The Influence of Cr-Additives on the Polarization Resistance of Praseodymium-Doped Ceria Cathodes for Solid Oxide Fuel Cells

Staerz, Anna; Seo, Han Gil; Klotz, Dino; Kim, Dennis S.; LeBeau, James M.; Tuller, Harry L.

doi:10.1149/1945-7111/ac67b2

The Influence of Cr-Additives on the Polarization Resistance of Praseodymium-Doped Ceria Cathodes for Solid Oxide Fuel Cells

Journal Article · Thu Apr 28 00:00:00 EDT 2022 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac67b2· OSTI ID:1865993

; ; ; ; ;

While Cr poisoning of the oxygen reduction reaction (ORR) at SOFC cathodes is widely agreed to involve deactivation of oxygen exchange sites, the degradation mechanism remains ambiguous. Here, we selected an alternative cathode material Pr _0.1 Ce _0.9 O ₂₋ $δ,$ free of Sr segregation, to systematically investigate the effect of Cr-induced degradation in ORR. We expand on our previous studies in which the acidity/basicity of binary additives was found to be a strong indicator of the rate of oxygen surface exchange, by electrochemically investigating the ORR activity of the PCO cathode by impedance spectroscopy. Serial infiltration with acidic Cr-based oxides was found to degrade ORR activity as reflected in a 20-fold increase in area specific resistance (ASR) without corresponding changes in activation energy, with the opposite trend obtained with Ca-based oxides. Detected changes in total capacitance, attributed to changes in surface capacitance, also suggest depressed/enhanced PCO surface redox behavior with Cr/Ca-based infiltrants. Taken together, these results point to a more universal source of ORR poisoning/activation, based on acidity/basicity, rather than physical blocking of active sites. With this improved understanding, one can expect progress to be made in the coming years in optimizing means for protecting catalytic surfaces from degradation and/or improving their performance.

View Journal Article

Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: National Research Foundation of Korea (NRF); USDOE; USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: FE0031668

OSTI ID:: 1865993

Alternate ID(s):: OSTI ID: 1908554

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 4 Vol. 169; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

