi.org/10.1016/j.jpowsour.2016.10.090	journal	January 2017
Effect of A-site lanthanum doping on the CO2 tolerance of SrCo0.8Fe0.2O3−-δ oxygen-transporting membranes Klande, Tobias; Ravkina, Olga; Feldhoff, Armin Journal of Membrane Science, Vol. 437 https://doi.org/10.1016/j.memsci.2013.02.051	journal	June 2013
Thermal and chemical lattice expansibility of La0.6Sr0.4Co1−yFeyO3−δ (y=0.2, 0.4, 0.6 and 0.8) Hashimoto, Shin-ichi; Fukuda, Yasuhiro; Kuhn, Melanie Solid State Ionics, Vol. 186, Issue 1 https://doi.org/10.1016/j.ssi.2011.01.014	journal	March 2011
Oxygen nonstoichiometry, thermo-chemical stability and lattice expansion of La0.6Sr0.4FeO3−δ Kuhn, M.; Hashimoto, S.; Sato, K. Solid State Ionics, Vol. 195, Issue 1 https://doi.org/10.1016/j.ssi.2011.05.013	journal	July 2011
Electrochemically driven cation segregation in the mixed conductor La0.6Sr0.4Co0.2Fe0.8O3−δ Finsterbusch, M.; Lussier, A.; Schaefer, J. A. Solid State Ionics, Vol. 212 https://doi.org/10.1016/j.ssi.2012.02.006	journal	March 2012
Chemical stability of La0.6Sr0.4CoO3−δ in oxygen permeation applications under exposure to N2 and CO2 Esposito, Vincenzo; Søgaard, Martin; Hendriksen, Peter Vang Solid State Ionics, Vol. 227 https://doi.org/10.1016/j.ssi.2012.08.015	journal	October 2012
Strontium surface segregation in La0.58Sr0.4Co0.2Fe0.8O3-δ annealed under compression Araki, Wakako; Yamaguchi, Toru; Arai, Yoshio Solid State Ionics, Vol. 268 https://doi.org/10.1016/j.ssi.2014.09.019	journal	December 2014
Strontium surface segregation in La0.6Sr0.4Co0.2Fe0.8O3−δ subjected to mechanical stress Araki, W.; Miyashita, M.; Arai, Y. Solid State Ionics, Vol. 290 https://doi.org/10.1016/j.ssi.2016.04.003	journal	July 2016
Segregated Chemistry and Structure on (001) and (100) Surfaces of (La _{1– x} Sr _x ) ₂ CoO ₄ Override the Crystal Anisotropy in Oxygen Exchange Kinetics Chen, Yan; Téllez, Helena; Burriel, Mónica Chemistry of Materials, Vol. 27, Issue 15 https://doi.org/10.1021/acs.chemmater.5b02292	journal	July 2015
Improving the Electrocatalytic Activity and Durability of the La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ Cathode by Surface Modification Chen, Huijun; Guo, Zheng; Zhang, Lei A. ACS Applied Materials & Interfaces, Vol. 10, Issue 46 https://doi.org/10.1021/acsami.8b14693	journal	October 2018
Oxygen Dissociation Kinetics of Concurrent Heterogeneous Reactions on Metal Oxides Huang, Yi-Lin; Pellegrinelli, Christopher; Wachsman, Eric D. ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b01096	journal	August 2017
Molecular Reactions of O ₂ and CO ₂ on Ionically Conducting Catalyst Huang, Yi-Lin; Pellegrinelli, Christopher; Sakbodin, Mann ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03467	journal	January 2018
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
Investigation of surface Sr segregation in model thin film solid oxidefuel cell perovskite electrodes Jung, WooChul; Tuller, Harry L. Energy Environ. Sci., Vol. 5, Issue 1 https://doi.org/10.1039/C1EE02762J	journal	January 2012
Suppression of Sr surface segregation in La _1−x Sr _x Co _1−y Fe _y O _3−δ : a first principles study Ding, Hepeng; Virkar, Anil V.; Liu, Meilin Phys. Chem. Chem. Phys., Vol. 15, Issue 2 https://doi.org/10.1039/C2CP43148C	journal	January 2013
Insight into surface segregation and chromium deposition on La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ cathodes of solid oxide fuel cells Zhao, Ling; Drennan, John; Kong, Chun J. Mater. Chem. A, Vol. 2, Issue 29 https://doi.org/10.1039/C4TA01426J	journal	January 2014
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
Suppressing cation segregation on lanthanum-based perovskite oxides to enhance the stability of solid oxide fuel cell cathodes Kwon, Hyunguk; Lee, Wonyoung; Han, Jeong Woo RSC Advances, Vol. 6, Issue 74 https://doi.org/10.1039/C6RA15253H	journal	January 2016
Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability Li, Yifeng; Zhang, Wenqiang; Zheng, Yun Chemical Society Reviews, Vol. 46, Issue 20 https://doi.org/10.1039/C7CS00120G	journal	January 2017
