AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Journal of Advanced Ceramics Article
PDF (2 MB)
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript AI Chat Paper
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article | Open Access

A high-entropy spinel ceramic oxide as the cathode for proton-conducting solid oxide fuel cells

Yangsen XUa,†, Xi XUb,†, Lei BIa( )
School of Resource Environment and Safety Engineering, University of South China, Hengyang 421001, China
Department of Materials, Imperial College London, London SW72BP, UK

† Yangsen Xu and Xi Xu contributed equally to this work.

Show Author Information

Graphical Abstract

Abstract

A high-entropy ceramic oxide is used as the cathode for the first time for proton-conducting solid oxide fuel cells (H-SOFCs). The Fe0.6Mn0.6Co0.6Ni0.6Cr0.6O4 (FMCNC) high-entropy spinel oxide has been successfully prepared, and the in situ chemical stability test demonstrates that the FMCNC material has good stability against CO2. The first-principles calculation indicates that the high-entropy structure enhances the properties of the FMCNC material that surpasses their individual components, leading to lower O2 adsorption energy for FMCNC than that for the individual components. The H-SOFC using the FMCNC cathode reaches an encouraging peak power density (PPD) of 1052 mW·cm−2 at 700 ℃, which is higher than those of the H-SOFCs reported recently. Additional comparison was made between the high-entropy FMCNC cathode and the traditional Mn1.6Cu1.4O4 (MCO) spinel cathode without the high-entropy structure, revealing that the formation of the high-entropy material allows the enhanced protonation ability as well as the movement of the O p-band center closer to the Fermi level, thus improving the cathode catalytic activity. As a result, the high-entropy FMCNC has a much-decreased polarization resistance of 0.057 Ω·cm2 at 700 ℃, which is half of that for the traditional MCO spinel cathode without the high-entropy design. The excellent performance of the FMCNC cell indicates that the high-entropy design makes a new life for the spinel oxide as the cathode for H-SOFCs, offering a novel and promising route for the development of high-performance materials for H-SOFCs.

Keywords

proton-conducting oxideshigh-entropy oxidescathodesolid oxide fuel cells (SOFCs)

Electronic Supplementary Material

Download File(s)
s40145-022-0573-7_ESM.pdf (1,022.6 KB)