Non-stoichiometry in Oxide Thin Films: A Chemical Capacitance Study of the Praseodymium-Cerium Oxide System Chen, Di; Bishop, Sean R.; Tuller, Harry L. Advanced Functional Materials, Vol. 23, Issue 17 https://doi.org/10.1002/adfm.201202104	journal	November 2012
Origin and Tunability of Unusually Large Surface Capacitance in Doped Cerium Oxide Studied by Ambient-Pressure X-Ray Photoelectron Spectroscopy Gopal, Chirranjeevi Balaji; Gabaly, Farid El; McDaniel, Anthony H. Advanced Materials, Vol. 28, Issue 23 https://doi.org/10.1002/adma.201506333	journal	March 2016
Exceptionally Enhanced Electrode Activity of (Pr,Ce)O ₂₋ _δ -Based Cathodes for Thin-Film Solid Oxide Fuel Cells Seo, Han Gil; Choi, Yoonseok; Jung, WooChul Advanced Energy Materials, Vol. 8, Issue 19 https://doi.org/10.1002/aenm.201703647	journal	March 2018
Ceria as a Thermochemical Reaction Medium for Selectively Generating Syngas or Methane from H ₂ O and CO ₂ Chueh, William C.; Haile, Sossina M. ChemSusChem, Vol. 2, Issue 8 https://doi.org/10.1002/cssc.200900138	journal	August 2009
Degradation of a High Performance SOFC Cathode by Cr-Poisoning at OCV-Conditions Kornely, M.; Menzler, N. H.; Weber, A. Fuel Cells, Vol. 13, Issue 4 https://doi.org/10.1002/fuce.201200182	journal	February 2013
Method to Measure Area Specific Resistance and Chromium Migration Simultaneously from Solid Oxide Fuel Cell Interconnect Materials Tallgren, J.; Himanen, O.; Bianco, M. Fuel Cells, Vol. 19, Issue 5 https://doi.org/10.1002/fuce.201800169	journal	July 2019
Cathode materials for solid oxide fuel cells: a review Sun, Chunwen; Hui, Rob; Roller, Justin Journal of Solid State Electrochemistry, Vol. 14, Issue 7 https://doi.org/10.1007/s10008-009-0932-0	journal	October 2009
Microstructural Features of RF-sputtered SOFC Anode and Electrolyte Materials La O., Gerardo Jose; Hertz, Joshua; Tuller, Harry Journal of Electroceramics, Vol. 13, Issue 1-3 https://doi.org/10.1007/s10832-004-5177-9	journal	July 2004
Praseodymium-cerium oxide thin film cathodes: Study of oxygen reduction reaction kinetics Chen, Di; Bishop, Sean R.; Tuller, Harry L. Journal of Electroceramics, Vol. 28, Issue 1 https://doi.org/10.1007/s10832-011-9678-z	journal	January 2012
Mixed ionic-electronic conductivity of La1−xSrxCo1−yFeyO3−δ perovskite-type oxides Teraoka, Y.; Zhang, H. M.; Okamoto, K. Materials Research Bulletin, Vol. 23, Issue 1 https://doi.org/10.1016/0025-5408(88)90224-3	journal	January 1988
Electrochemical properties of a SOFC cathode in contact with a chromium-containing alloy separator Matsuzaki, Y. Solid State Ionics, Vol. 132, Issue 3-4 https://doi.org/10.1016/S0167-2738(00)00654-8	journal	July 2000
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
Interaction between chromia forming alloy interconnects and air electrode of solid oxide fuel cells Badwal, S.; Deller, R.; Foger, K. Solid State Ionics, Vol. 99, Issue 3-4 https://doi.org/10.1016/S0167-2738(97)00247-6	journal	August 1997
Electrochemical properties of A-site deficient SOFC cathodes under Cr poisoning conditions Fu, C. J.; Sun, K. N.; Chen, X. B. Electrochimica Acta, Vol. 54, Issue 28 https://doi.org/10.1016/j.electacta.2009.07.055	journal	December 2009
Influence of the Discretization Methods on the Distribution of Relaxation Times Deconvolution: Implementing Radial Basis Functions with DRTtools Wan, Ting Hei; Saccoccio, Mattia; Chen, Chi Electrochimica Acta, Vol. 184 https://doi.org/10.1016/j.electacta.2015.09.097	journal	December 2015
Chromium deposition and poisoning on Ba0.9Co0.7Fe0.2Nb0.1O3−δ cathode of solid oxide fuel cells Wang, Jingle; Yang, Zhibin; Yang, Kaichuang Electrochimica Acta, Vol. 289 https://doi.org/10.1016/j.electacta.2018.08.092	journal	November 2018
Evaluation of the oxidation and Cr evaporation properties of selected FeCr alloys used as SOFC interconnects Sachitanand, Rakshith; Sattari, Mohammad; Svensson, Jan-Erik International Journal of Hydrogen Energy, Vol. 38, Issue 35 https://doi.org/10.1016/j.ijhydene.2013.09.044	journal	November 2013
Chromium deposition and poisoning of cathodes of solid oxide fuel cells – A review Jiang, San Ping; Chen, Xinbing International Journal of Hydrogen Energy, Vol. 39, Issue 1 https://doi.org/10.1016/j.ijhydene.2013.10.042	journal	January 2014
Degradation analysis of commercial interconnect materials for solid oxide fuel cells in stacks operated up to 18000 hours Bianco, Manuel; Ouweltjes, Jan Pieter; Van herle, Jan International Journal of Hydrogen Energy, Vol. 44, Issue 59 https://doi.org/10.1016/j.ijhydene.2019.09.218	journal	November 2019
Sr Segregation in Perovskite Oxides: Why It Happens and How It Exists Koo, Bonjae; Kim, Kyeounghak; Kim, Jun Kyu Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.07.016	journal	August 2018
