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; Liu, Meilin; Alamgir, Faisal M.

doi:10.1002/cssc.201402670

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

Journal Article · Tue Sep 09 04:00:00 EDT 2014 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.201402670· OSTI ID:1370161

Lai, Samson Y.; Ding, Dong; Liu, Mingfei; Liu, Meilin; Alamgir, Faisal M.

Information from ex situ characterization can fall short in describing complex materials systems simultaneously exposed to multiple external stimuli. Operando X-ray absorption spectroscopy (XAS) was used to probe the local atomistic and electronic structure of specific elements in a La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) thin film cathode exposed to air contaminated with H₂O and CO₂ under operating conditions. While impedance spectroscopy showed that the polarization resistance of the LSCF cathode increased upon exposure to both contaminants at 750°C, XAS near-edge and extended fine structure showed that the degree of oxidation for Fe and Co decreases with increasing temperature. Synchrotron-based X-ray photoelectron spectroscopy tracked the formation and removal of a carbonate species, a Co phase, and different oxygen moieties as functions of temperature and gas. The combined information provides insight into the fundamental mechanism by which H₂O and CO₂ cause degradation in the cathode of solid oxide fuel cells.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Heterogeneous Functional Materials Center (HeteroFoaM)

Sponsoring Organization:: USDOE SC Office of Basic Energy Sciences (SC-22)

DOE Contract Number:: SC0001061

OSTI ID:: 1370161

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 11 Vol. 7; ISSN 1864-5631

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

References (32)