References

[1]
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.
Crossref Google Scholar
[2]
Su HR, Hu YH. Progress in low-temperature solid oxide fuel cells with hydrocarbon fuels. Chem Eng J 2020, 402: 126235.
Crossref Google Scholar
[3]
Chen M, Xie XB, Guo JH, 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.
Crossref Google Scholar
[4]
Zhang W, Hu YH. Progress in proton-conducting oxides as electrolytes for low-temperature solid oxide fuel cells: From materials to devices. Energy Sci Eng 2021, 9: 984–1011.
Crossref Google Scholar
[5]
Wu S, Xu X, Li XM, 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.
Crossref Google Scholar
[6]
Chen M, Chen DC, 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.
Crossref Google Scholar
[7]
Li J, Wang C, Wang XF, et al. Sintering aids for proton-conducting oxides—A double-edged sword? A mini review. Electrochem Commun 2020, 112: 106672.
Crossref Google Scholar
[8]
Li PZ, Yang W, Tian CJ, et al. Electrochemical performance of La2NiO4+δ–Ce0.55La0.45O2−δ as a promising bifunctional oxygen electrode for reversible solid oxide cells. J Adv Ceram 2021, 10: 328–337.
Crossref Google Scholar
[9]
Zhou C, Sunarso J, Song YF, 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.
Crossref Google Scholar
[10]
Song YF, Chen YB, Wang W, et al. Self-assembled triple-conducting nanocomposite as a superior protonic ceramic fuel cell cathode. Joule 2019, 3: 2842–2853.
Crossref Google Scholar
[11]
Sun ZH, Gopalan S, Pal UB, et al. Cu1.3Mn1.7O4 spinel coatings deposited by electrophoretic deposition on Crofer 22 APU substrates for solid oxide fuel cell applications. Surf Coat Technol 2017, 323: 49–57.
Crossref Google Scholar
[12]
Talic B, Molin S, Wiik K, et al. Comparison of iron and copper doped manganese cobalt spinel oxides as protective coatings for solid oxide fuel cell interconnects. J Power Sources 2017, 372: 145–156.
Crossref Google Scholar
[13]
Liu HY, Zhu XF, Cheng MJ, et al. Novel Mn1.5Co1.5O4 spinel cathodes for intermediate temperature solid oxidefuel cells. Chem Commun 2011, 47: 2378–2380.
Crossref Google Scholar
[14]
Zhen SY, Sun W, Li PQ, et al. High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode. J Power Sources 2016, 315: 140–144.
Crossref Google Scholar
[15]
Sun YN, Xiang HM, Dai FZ, et al. Preparation and properties of CMAS resistant bixbyite structured high-entropy oxides RE2O3 (RE = Sm, Eu, Er, Lu, Y, and Yb): Promising environmental barrier coating materials for Al2O3f/Al2O3 composites. J Adv Ceram 2021, 10: 596–613.
Crossref Google Scholar
[16]
Oses C, Toher C, Curtarolo S. High-entropy ceramics. Nat Rev Mater 2020, 5: 295–309.
Crossref Google Scholar
[17]
Xiang HM, Xing Y, Dai FZ, et al. High-entropy ceramics: Present status, challenges, and a look forward. J Adv Ceram 2021, 10: 385–441.
Crossref Google Scholar
[18]
Qin MD, Yan QZ, Liu Y, et al. A new class of high-entropy M3B4 borides. J Adv Ceram 2021, 10: 166–172.
Crossref Google Scholar
[19]
Zhang Y, Sun SK, Guo WM, et al. Optimal preparation of high-entropy boride-silicon carbide ceramics. J Adv Ceram 2021, 10: 173–180.
Crossref Google Scholar
[20]
Yang Y, Bao H, Ni H, et al. A novel facile strategy to suppress Sr segregation for high-entropy stabilized La0.8Sr0.2MnO3−δ cathode. J Power Sources 2021, 482: 228959.
Crossref Google Scholar
[21]
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: e1801231.
Crossref Google Scholar
[22]
Hohenberg P, Kohn W. Inhomogeneous electron gas. Phys Rev 1964, 136: B864–B871.
Crossref Google Scholar
[23]
Blöchl PE, Jepsen O, Andersen OK. Improved tetrahedron method for Brillouin-zone integrations. Phys Rev B 1994, 49: 16223–16233.
Crossref Google Scholar
[24]
Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter 1996, 54: 11169–11186.
Crossref Google Scholar
[25]
Xu X, Wang HQ, 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.
Crossref Google Scholar
[26]
Yin YR, Yu SF, Dai HL, 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.
Crossref Google Scholar
[27]
Ji QQ, Xu X, Liu XH, et al. Improvement of the catalytic properties of porous lanthanum manganite for the oxygen reduction reaction by partial substitution of strontium for lanthanum. Electrochem Commun 2021, 124: 106964.
Crossref Google Scholar
[28]
Wang B, Bi L, Zhao XS. Fabrication of one-step co-fired proton-conducting solid oxide fuel cells with the assistance of microwave sintering. J Eur Ceram Soc 2018, 38: 5620– 5624.
Crossref Google Scholar
[29]
Xu X, Bi L, Zhao XS. Highly-conductive proton-conducting electrolyte membranes with a low sintering temperature for solid oxide fuel cells. J Membr Sci 2018, 558: 17–25.
Crossref Google Scholar
[30]
Grzesik Z, Smoła G, Miszczak M, et al. Defect structure and transport properties of (Co,Cr,Fe,Mn,Ni)3O4 spinel-structured high entropy oxide. J Eur Ceram Soc 2020, 40: 835–839.
Crossref Google Scholar
[31]
Zhang XH, Pei CL, Chang X, et al. FeO6 octahedral distortion activates lattice oxygen in perovskite ferrite for methane partial oxidation coupled with CO2 splitting. J Am Chem Soc 2020, 142: 11540–11549.
Crossref Google Scholar
[32]
Zhang LL, Yin YR, Xu YS, 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, .
Crossref Google Scholar
[33]
Xu YS, Liu XH, Cao N, et al. Defect engineering for electrocatalytic nitrogen reduction reaction at ambient conditions. Sustain Mater Technol 2021, 27: e00229.
Crossref Google Scholar
[34]
Kilner JA, Burriel M. Materials for intermediate-temperature solid-oxide fuel cells. Annu Rev Mater Res 2014, 44: 365– 393.