Degradation of anode supported cell (ASC) performance by Cr-poisoning Kornely, Michael; Neumann, Anita; Menzler, Norbert H. Journal of Power Sources, Vol. 196, Issue 17 https://doi.org/10.1016/j.jpowsour.2010.10.033	journal	September 2011
Coated stainless steel 441 as interconnect material for solid oxide fuel cells: Oxidation performance and chromium evaporation Grolig, J. G.; Froitzheim, J.; Svensson, J. -E. Journal of Power Sources, Vol. 248 https://doi.org/10.1016/j.jpowsour.2013.08.089	journal	February 2014
Praseodymium and gadolinium doped ceria as a cathode material for low temperature solid oxide fuel cells Chockalingam, Rajalekshmi; Ganguli, Ashok Kumar; Basu, Suddhasatwa Journal of Power Sources, Vol. 250 https://doi.org/10.1016/j.jpowsour.2013.10.105	journal	March 2014
Model-assisted identification of solid oxide cell elementary processes by electrochemical impedance spectroscopy measurements Caliandro, P.; Nakajo, A.; Diethelm, S. Journal of Power Sources, Vol. 436 https://doi.org/10.1016/j.jpowsour.2019.226838	journal	October 2019
Characteristics of ABO3 and A2BO4 (ASm, Sr; BCo, Fe, Ni) samarium oxide system as cathode materials for intermediate temperature-operating solid oxide fuel cell Baek, Seung-Wook; Kim, Jung Hyun; Bae, Joongmyeon Solid State Ionics, Vol. 179, Issue 27-32 https://doi.org/10.1016/j.ssi.2007.12.010	journal	September 2008
Mechanism of Cr deposition and its application in the development of Cr-tolerant cathodes of solid oxide fuel cells Jiang, San Ping; Zhen, Yongda Solid State Ionics, Vol. 179, Issue 27-32 https://doi.org/10.1016/j.ssi.2008.01.006	journal	September 2008
Oxygen nonstoichiometry and exchange kinetics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ Bucher, Edith; Egger, Andreas; Ried, Peter Solid State Ionics, Vol. 179, Issue 21-26 https://doi.org/10.1016/j.ssi.2008.01.089	journal	September 2008
Comparison of oxygen exchange kinetics of the IT-SOFC cathode materials La0.5Sr0.5CoO3−δ and La0.6Sr0.4CoO3−δ Egger, Andreas; Bucher, Edith; Yang, Min Solid State Ionics, Vol. 225 https://doi.org/10.1016/j.ssi.2012.02.050	journal	October 2012
Improving the Si Impurity Tolerance of Pr _0.1 Ce _0.9 O _2−δ SOFC Electrodes with Reactive Surface Additives Zhao, Liang; Perry, Nicola H.; Daio, Takeshi Chemistry of Materials, Vol. 27, Issue 8 https://doi.org/10.1021/acs.chemmater.5b00501	journal	April 2015
Effect of Sr Content and Strain on Sr Surface Segregation of La _{1– x} Sr _x Co _0.2 Fe _0.8 O _3−δ as Cathode Material for Solid Oxide Fuel Cells Yu, Yang; Ludwig, Karl F.; Woicik, Joseph C. ACS Applied Materials & Interfaces, Vol. 8, Issue 40 https://doi.org/10.1021/acsami.6b07118	journal	September 2016
Chromium Poisoning Effects on Surface Exchange Kinetics of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3−δ Huang, Yi-Lin; Hussain, A. Mohammed; Pellegrinelli, Christopher ACS Applied Materials & Interfaces, Vol. 9, Issue 19 https://doi.org/10.1021/acsami.7b02762	journal	May 2017
Chemical Heterogeneities on La _0.6 Sr _0.4 CoO _3−δ Thin Films—Correlations to Cathode Surface Activity and Stability Cai, Zhuhua; Kubicek, Markus; Fleig, Jürgen Chemistry of Materials, Vol. 24, Issue 6 https://doi.org/10.1021/cm203501u	journal	March 2012
Nonstoichiometry in Oxide Thin Films Operating under Anodic Conditions: A Chemical Capacitance Study of the Praseodymium–Cerium Oxide System Chen, Di; Bishop, Sean R.; Tuller, Harry L. Chemistry of Materials, Vol. 26, Issue 22 https://doi.org/10.1021/cm503440v	journal	November 2014
Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes ^† Adler, Stuart B. Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020724o	journal	October 2004
An acidity scale for binary oxides Smith, Derek W. Journal of Chemical Education, Vol. 64, Issue 6 https://doi.org/10.1021/ed064p480	journal	June 1987
A high-performance cathode for the next generation of solid-oxide fuel cells Shao, Zongping; Haile, Sossina M. Nature, Vol. 431, Issue 7005, p. 170-173 https://doi.org/10.1038/nature02863	journal	September 2004
Non-noble, efficient catalyst of unsupported α-Cr2O3 nanoparticles for low temperature CO Oxidation Bumajdad, Ali; Al-Ghareeb, Shaimaa; Madkour, Metwally Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-14779-x	journal	November 2017
Acidity of surface-infiltrated binary oxides as a sensitive descriptor of oxygen exchange kinetics in mixed conducting oxides Nicollet, Clement; Toparli, Cigdem; Harrington, George F. Nature Catalysis, Vol. 3, Issue 11 https://doi.org/10.1038/s41929-020-00520-x	journal	October 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
Trends in electrode development for next generation solid oxide fuel cells Kan, Wang Hay; Samson, Alfred Junio; Thangadurai, Venkataraman Journal of Materials Chemistry A, Vol. 4, Issue 46 https://doi.org/10.1039/C6TA06757C	journal	January 2016