Systematic XPS studies of metal oxides, hydroxides and peroxides Dupin, Jean-Charles; Gonbeau, Danielle; Vinatier, Philippe Physical Chemistry Chemical Physics, Vol. 2, Issue 6 https://doi.org/10.1039/a908800h	journal	January 2000
Solid oxide fuel cell technology?features and applications Minh, N. Solid State Ionics, Vol. 174, Issue 1-4 https://doi.org/10.1016/j.ssi.2004.07.042	journal	October 2004
Performance of a fuel cell optimized for in situ X-ray absorption experiments Principi, Emiliano; Di Cicco, Andrea; Witkowska, Agnieszka Journal of Synchrotron Radiation, Vol. 14, Issue 3 https://doi.org/10.1107/S0909049507013593	journal	April 2007
High-Temperature “Spectrochronopotentiometry”: Correlating Electrochemical Performance with In Situ Raman Spectroscopy in Solid Oxide Fuel Cells Kirtley, John D.; Halat, David M.; McIntyre, Melissa D. Analytical Chemistry, Vol. 84, Issue 22 https://doi.org/10.1021/ac301504g	journal	October 2012
Electron Transfer Mechanisms upon Lithium Deintercalation from LiCoO ₂ to CoO ₂ Investigated by XPS Dahéron, L.; Dedryvère, R.; Martinez, H. Chemistry of Materials, Vol. 20, Issue 2 https://doi.org/10.1021/cm702546s	journal	January 2008
Designing a miniaturised heated stage for in situ optical measurements of solid oxide fuel cell electrode surfaces, and probing the oxidation of solid oxide fuel cell anodes using in situ Raman spectroscopy Brightman, E.; Maher, R.; Offer, G. J. Review of Scientific Instruments, Vol. 83, Issue 5 https://doi.org/10.1063/1.4719955	journal	May 2012
X-ray photoelectron spectroscopy study of Sr and Ba compounds Vasquez, R. P. Journal of Electron Spectroscopy and Related Phenomena, Vol. 56, Issue 3 https://doi.org/10.1016/0368-2048(91)85005-E	journal	June 1991
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
Systematic x-ray photoelectron spectroscopic study of La1?xSrx-based perovskite-type oxides van der Heide, P. A. W. Surface and Interface Analysis, Vol. 33, Issue 5 https://doi.org/10.1002/sia.1227	journal	January 2002
The specificity of surface oxygen in the activation of adsorbed water at metal surfaces Carley, A. F.; Rassias, S.; Roberts, M. W. Surface Science, Vol. 135, Issue 1-3 https://doi.org/10.1016/0039-6028(83)90208-X	journal	December 1983
Impact of Sr segregation on the electronic structure and oxygen reduction activity of SrTi1−xFexO3 surfaces Chen, Yan; Jung, WooChul; Cai, Zhuhua Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21463f	journal	January 2012
Enhanced performance of LSCF cathode through surface modification Liu, Mingfei; Ding, Dong; Blinn, Kevin International Journal of Hydrogen Energy, Vol. 37, Issue 10 https://doi.org/10.1016/j.ijhydene.2012.02.139	journal	May 2012
In Situ Ambient Pressure X-ray Photoelectron Spectroscopy of Cobalt Perovskite Surfaces under Cathodic Polarization at High Temperatures Crumlin, Ethan J.; Mutoro, Eva; Hong, Wesley T. The Journal of Physical Chemistry C, Vol. 117, Issue 31 https://doi.org/10.1021/jp4051963	journal	July 2013
Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells Yang, Lei; Choi, YongMan; Qin, Wentao Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1359	journal	June 2011
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
Redox dynamics of sulphur with Ni/GDC anode during SOFC operation at mid- and low-range temperatures: An operando S K-edge XANES study Nurk, G.; Huthwelker, T.; Braun, A. Journal of Power Sources, Vol. 240 https://doi.org/10.1016/j.jpowsour.2013.03.187	journal	October 2013
Surface strontium enrichment on highly active perovskites for oxygen electrocatalysis in solid oxide fuel cells Crumlin, Ethan J.; Mutoro, Eva; Liu, Zhi Energy & Environmental Science, Vol. 5, Issue 3 https://doi.org/10.1039/c2ee03397f	journal	January 2012
Oxidation stages of Ni electrodes in solid oxide fuel cell environments El Gabaly, Farid; McCarty, Kevin F.; Bluhm, Hendrik Physical Chemistry Chemical Physics, Vol. 15, Issue 21 https://doi.org/10.1039/c3cp50366f	journal	January 2013
Investigation of sheet resistance in thin-film mixed-conducting solid oxide fuel cell cathode test cells Lynch, Matthew E.; Liu, Meilin Journal of Power Sources, Vol. 195, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.03.017	journal	August 2010
The effect of carbonate contaminations on the XPS O 1s band structure in metal oxides Stoch, J.; Gablankowska-Kukucz, J. Surface and Interface Analysis, Vol. 17, Issue 3 https://doi.org/10.1002/sia.740170308	journal	March 1991
Enhancement of La0.6Sr0.4Co0.2Fe0.8O3-δ durability and surface electrocatalytic activity by La0.85Sr0.15MnO3±δ investigated using a new test electrode platform Lynch, Matthew E.; Yang, Lei; Qin, Wentao Energy & Environmental Science, Vol. 4, Issue 6 https://doi.org/10.1039/c1ee01188j	journal	January 2011
Investigation of solid/vapor interfaces using ambient pressure X-ray photoelectron spectroscopy Starr, D. E.; Liu, Z.; Hävecker, M. Chemical Society Reviews, Vol. 42, Issue 13 https://doi.org/10.1039/c3cs60057b	journal	January 2013
3 In situ and operando determination of the water content distribution in proton conducting membranes for fuel cells: a critical review Deabate, Stefano; Gebel, Gérard; Huguet, Patrice Energy & Environmental Science, Vol. 5, Issue 10 https://doi.org/10.1039/c2ee21834h	journal	January 2012
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Enhanced Sulfur and Coking Tolerance of a Mixed Ion Conductor for SOFCs: BaZr_0.1Ce_0.7Y_0.2–xYb_xO_3–δ Yang, L.; Wang, S.; Blinn, K. Science, Vol. 326, Issue 5949, p. 126-129 https://doi.org/10.1126/science.1174811	journal	October 2009
In situ X-ray absorption spectroscopy and X-ray diffraction of fuel cell electrocatalysts Russell, Andrea E.; Maniguet, Stephanie; Mathew, Rebecca J. Journal of Power Sources, Vol. 96, Issue 1 https://doi.org/10.1016/S0378-7753(01)00573-0	journal	June 2001
XPS Study of group IA carbonates Shchukarev, A.; Korolkov, D. Open Chemistry, Vol. 2, Issue 2 https://doi.org/10.2478/BF02475578	journal	January 2004
Operando X-ray absorption and infrared fuel cell spectroscopy Lewis, Emily A.; Kendrick, Ian; Jia, Qingying Electrochimica Acta, Vol. 56, Issue 24 https://doi.org/10.1016/j.electacta.2011.07.091	journal	October 2011
Rational SOFC material design: new advances and tools Liu, Meilin; Lynch, Matthew E.; Blinn, Kevin Materials Today, Vol. 14, Issue 11 https://doi.org/10.1016/S1369-7021(11)70279-6	journal	November 2011
In Situ Measurements on Solid Oxide Fuel Cell Cathodes - Simultaneous X-Ray Absorption and AC Impedance Spectroscopy on Symmetrical Cells Woolley, R. J.; Ryan, M. P.; Skinner, S. J. Fuel Cells, Vol. 13, Issue 6 https://doi.org/10.1002/fuce.201300174	journal	November 2013
Catalytically Active Oxygen Species in La ₁ _- _x Sr _x CoO ₃ _- _δ Studied by XPS and XAFS Spectroscopy Imamura, M.; Matsubayashi, N.; Shimada, H. The Journal of Physical Chemistry B, Vol. 104, Issue 31 https://doi.org/10.1021/jp994148k	journal	August 2000
X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper McIntyre, N. S.; Cook, M. G. Analytical Chemistry, Vol. 47, Issue 13 https://doi.org/10.1021/ac60363a034	journal	November 1975

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