Examination of the mechanism for the reversible aging behavior at open circuit when changing the operating temperature of (La0.8Sr0.2)0.95 MnO3 electrodes
Abstract
The aging behavior of symmetrical cells, consisting of either (La0.8Sr0.2)0.95 MnO3 (LSM) or La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) electrodes screen printed on either 8 mol% yttria-stabilized zirconia (YSZ) or Ce0.8Gd0.2O2 (GDC) electrolyte substrates, is reported as the symmetrical cell is thermally cycled between 700 °C and 800 °C. For LSM, between 700 °C and 850 °C, the polarization resistance exhibits slow increases or decreases with time (on the order of days) after a quick change in temperature. When increasing the temperature, the polarization resistance decreases with time, and when decreasing the temperature, the polarization resistance slowly increases with time. In a previous work, the authors had explained these results with LSM by connecting the testing conditions to literature reports of surface analysis of LSM thin films which demonstrated a change in the amount of surface cation segregation as a function of temperature. In this work, TEM/EDS/XPS analysis of dense LSM pellets thermally cycled under the same conditions as the symmetrical cells does not indicate any significant reversible change in the surface composition of the LSM pellet between 700 °C and 800 °C. An alternative hypothesis is proposed to explain the relationship between polarization resistance and the LSM cation/anion vacancy concentrations controlled by themore »
- Authors:
-
- National Energy Technology Lab. (NETL), Morgantown, MW (United States); URS Corporation, Morgantown, MW (United States)
- National Energy Technology Lab. (NETL), Morgantown, MW (United States); West Virginia Univ., Morgantown, WV (United States)
- National Energy Technology Lab. (NETL), Morgantown, MW (United States)
- Publication Date:
- Research Org.:
- National Energy Technology Lab. (NETL), Albany, OR (United States)
- Sponsoring Org.:
- USDOE Office of Fossil Energy (FE)
- OSTI Identifier:
- 1225779
- Report Number(s):
- A-CONTR-PUB-051
Journal ID: ISSN 0167-2738; PII: S0167273815000259
- Grant/Contract Number:
- FE0004000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Solid State Ionics
- Additional Journal Information:
- Journal Volume: 272; Journal Issue: C; Journal ID: ISSN 0167-2738
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING; SOFC cathode; aging; LSM; cation; segregation; Schottky defect
Citation Formats
Abernathy, Harry, Finklea, Harry O., Mebane, David S., Song, Xueyan, Chen, Yun, and Gerdes, Kirk. Examination of the mechanism for the reversible aging behavior at open circuit when changing the operating temperature of (La0.8Sr0.2)0.95 MnO3 electrodes. United States: N. p., 2015.
Web. doi:10.1016/j.ssi.2015.01.013.
Abernathy, Harry, Finklea, Harry O., Mebane, David S., Song, Xueyan, Chen, Yun, & Gerdes, Kirk. Examination of the mechanism for the reversible aging behavior at open circuit when changing the operating temperature of (La0.8Sr0.2)0.95 MnO3 electrodes. United States. https://doi.org/10.1016/j.ssi.2015.01.013
Abernathy, Harry, Finklea, Harry O., Mebane, David S., Song, Xueyan, Chen, Yun, and Gerdes, Kirk. Tue .
"Examination of the mechanism for the reversible aging behavior at open circuit when changing the operating temperature of (La0.8Sr0.2)0.95 MnO3 electrodes". United States. https://doi.org/10.1016/j.ssi.2015.01.013. https://www.osti.gov/servlets/purl/1225779.