Cobalt-substituted SrTi _0.3 Fe _0.7 O _3−δ : a stable high-performance oxygen electrode material for intermediate-temperature solid oxide electrochemical cells Zhang, Shan-Lin; Wang, Hongqian; Lu, Matthew Y. Energy & Environmental Science, Vol. 11, Issue 7 https://doi.org/10.1039/C8EE00449H	journal	January 2018
Oxygen exchange kinetics on systematically doped ceria: a pulsed isotope exchange study Schaube, Maximilian; Merkle, Rotraut; Maier, Joachim Journal of Materials Chemistry A, Vol. 7, Issue 38 https://doi.org/10.1039/C9TA05908C	journal	January 2019
Silica: ubiquitous poison of metal oxide interfaces Staerz, Anna; Seo, Han Gil; Defferriere, Thomas Journal of Materials Chemistry A, Vol. 10, Issue 6 https://doi.org/10.1039/D1TA08469K	journal	January 2022
Generalised equivalent circuits for mass and charge transport: chemical capacitance and its implications Jamnik, J.; Maier, J. Physical Chemistry Chemical Physics, Vol. 3, Issue 9 https://doi.org/10.1039/b100180i	journal	January 2001
Enhancing SOFC cathode performance by surface modification through infiltration Ding, Dong; Li, Xiaxi; Lai, Samson Yuxiu Energy & Environmental Science, Vol. 7, Issue 2 https://doi.org/10.1039/c3ee42926a	journal	January 2014
Solute Segregation and Grain-Boundary Impedance in High-Purity Stabilized Zirconia Aoki, Makoto; Chiang, Yet-Ming; Kosacki, Igor Journal of the American Ceramic Society, Vol. 79, Issue 5 https://doi.org/10.1111/j.1151-2916.1996.tb08569.x	journal	May 1996
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
Materials for Intermediate-Temperature Solid-Oxide Fuel Cells Kilner, John A.; Burriel, Mónica Annual Review of Materials Research, Vol. 44, Issue 1 https://doi.org/10.1146/annurev-matsci-070813-113426	journal	July 2014
Compensation for Oxygen Exchange Rate Limiting Impurities on a Pr _0.1 Ce _0.9 O _2- _d SOFC Electrode Material Bishop, Sean R.; Druce, John; Kilner, John A. ECS Transactions, Vol. 57, Issue 1 https://doi.org/10.1149/05701.2003ecst	journal	October 2013
Deposition of Chromium Species at Sr-Doped LaMnO[sub 3] Electrodes in Solid Oxide Fuel Cells. I. Mechanism and Kinetics Jiang, S. P.; Zhang, J. P.; Apateanu, L. Journal of The Electrochemical Society, Vol. 147, Issue 11 https://doi.org/10.1149/1.1394012	journal	January 2000
Determination of Oxygen Vacancy Concentration in a Thin Film of La[sub 0.6]Sr[sub 0.4]CoO[sub 3−δ] by an Electrochemical Method Kawada, T.; Suzuki, J.; Sase, M. Journal of The Electrochemical Society, Vol. 149, Issue 7 https://doi.org/10.1149/1.1479728	journal	January 2002
Silicon Contamination of the Praseodymium Doped Ceria Oxygen Surface Exchange Coefficient Ma, Yuxi; Nicholas, Jason D. Journal of The Electrochemical Society, Vol. 168, Issue 10 https://doi.org/10.1149/1945-7111/ac2e1d	journal	October 2021
Detailed Electrochemical Study on Nanoscaled La _0.6 Sr _0.4 CoO _3-δ SOFC Thin-Film Cathodes in Dry, Humid and CO ₂ -Containing Atmospheres Hayd, J.; Ivers-Tiffée, E. Journal of The Electrochemical Society, Vol. 160, Issue 11 https://doi.org/10.1149/2.026311jes	journal	January 2013
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
Effect of Chromium on La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3-δ Solid Oxide Fuel Cell Cathodes Lee, Soo-Na; Atkinson, Alan; Kilner, John A. Journal of The Electrochemical Society, Vol. 160, Issue 6 https://doi.org/10.1149/2.099306jes	journal	January 2013
Evaluation of electrochemical impedance spectra by the distribution of relaxation times Ivers-TiffÉE, Ellen; Weber, André Journal of the Ceramic Society of Japan, Vol. 125, Issue 4 https://doi.org/10.2109/jcersj2.16267	journal	January 2017
Accelerated Testing of Chromium Poisoning of Sr-Containing Mixed Conducting Solid Oxide Cell Air Electrodes Beez, Alexander; Schiemann, Kevin; Menzler, Norbert H. Frontiers in Energy Research, Vol. 6 https://doi.org/10.3389/fenrg.2018.00070	journal	July 2018

Similar Records

Degradation and recovery of solid oxide fuel cell performance by control of cathode surface acidity: Case study – Impact of Cr followed by Ca infiltration

Journal Article · Thu Jan 05 19:00:00 EST 2023 · Journal of Power Sources · OSTI ID:1908560

Robust highly durable solid oxide fuel cell cathodes – Improved materials compatibility & self-regulating surface chemistry

Technical Report · Thu Mar 02 23:00:00 EST 2023 · OSTI ID:1960547

Related Subjects

25 ENERGY STORAGE
cathode poisoning
impedance spectroscopy
oxygen exchange kinetics
praseodymia-ceria
solid oxide fuel cells

The Influence of Cr-Additives on the Polarization Resistance of Praseodymium-Doped Ceria Cathodes for Solid Oxide Fuel Cells

Citation Formats

References (57)

Similar Records

Related Subjects