Direct observation of enhanced water and carbon dioxide reactivity on multivalent metal oxides and their composites Huang, Yi-Lin; Pellegrinelli, Christopher; Geller, Aaron Energy & Environmental Science, Vol. 10, Issue 4 https://doi.org/10.1039/C7EE00363C	journal	January 2017
Effect of crystal orientation on the segregation of aliovalent dopants at the surface of La _0.6 Sr _0.4 CoO ₃ Pişkin, Fatih; Bliem, Roland; Yildiz, Bilge Journal of Materials Chemistry A, Vol. 6, Issue 29 https://doi.org/10.1039/C8TA01293H	journal	January 2018
In situ study of strontium segregation in La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ in ambient atmospheres using high-temperature environmental scanning electron microscopy Niania, Mathew; Podor, Renaud; Britton, T. Ben Journal of Materials Chemistry A, Vol. 6, Issue 29 https://doi.org/10.1039/C8TA01341A	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
Trainable Weka Segmentation: a machine learning tool for microscopy pixel classification Arganda-Carreras, Ignacio; Kaynig, Verena; Rueden, Curtis Bioinformatics, Vol. 33, Issue 15 https://doi.org/10.1093/bioinformatics/btx180	journal	March 2017
Lowering the Temperature of Solid Oxide Fuel Cells Wachsman, E. D.; Lee, K. T. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1204090	journal	November 2011
(Invited) Towards a Fundamental Understanding of the Cathode Degradation Mechanisms Wachsman, E. D.; Huang, Y. -L.; Pellegrinelli, C. ECS Transactions, Vol. 61, Issue 1 https://doi.org/10.1149/06101.0047ecst	journal	March 2014
Thermodynamic Stability of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3- _δ in Carbon Dioxide Impurity: A Comprehensive Experimental and Computational Assessment Darvish, Shadi; Zhong, Yu; Gopalan, Srikanth ECS Transactions, Vol. 78, Issue 1 https://doi.org/10.1149/07801.1021ecst	journal	May 2017
Degradation of La[sub 0.6]Sr[sub 0.4]Fe[sub 0.8]Co[sub 0.2]O[sub 3−δ] in Carbon Dioxide and Water Atmospheres Benson, S. J. Journal of The Electrochemical Society, Vol. 146, Issue 4 https://doi.org/10.1149/1.1391762	journal	January 1999
Strong Performance Improvement of La[sub 0.6]Sr[sub 0.4]Co[sub 0.8]Fe[sub 0.2]O[sub 3−δ] SOFC Cathodes by Electrochemical Activation Baumann, Frank S.; Fleig, Jürgen; Konuma, Mitsuharu Journal of The Electrochemical Society, Vol. 152, Issue 10 https://doi.org/10.1149/1.2034529	journal	January 2005
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
A Kinetic Study of Catalytic Activity Degradation of La0.6Sr0.4Co0.2Fe0.8O3-δ Oh, Dongjo; Yoo, Jiho; Gostovic, Danijel ECS Transactions, Vol. 16, Issue 51 https://doi.org/10.1149/1.3242224	journal	August 2009
Mechanisms of Performance Degradation of (La,Sr)(Co,Fe)O _3-δ Solid Oxide Fuel Cell Cathodes Wang, Hongqian; Yakal-Kremski, Kyle J.; Yeh, Ted Journal of The Electrochemical Society, Vol. 163, Issue 6 https://doi.org/10.1149/2.0031607jes	journal	January 2016
Surface Strontium Segregation of Solid Oxide Fuel Cell Cathodes Proved by In Situ Depth-Resolved X-ray Absorption Spectroscopy Orikasa, Y.; Crumlin, E. J.; Sako, S. ECS Electrochemistry Letters, Vol. 3, Issue 4 https://doi.org/10.1149/2.006404eel	journal	January 2014
Oxygen Nonstoichiometry and Thermo-Chemical Stability of Perovskite-Type La _0.6 Sr _0.4 Co _{1- y} Fe _y O _3- _δ ( y = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1) Materials Kuhn, M.; Fukuda, Y.; Hashimoto, S. Journal of The Electrochemical Society, Vol. 160, Issue 1 https://doi.org/10.1149/2.050301jes	journal	November 2012
Mechanism of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O ₃ cathode degradation Oh, Dongjo; Gostovic, Danijel; Wachsman, Eric D. Journal of Materials Research, Vol. 27, Issue 15 https://doi.org/10.1557/jmr.2012.222	journal	July 2012

Similar Records

Surface Gibbs free energy analyses of Sr segregation in lanthanum strontium iron oxide

Journal Article · Fri Feb 24 19:00:00 EST 2023 · Surface Science · OSTI ID:2204046

Unraveling the Role of Transport, Electrocatalysis, and Surface Science in the Solid Oxide Fuel Cell Cathode Oxygen Reduction Reaction

Technical Report · Thu Apr 06 00:00:00 EDT 2017 · OSTI ID:1349870

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Effects of surface chemical potentials on cation segregation

Citation Formats

References (47)

Similar Records

Related Subjects