Abstract
The Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) + Co3O4 composite material is evaluated as a cathode for proton-conducting solid oxide fuel cells (H-SOFCs), which provides a new strategy to solve the thermal mismatch problem between the cathode and electrolyte without impairing the cathode performance. BSCF is a well-known cathode material for intermediate-temperature SOFCs, but its performance for H-SOFCs is unsatisfactory. One reason for the relatively low performance is the poor contact between the BSCF cathode and the electrolyte due to the high thermal expansion of BSCF. The relatively low melting point of Co3O4 is taken in this study as an advantage to bond the BSCF cathode to the electrolyte, mitigating the poor contact problem for the BSCF with the electrolyte. Furthermore, the addition of Co3O4 promotes the catalytic activity of the BSCF cathode as demonstrated by experimental studies and first-principles calculations, leading to an impressively high performance of BSCF-based cathodes for H-SOFCs.
摘要
Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) + Co3O4复合材料作为质子导体固体氧化物燃料电池(H-SOFC)的阴极为在不影响阴极性能的前提下解决阴极与电解质之间热匹配的问题提供了一种新的策略. BSCF是中温氧离子导体SOFC中受到广泛认可的一种阴极材料, 但其在H-SOFC中的表现并不突出, 其中一个主要的原因是由于BSCF较高的热膨胀系数使其与电解质的接触不好. 在本研究中, 利用Co3O4熔点较低的特性将BSCF阴极粘结到电解质上, 以缓解BSCF与电解质之间接触不好的问题. 此外, 实验研究和第一性原理计算都证明了Co3O4的添加有效地增强了BSCF阴极的催化活性, 从而使该阴极展现出良好的电化学性能以及燃料电池输出性能.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Zhou Y, Guan X, Zhou H, et al. Strongly correlated perovskite fuel cells. Nature, 2016, 534: 231–234
Boldrin P, Brandon NP. Progress and outlook for solid oxide fuel cells for transportation applications. Nat Catal, 2019, 2: 571–577
Shin JF, Xu W, Zanella M, et al. Self-assembled dynamic perovskite composite cathodes for intermediate temperature solid oxide fuel cells. Nat Energy, 2017, 2: 16214
Zhang Y, Knibbe R, Sunarso J, et al. Recent progress on advanced materials for solid-oxide fuel cells operating below 500°C. Adv Mater, 2017, 29: 1700132
Xi X, Fan Y, Zhang J, et al. In situ construction of hetero-structured perovskite composites with exsolved Fe and Cu metallic nanoparticles as efficient CO2 reduction electrocatalysts for high performance solid oxide electrolysis cells. J Mater Chem A, 2022, 10: 2509–2518
Chen M, Xie X, Guo J, et al. Space charge layer effect at the platinum anode/BaZr0.9Y0.1O3−δ electrolyte interface in proton ceramic fuel cells. J Mater Chem A, 2020, 8: 12566–12575
Zvonareva I, Fu XZ, Medvedev D, et al. Electrochemistry and energy conversion features of protonic ceramic cells with mixed ionic-electronic electrolytes. Energy Environ Sci, 2022, 15: 439–465
Gu H, Xu M, Song Y, et al. SrC0.8Ti0.1Ta0.1O3−ä perovskite: A new highly active and durable cathode material for intermediate-temperature solid oxide fuel cells. Compos Part B-Eng, 2021, 213: 108726
Liu Z, Cheng D, Zhu Y, et al. Robust bifunctional phosphorus-doped perovskite oxygen electrode for reversible proton ceramic electrochemical cells. Chem Eng J, 2022, 450: 137787
Dai H, Kou H, Wang H, et al. Electrochemical performance of protonic ceramic fuel cells with stable BaZrO3-based electrolyte: A mini-review. Electrochem Commun, 2018, 96: 11–15
Chen M, Chen D, Wang K, et al. Densification and electrical conducting behavior of BaZr0.9Y0.1O3−δ proton conducting ceramics with NiO additive. J Alloys Compd, 2019, 781: 857–865
Medvedev DA, Lyagaeva JG, Gorbova EV, et al. Advanced materials for SOFC application: Strategies for the development of highly conductive and stable solid oxide proton electrolytes. Prog Mater Sci, 2016, 75: 38–79
Duan C, Tong J, Shang M, et al. Readily processed protonic ceramic fuel cells with high performance at low temperatures. Science, 2015, 349: 1321–1326
Ding H, Wu W, Jiang C, et al. Self-sustainable protonic ceramic electrochemical cells using a triple conducting electrode for hydrogen and power production. Nat Commun, 2020, 11: 1907