@article{osti_1225779,
title = {Examination of the mechanism for the reversible aging behavior at open circuit when changing the operating temperature of (La0.8Sr0.2)0.95 MnO3 electrodes},
author = {Abernathy, Harry and Finklea, Harry O. and Mebane, David S. and Song, Xueyan and Chen, Yun and Gerdes, Kirk},
abstractNote = {The aging behavior of symmetrical cells, consisting of either (La0.8Sr0.2)0.95 MnO3 (LSM) or La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) electrodes screen printed on either 8 mol% yttria-stabilized zirconia (YSZ) or Ce0.8Gd0.2O2 (GDC) electrolyte substrates, is reported as the symmetrical cell is thermally cycled between 700 °C and 800 °C. For LSM, between 700 °C and 850 °C, the polarization resistance exhibits slow increases or decreases with time (on the order of days) after a quick change in temperature. When increasing the temperature, the polarization resistance decreases with time, and when decreasing the temperature, the polarization resistance slowly increases with time. In a previous work, the authors had explained these results with LSM by connecting the testing conditions to literature reports of surface analysis of LSM thin films which demonstrated a change in the amount of surface cation segregation as a function of temperature. In this work, TEM/EDS/XPS analysis of dense LSM pellets thermally cycled under the same conditions as the symmetrical cells does not indicate any significant reversible change in the surface composition of the LSM pellet between 700 °C and 800 °C. An alternative hypothesis is proposed to explain the relationship between polarization resistance and the LSM cation/anion vacancy concentrations controlled by the Schottky reaction. The timescale of aging behavior is related to the time necessary for the cations to move to or from the LSM surface to adjust to the new equilibrium at each temperature. Furthermore, the relevance in understanding the mechanism behind the aging behavior is emphasized with respect to fuel cell sample/stack modeling as well as to proper testing procedures for reaching reliable conclusions when comparing different electrode samples.},
doi = {10.1016/j.ssi.2015.01.013},
journal = {Solid State Ionics},
number = C,
volume = 272,
place = {United States},
year = {Tue Feb 17 00:00:00 EST 2015},
month = {Tue Feb 17 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
In situ study of activation and de-activation of LSM fuel cell cathodes – Electrochemistry and surface analysis of thin-film electrodes
journal, October 2012
- Huber, Anne-Katrin; Falk, Mareike; Rohnke, Marcus
- Journal of Catalysis, Vol. 294
Surface segregation and restructuring of colossal-magnetoresistant manganese perovskites
journal, December 2000
- Dulli, Hani; Dowben, P. A.; Liou, S. -H.
- Physical Review B, Vol. 62, Issue 22
In situ characterization of strontium surface segregation in epitaxial La0.7Sr0.3MnO3 thin films as a function of oxygen partial pressure
journal, October 2008
- Fister, Tim T.; Fong, Dillon D.; Eastman, Jeffrey A.
- Applied Physics Letters, Vol. 93, Issue 15
Soft X-Ray Spectroscopic Study of Dense Strontium-Doped Lanthanum Manganite Cathodes for Solid Oxide Fuel Cell Applications
journal, January 2011
- Piper, L. F. J.; Preston, A. R. H.; Cho, S. -W.
- Journal of The Electrochemical Society, Vol. 158, Issue 2
Evidence for strontium segregation in La 0.7 Sr 0.3 MnO 3 thin films grown by pulsed laser deposition: consequences for tunnelling junctions
journal, June 2002
- Bertacco, R.; Contour, J. P.; Barthélemy, A.
- Surface Science, Vol. 511, Issue 1-3
Cation Size Mismatch and Charge Interactions Drive Dopant Segregation at the Surfaces of Manganite Perovskites
journal, May 2013
- Lee, Wonyoung; Han, Jeong Woo; Chen, Yan
- Journal of the American Chemical Society, Vol. 135, Issue 21
X-ray photoelectron spectroscopy of La0.5Sr0.5MnO3
journal, July 2005
- Wu, Qi-Hui; Liu, Meilin; Jaegermann, W.
- Materials Letters, Vol. 59, Issue 16
Investigation of chemisorbed oxygen, surface segregation and effect of post-treatments on La0.8Sr0.2MnO3 powder and screen-printed layers for solid oxide fuel cell cathodes
journal, March 2007
- Caillol, N.; Pijolat, M.; Siebert, E.