Crossref Google Scholar
[35]
Lu XK, Yang X, Jia LC, et al. First principles study on the oxygen reduction reaction of the La1−xSrxMnO3−δ coated Ba1−xSrxCo1−yFeyO3−δ cathode for solid oxide fuel cells. Int J Hydrog Energy 2019, 44: 16359–16367.
Crossref Google Scholar
[36]
Tao ZR, 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.
Crossref Google Scholar
[37]
Xu X, Xu YS, Ma JM, et al. Tailoring electronic structure of perovskite cathode for proton-conducting solid oxide fuel cells with high performance. J Power Sources 2021, 489: 229486.
Crossref Google Scholar
[38]
Duan CC, Huang J, Sullivan N, et al. Proton-conducting oxides for energy conversion and storage. Appl Phys Rev 2020, 7: 011314.
Crossref Google Scholar
[39]
Duan CC, Tong JH, Shang M, et al. Readily processed protonic ceramic fuel cells with high performance at low temperatures. Science 2015, 349: 1321–1326.
Crossref Google Scholar
[40]
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.
Crossref Google Scholar
[41]
Xie Y, Shi N, Huan DM, et al. A stable and efficient cathode for fluorine-containing proton-conducting solid oxide fuel cells. ChemSusChem 2018, 11: 3423–3430.
Crossref Google Scholar
[42]
Fabbri E, Bi L, Pergolesi D, et al. High-performance composite cathodes with tailored mixed conductivity for intermediate temperature solid oxide fuel cells using proton conducting electrolytes. Energy Environ Sci 2011, 4: 4984– 4993.
Crossref Google Scholar
[43]
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.
Crossref Google Scholar
[44]
Chen JY, Li J, Jia LC, et al. A novel layered perovskite Nd(Ba0.4Sr0.4Ca0.2)Co1.6Fe0.4O5+δ as cathode for proton-conducting solid oxide fuel cells. J Power Sources 2019, 428: 13–19.
Crossref Google Scholar
[45]
Lee YL, Kleis J, Rossmeisl J, et al. Prediction of solid oxide fuel cell cathode activity with first-principles descriptors. Energy Environ Sci 2011, 4: 3966–3970.
Crossref Google Scholar
[46]
Zhao L, Li G, Chen KF, et al. Sm0.5Sr0.5CoO3−δ infiltrated Ce0.9Gd0.1O2−δ composite cathodes for high performance protonic ceramic fuel cells. J Power Sources 2016, 333: 24–29.
Crossref Google Scholar
[47]
Shan D, Gong Z, Wu YS, et al. A novel BaCe0.5Fe0.3Bi0.2O3−δ perovskite-type cathode for proton-conducting solid oxide fuel cells. Ceram Int 2017, 43: 3660–3663.
Crossref Google Scholar
[48]
Cui JJ, Wang JK, Fan WW, et al. Porous YFe0.5Co0.5O3 thin sheets as cathode for intermediate-temperature solid oxide fuel cells. Int J Hydrog Energy 2017, 42: 20164–20175.
Crossref Google Scholar
[49]
Choi S, Kucharczyk CJ, Liang YG, et al. Exceptional power density and stability at intermediate temperatures in protonic ceramic fuel cells. Nat Energy 2018, 3: 202–210.
Crossref Google Scholar
[50]
Tang HD, Jin ZZ, Wu YS, et al. Cobalt-free nanofiber cathodes for proton conducting solid oxide fuel cells. Electrochem Commun 2019, 100: 108–112.
Crossref Google Scholar
[51]
Liu WY, Kou HN, Wang XF, et al. Improving the performance of the Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode for proton-conducting SOFCs by microwave sintering. Ceram Int 2019, 45: 20994–20998.
Crossref Google Scholar
[52]
Xu X, Wang HQ, Ma JM, et al. Impressive performance of proton-conducting solid oxide fuel cells using a first-generation cathode with tailored cations. J Mater Chem A 2019, 7: 18792–18798.
Crossref Google Scholar
[53]
Li J, Hou J, Lu Y, et al. Ca-containing Ba0.95Ca0.05Co0.4 Fe0.4Zr0.1Y0.1O3−δ cathode with high CO2- poisoning tolerance for proton-conducting solid oxide fuel cells. J Power Sources 2020, 453: 227909.
Google Scholar
[54]
Ma JM, Tao ZT, Kou HN, et al. Evaluating the effect of Pr-doping on the performance of strontium-doped lanthanum ferrite cathodes for protonic SOFCs. Ceram Int 2020, 46: 4000–4005.
Crossref Google Scholar
[55]
Ren RZ, Wang ZH, Meng XG, 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.
Crossref Google Scholar
[56]
Kim J, Sengodan S, Kwon G, et al. Triple-conducting layered perovskites as cathode materials for proton-conducting solid oxide fuel cells. ChemSusChem 2014, 7: 2811–2815.
Crossref Google Scholar
[57]
Chen Y, Yoo S, Pei K, et al. An in situ formed, dual-phase cathode with a highly active catalyst coating for protonic ceramic fuel cells. Adv Funct Mater 2018, 28: 1704907.
Crossref Google Scholar
[58]
He F, Gao QN, Liu ZQ, et al. A new Pd doped proton conducting perovskite oxide with multiple functionalities for efficient and stable power generation from ammonia at reduced temperatures. Adv Energy Mater 2021, 11: 2003916.
Crossref Google Scholar
[59]
Zhu ZW, Qian J, Wang ZT, et al. High-performance anode-supported solid oxide fuel cells based on nickel-based cathode and Ba(Zr0.1Ce0.7Y0.2)O3−δ electrolyte. J Alloys Compd 2013, 581: 832–835.
Crossref Google Scholar
Journal of Advanced Ceramics
Volume 11 Issue 5,
May 2022
Pages 794-804
DOI: 10.1007/s40145-022-0573-7
Cite this article:
XU Y, XU X, BI L. A high-entropy spinel ceramic oxide as the cathode for proton-conducting solid oxide fuel cells. Journal of Advanced Ceramics, 2022, 11(5): 794-804. https://doi.org/10.1007/s40145-022-0573-7

2385

Views

479

Downloads

146

Crossref

140

Web of Science

149

Scopus

16

CSCD

Altmetrics
Received: 15 July 2021
Revised: 14 January 2022
Accepted: 16 January 2022
Published: 20 April 2022
© The Author(s) 2022.

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are includ ed in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
Return