Dai H, Yin Y, Li X, et al. A new Sc-doped La0.5Sra5MnO3−δ cathode allows high performance for proton-conducting solid oxide fuel cells. Sustain Mater Technol, 2022, 32: e00409
Li P, Yang W, Tian C, et al. Electrochemical performance of La2NiO4+δ-Ce0.55La0.45 O2−δ as a promising bifunctional oxygen electrode for reversible solid oxide cells. J Adv Ceram, 2021, 10: 328–337
Fu XZ, Luo JL, Sanger AR, et al. Y-doped BaCeO3−δ nanopowders as proton-conducting electrolyte materials for ethane fuel cells to co-generate ethylene and electricity. J Power Sources, 2010, 195: 2659–2663
Han D, Uemura S, Hiraiwa C, et al. Detrimental effect of sintering additives on conducting ceramics: Yttrium-doped barium zirconate. ChemSusChem, 2018, 11: 4102–4113
Zhou C, Sunarso J, Song Y, et al. New reduced-temperature ceramic fuel cells with dual-ion conducting electrolyte and triple-conducting double perovskite cathode. J Mater Chem A, 2019, 7: 13265–13274
Wang Q, Hou J, Fan Y, et al. Pr2BaNiMnO7−δ double-layered Ruddlesden-Popper perovskite oxides as efficient cathode electrocatalysts for low temperature proton conducting solid oxide fuel cells. J Mater Chem A, 2020, 8: 7704–7712
Zhang L, Yin Y, Xu Y, et al. Tailoring Sr2Fe1.5Mo0.5O6−δ with Sc as a new single-phase cathode for proton-conducting solid oxide fuel cells. Sci China Mater, 2022, 65: 1485–1494
Wu S, Xu X, Li X, et al. High-performance proton-conducting solid oxide fuel cells using the first-generation Sr-doped LaMnO3 cathode tailored with Zn ions. Sci China Mater, 2022, 65: 675–682
Song Y, Chen J, Yang M, et al. Realizing simultaneous detrimental reactions suppression and multiple benefits generation from nickel doping toward improved protonic ceramic fuel cell performance. Small, 2022, 18: 2200450
Song Y, Chen Y, Xu M, et al. A cobalt-free multi-phase nanocomposite as near-ideal cathode of intermediate-temperature solid oxide fuel cells developed by smart self-assembly. Adv Mater, 2020, 32: 1906979
Peng R, Wu T, Liu W, et al. Cathode processes and materials for solid oxide fuel cells with proton conductors as electrolytes. J Mater Chem, 2010, 20: 6218–6225
Xu X, Xu Y, Ma J, et al. Tailoring electronic structure of perovskite cathode for proton-conducting solid oxide fuel cells with high performance. J Power Sources, 2021, 489: 229486
Wang N, Hinokuma S, Ina T, et al. Mixed proton-electron-oxide ion triple conducting manganite as an efficient cobalt-free cathode for protonic ceramic fuel cells. J Mater Chem A, 2020, 8: 11043–11055
Tian H, Li W, Ma L, et al. Deconvolution of water-splitting on the triple-conducting Ruddlesden-Popper-phase anode for protonic ceramic electrolysis cells. ACS Appl Mater Interfaces, 2020, 12: 49574–49585
Zou D, Yi Y, Song Y, et al. The BaCe0.16Ya0.04Fe0.8O3−δ nanocomposite: A new high-performance cobalt-free triple-conducting cathode for protonic ceramic fuel cells operating at reduced temperatures. J Mater Chem A, 2022, 10: 5381–5390
Yin Y, Dai H, Yu S, et al. Tailoring cobalt-free La0.5Sr0.5FeO3−δ cathode with a nonmetal cation-doping strategy for high-performance proton-conducting solid oxide fuel cells. SusMat, 2022, 2: 607–616
Ren R, Wang Z, Meng X, et al. Tailoring the oxygen vacancy to achieve fast intrinsic proton transport in a perovskite cathode for protonic ceramic fuel cells. ACS Appl Energy Mater, 2020, 3: 4914–4922
Song Y, Chen Y, Wang W, et al. Self-assembled triple-conducting nanocomposite as a superior protonic ceramic fuel cell cathode. Joule, 2019, 3: 2842–2853
Tarutin AP, Lyagaeva JG, Medvedev DA, et al. Recent advances in layered Ln2NiO4+δ nickelates: Fundamentals and prospects of their applications in protonic ceramic fuel and electrolysis cells. J Mater Chem A, 2021, 9: 154–195
Tao Z, Xu X, Bi L Density functional theory calculations for cathode materials of proton-conducting solid oxide fuel cells: A mini-review. Electrochem Commun, 2021, 129: 107072
Bu Y, Joo S, Zhang Y, et al. A highly efficient composite cathode for proton-conducting solid oxide fuel cells. J Power Sources, 2020, 451: 227812