- Applied Surface Science, Vol. 253, Issue 10
Stabilities of La0.6Sr0.4Co0.2Fe0.8O3−δ oxygen separation membranes—Effects of kinetic demixing/decomposition and impurity segregation
journal, November 2009
- Wang, Bo; Zydorczak, B.; Wu, Zhen-Tao
- Journal of Membrane Science, Vol. 344, Issue 1-2
Systematic x-ray photoelectron spectroscopic study of La1?xSrx-based perovskite-type oxides
journal, January 2002
- van der Heide, P. A. W.
- Surface and Interface Analysis, Vol. 33, Issue 5
Mechanism of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 cathode degradation
journal, July 2012
- Oh, Dongjo; Gostovic, Danijel; Wachsman, Eric D.
- Journal of Materials Research, Vol. 27, Issue 15
Hard X-ray Fluorescence Measurements of Heteroepitaxial Solid Oxide Fuel Cell Cathode Materials
journal, May 2012
- Davis, Jacob N.; Miara, Lincoln J.; Saraf, Laxmikant
- ECS Transactions, Vol. 41, Issue 11
Surface composition of perovskite-type materials studied by Low Energy Ion Scattering (LEIS)
journal, September 2014
- Druce, John; Ishihara, Tatsumi; Kilner, John
- Solid State Ionics, Vol. 262
Surface Segregation and Chromium Deposition and Poisoning on La0.6Sr0.4Co0.2Fe0.8O3- Cathodes of Solid Oxide Fuel Cells
journal, October 2013
- Zhao, L.; Drennan, J.; Kong, C.
- ECS Transactions, Vol. 57, Issue 1
Long-term operation of a La0.58Sr0.4Co0.2Fe0.8O3−δ-membrane for oxygen separation
journal, April 2010
- Schlehuber, D.; Wessel, E.; Singheiser, L.
- Journal of Membrane Science, Vol. 351, Issue 1-2
In situ X-ray studies of film cathodes for solid oxide fuel cells
journal, October 2013
- Fuoss, Paul; Chang, Kee-Chul; You, Hoydoo
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
Relationship between Cation Segregation and the Electrochemical Oxygen Reduction Kinetics of La0.6Sr0.4CoO3−δ Thin Film Electrodes
journal, January 2011
- Kubicek, Markus; Limbeck, Andreas; Frömling, Till
- Journal of The Electrochemical Society, Vol. 158, Issue 6
Cation diffusion in La0.6Sr0.4CoO3−δ below 800 °C and its relevance for Sr segregation
journal, January 2014
- Kubicek, Markus; Rupp, Ghislain M.; Huber, Stefanie
- Physical Chemistry Chemical Physics, Vol. 16, Issue 6
Chemical Heterogeneities on La 0.6 Sr 0.4 CoO 3−δ Thin Films—Correlations to Cathode Surface Activity and Stability
journal, March 2012
- Cai, Zhuhua; Kubicek, Markus; Fleig, Jürgen
- Chemistry of Materials, Vol. 24, Issue 6
Reversible aging behavior of La0.8Sr0.2MnO3 electrodes at open circuit
journal, October 2012
- Abernathy, Harry; Finklea, Harry O.; Mebane, David S.
- Journal of Power Sources, Vol. 216
Development of lanthanum strontium manganite perovskite cathode materials of solid oxide fuel cells: a review
journal, November 2008
- Jiang, San Ping
- Journal of Materials Science, Vol. 43, Issue 21
Crystal structure and thermal expansion behavior of oxygen stoichiometric lanthanum strontium manganite at high temperature
journal, March 2014
- Shirai, Yoshikazu; Hashimoto, Shin-ichi; Sato, Kazuhisa
- Solid State Ionics, Vol. 256
Phase Behavior of Lanthanum Strontium Manganites
journal, January 1999
- Zheng, Feng
- Journal of The Electrochemical Society, Vol. 146, Issue 8
Anisotropic Thermal and Chemical Expansion in Sr-Substituted LaMnO 3+δ : Implications for Chemical Strain Relaxation
journal, December 2011
- Grande, Tor; Tolchard, Julian R.; Selbach, Sverre M.
- Chemistry of Materials, Vol. 24, Issue 2
Strain Effects on the Surface Chemistry of La 0.7 Sr 0.3 MnO 3
journal, April 2011
- Han, Jeong Woo; Jalili, Helia; Kuru, Yener
- ECS Transactions, Vol. 35, Issue 1
A comparative study of the surface and bulk properties of lanthanum-strontium-manganese oxides La1âxSrxMnO3±δ as a function of Sr-content, oxygen potential and temperature
journal, February 1999
- Decorse, P.
- Solid State Ionics, Vol. 117, Issue 1-2
Activity Enhancement of Dense Strontium-Doped Lanthanum Manganite Thin Films under Cathodic Polarization: A Combined AES and XPS Study
journal, January 2009
- la O’, G. J.; Savinell, R. F.; Shao-Horn, Y.
- Journal of The Electrochemical Society, Vol. 156, Issue 6
Electronic structure of La0.7Sr0.3MnO3 thin films for hybrid organic/inorganic spintronics applications
journal, December 2003
- de Jong, M. P.; Dediu, V. A.; Taliani, C.
- Journal of Applied Physics, Vol. 94, Issue 11
New Insights into the Strain Coupling to Surface Chemistry, Electronic Structure, and Reactivity of La 0.7 Sr 0.3 MnO 3
journal, March 2011
- Jalili, Helia; Han, Jeong Woo; Kuru, Yener
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 7
Refinement of the bulk defect model for LaxSr1−xMnO3±δ☆
journal, March 2008
- Mebane, D.
- Solid State Ionics, Vol. 178, Issue 39-40
Defect chemistry modelling of oxygen-stoichiometry, vacancy concentrations, and conductivity of (La1−xSrx)yMnO3±δ
journal, April 2000
- Poulsen, F.
- Solid State Ionics, Vol. 129, Issue 1-4
Impurity diffusion of 141Pr in LaMnO3, LaCoO3 and LaFeO3 materials
journal, January 2008
- Palcut, Marián; Christensen, Jens S.; Wiik, Kjell
- Physical Chemistry Chemical Physics, Vol. 10, Issue 43
Cation tracer diffusion of 138 La, 84 Sr and 25 Mg in polycrystalline La 0.9 Sr 0.1 Ga 0.9 Mg 0.1 O 2.9
journal, January 2003
- Schulz, Olaf; Martin, Manfred; Argirusis, Christos
- Phys. Chem. Chem. Phys., Vol. 5, Issue 11
Solid‐State Reaction Kinetics of LaCrO3 from the Oxides and Determination of La3 + Diffusion Coefficient
journal, June 1998
- Akashi, Takaya; Nanko, Makoto; Maruyama, Toshio
- Journal of The Electrochemical Society, Vol. 145, Issue 6
Simulation of Surface-Potential Driven ORR Kinetics on SOFC Cathode with Parallel Reaction Pathways
journal, December 2013
- Gong, Mingyang; Gemmen, Randall S.; Mebane, David S.
- Journal of The Electrochemical Society, Vol. 161, Issue 3
Micro scale dynamic modeling of LSM/YSZ composite cathodes
journal, May 2014
- Pakalapati, Suryanarayana; Gerdes, Kirk; Finklea, Harry
- Solid State Ionics, Vol. 258
Analysis of SOFCs Using Reference Electrodes
journal, January 2013
- Finklea, Harry; Chen, Xiaoke; Gerdes, Kirk
- Journal of The Electrochemical Society, Vol. 160, Issue 9
Works referencing / citing this record:
Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers
journal, January 2016
- Irvine, John T. S.; Neagu, Dragos; Verbraeken, Maarten C.
- Nature Energy, Vol. 1, Issue 1