Bae K, Jang DY, Choi HJ, et al. Demonstrating the potential of yttrium-doped barium zirconate electrolyte for high-performance fuel cells. Nat Commun, 2017, 8: 14553
Yin Y, Yu S, Dai H, et al. Triggering interfacial activity of the traditional La0.5Sr0.5MnO3 cathode with Co-doping for proton-conducting solid oxide fuel cells. J Mater Chem A, 2022, 10: 1726–1734
Zhou W, Ran R, Shao Z Progress in understanding and development of Ba0.5Sr0.5Coa8Fe0.2O3−δ-based cathodes for intermediate-temperature solid-oxide fuel cells: A review. J Power Sources, 2009, 192: 231–246
Guo Y, Lin Y, Ran R, et al. Zirconium doping effect on the performance of proton-conducting BaZryCe0.8−yY0.2O3−δ (0.0 ⩽ y ⩽ 0.8) for fuel cell applications. J Power Sources, 2009, 193: 400–407
Lin Y, Ran R, Zheng Y, et al. Evaluation of Ba0.5Sr0.5Co0.8Fe0.2O3−δ as a potential cathode for an anode-supported proton-conducting solidoxide fuel cell. J Power Sources, 2008, 180: 15–22
Zhang Y, Chen B, Guan D, et al. Thermal-expansion offset for highperformance fuel cell cathodes. Nature, 2021, 591: 246–251
Han X, Cheng F, Chen C, et al. A Co3O4@MnO2/Ni nanocomposite as a carbon- and binder-free cathode for rechargeable Li-O2 batteries. Inorg Chem Front, 2016, 3: 866–871
Wang W, Wang Z, Hu Y, et al. A potential-driven switch of activity promotion mode for the oxygen evolution reaction at Co3O4/NiOxHy interface. eScience, 2022, 2: 438–444
Zhang H, Liu H, Cong Y, et al. Investigation of Sma5Sr0.5CoO3−δ/Co3O4 composite cathode for intermediate-temperature solid oxide fuel cells. J Power Sources, 2008, 185: 129–135
Bi L, Shafi SP, Da’as EH, et al. Tailoring the cathode-electrolyte interface with nanoparticles for boosting the solid oxide fuel cell performance of chemically stable proton-conducting electrolytes. Small, 2018, 14: 1801231
Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169–11186
Dan X, Wang C, Xu X, et al. Improving the sinterability of CeO2 by using plane-selective nanocubes. J Eur Ceramic Soc, 2019, 39: 4429–4434
Xi X, Liu J, Fan Y, et al. Reducing d-p band coupling to enhance CO2 electrocatalytic activity by Mg-doping in Sr2FeMoO6−δ double perovskite for high performance solid oxide electrolysis cells. Nano Energy, 2021, 82: 105707
Kilner JA, Burriel M Materials for intermediate-temperature solidoxide fuel cells. Annu Rev Mater Res, 2014, 44: 365–393
Broemme ADD Correlation between thermal expansion and Seebeck coefficient in polycrystalline Co3O4. IEEE Trans Elect Insul, 1991, 26: 49–52
Zhang H, Yang W Highly efficient electrocatalysts for oxygen reduction reaction. Chem Commun, 2007, 4215
Zhi M, Zhou G, Hong Z, et al. Single crystalline La0.5Sr0.5MnO3 microcubes as cathode of solid oxidefuel cell. Energy Environ Sci, 2011, 4: 139–144
Xu Y, Xu X, Bi L A high-entropy spinel ceramic oxide as the cathode for proton-conducting solid oxide fuel cells. J Adv Ceram, 2022, 11: 794–804
Zhou M, Liu J, Ye Y, et al. Enhancing the intrinsic activity and stability of perovskite cobaltite at elevated temperature through surface stress. Small, 2021, 17: 2104144
Ji Q, Bi L, Zhang J, et al. The role of oxygen vacancies of ABO3 perovskite oxides in the oxygen reduction reaction. Energy Environ Sci, 2020, 13: 1408–1428
Xi X, Liu J, Luo W, et al. Unraveling the enhanced kinetics of Sr2Fe1+xMo1−xO6−δ electrocatalysts for high-performance solid oxide cells. Adv Energy Mater, 2021, 11: 2102845
Chen C, Wang XT, Zhong JH, et al. Epitaxially grown heterostructured SrMn3O6−x-SrMnO3 with high-valence Mn3+/4+ for improved oxygen reduction catalysis. Angew Chem Int Ed, 2021, 60: 22043–22050
Muñoz-García AB, Tuccillo M, Pavone M. Computational design of cobalt-free mixed proton-electron conductors for solid oxide electrochemical cells. J Mater Chem A, 2017, 5: 11825–11833
Hong WT, Stoerzinger KA, Lee YL, et al. Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides. Energy Environ Sci, 2017, 10: 2190–2200
Ranran P, Yan W, Lizhai Y, et al. Electrochemical properties of intermediate-temperature SOFCs based on proton conducting Sm-doped BaCeO3 electrolyte thin film. Solid State Ion, 2006, 177: 389–393
Wan TT, Zhu AK, Li HB, et al. Performance variability of Ba0.5Sr0.5-Co0.8Fe0.2O3−ä cathode on proton-conducting electrolyte SOFCs with Ag and Au current collectors. Rare Met, 2018, 37: 633–641
Xie Y, Shi N, Huan D, et al. A stable and efficient cathode for fluorine-containing proton-conducting solid oxide fuel cells. ChemSusChem, 2018, 11: 3423–3430
Guan B, Lü Z, Wang G, et al. A performance study of solid oxide fuel cells with BaZr0.1Ce0.7Y0.2O3−δ electrolyte developed by spray-modified pressing method. Fuel Cells, 2012, 12: 141–145
Grimaud A, Mauvy F, Bassat JM, et al. Hydration properties and rate determining steps of the oxygen reduction reaction of perovskite-related oxides as H+-SOFC cathodes. J Electrochem Soc, 2012, 159: B683–B694
Sun S, Cheng Z Electrochemical behaviors for Ag, LSCF and BSCF as oxygen electrodes for proton conducting IT-SOFC. J Electrochem Soc, 2017, 164: F3104–F3113
Liu W, Kou H, Wang X, et al. Improving the performance of the Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode for proton-conducting SOFCs by microwave sintering. Ceramics Int, 2019, 45: 20994–20998
Xu X, Wang H, Fronzi M, et al. Tailoring cations in a perovskite cathode for proton-conducting solid oxide fuel cells with high performance. J Mater Chem A, 2019, 7: 20624–20632
Li X, Liu Y, Liu W, et al. Mo-doping allows high performance for a perovskite cathode applied in proton-conducting solid oxide fuel cells. Sustain Energy Fuels, 2021, 5: 4261–4267
Lin Y, Ran R, Shao Z. Silver-modified Ba0.5Sr0.5Co0.8Fe0.2O3−δ as cathodes for a proton conducting solid-oxide fuel cell. Int J Hydrogen Energy, 2010, 35: 8281–8288
Acknowledgements
This work was supported by the National Natural Science Foundation of China (51972183), the Hundred Youth Talents Program of Hunan, and the Startup Funding for Talents at the University of South China
Author information
Authors and Affiliations
Contributions
Author contributions Bi L designed the study. Yang X and Yu S performed the experiments Yin Y performed the DFT calculations and analyzed the data Bi L wrote the manuscript with other co-authors, and all authors discussed the results and provided their approval for the final version.
Corresponding author
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Supplementary information Supporting data are available in the online version of the paper.
Xuan Yang is an undergraduate student in the group of Professor Lei Bi at the University of South China. Her research activities mainly focus on the synthesis and design of new cathode materials for H-SOFCs, revealing the relationship between the structures of materials and their electrochemical performance.
Yanru Yin is a staff researcher in the group of Professor Lei Bi at the University of South China. Her research interest is to tailor the structures and properties of proton-conducting oxides, aiming to understand the transportation mechanism of charge carriers in proton-conducting oxides and then boost the performance of H-SOFCs.
Lei Bi is a full professor at the University of South China and leads a research group working on H-SOFCs, using both the first-principles calculation method and experimental approaches. He has been working in the field of H-SOFCs for more than 15 years His research interests cover the development and optimization of key materials for H-SOFCs and the new technologies for fuel cell fabrications.
Rights and permissions
About this article
Cite this article
Yang, X., Yin, Y., Yu, S. et al. Gluing Ba0.5Sr0.5Co0.8Fe0.2O3−δ with Co3O4 as a cathode for proton-conducting solid oxide fuel cells. Sci. China Mater. 66, 955–963 (2023). https://doi.org/10.1007/s40843-022-2240-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-022-2240-y