Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

He, Fan; Liu, Hao; Xu, Yangsen; Zhu, Feng; Sasaki, Kotaro; Choi, YongMan; Liu, Ying; Chen, Yu

doi:10.1016/j.joule.2025.101957

Conformal high-entropy oxide coatings enable fast and durable surface oxygen reactions

Journal Article · Thu May 15 00:00:00 EDT 2025 · Joule

DOI:https://doi.org/10.1016/j.joule.2025.101957· OSTI ID:2574073

He, Fan ^[1]; Liu, Hao ^[1]; Xu, Yangsen ^[1]; Zhu, Feng ^[1]; ^[2]; Choi, YongMan ^[3]; Liu, Ying ^[4]; ^[1]

South China Univ. of Technology (SCUT), Guangzhou (China)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
National Yang Ming Chiao Tung Univ., Tainan (Taiwan)
Zijin Mining Group Co., Ltd., Xiamen (China)

Developing active and durable air electrodes for efficient oxygen reactions is challenging for protonic ceramic cells (PCCs), especially at temperatures below 550°C. Here, in this study, we report a rationally designed conformal coating with a high-entropy PrNi_0.2Mn_0.2Co_0.2Fe_0.2Cu_0.2O_3−δ (PNMCFC) perovskite structure on the surface of a state-of-the-art PrBaCo₂O_5+δ (PBC) air electrode. The formed hybrid air electrode (PNMCFC-PBC) shows faster surface oxygen kinetics and a more stable phase structure in high-humidity air than the bare PBC electrode. Further density functional theory calculations suggest that the conformal coating mitigates Ba segregation at the interface and improves oxygen-related reactions, enhancing overall stability and electrocatalytic performance. The cells with the developed hybrid electrodes show encouraging electrochemical performance at 550°C: a polarization resistance of 0.72 Ω cm², a peak power density of 1.30 W cm⁻², an electrolysis current density of −1.36 A cm⁻² at 1.3 V, and reasonable operating stabilities (∼200 h at 550°C).

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); National Science and Technology Council (NSTC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2574073

Report Number(s):: BNL--228501-2025-JAAM

Journal Information:: Joule, Journal Name: Joule Journal Issue: 6 Vol. 9; ISSN 2542-4351

Publisher:: Elsevier - Cell PressCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

An Efficient Bifunctional Air Electrode for Reversible Protonic Ceramic Electrochemical Cells Zhou, Yucun; Zhang, Weilin; Kane, Nicholas Advanced Functional Materials, Vol. 31, Issue 40 https://doi.org/10.1002/adfm.202105386	journal	July 2021
Utilizing High Entropy Effects for Developing Chromium‐Tolerance Cobalt‐Free Cathode for Solid Oxide Fuel Cells Han, Xu; Ling, Yihan; Yang, Yang Advanced Functional Materials, Vol. 33, Issue 43 https://doi.org/10.1002/adfm.202304728	journal	June 2023
Effective Promotion of the Activity and Stability of Cathodes for Protonic Ceramic Fuel Cells Gao, Hui; He, Fan; Zhu, Feng Advanced Functional Materials, Vol. 34, Issue 33 https://doi.org/10.1002/adfm.202401747	journal	March 2024
A Highly Efficient Sandwich-Like Symmetrical Dual-Phase Oxygen-Transporting Membrane Reactor for Hydrogen Production by Water Splitting Fang, Wei; Steinbach, Frank; Cao, Zhongwei Angewandte Chemie International Edition, Vol. 55, Issue 30 https://doi.org/10.1002/anie.201603528	journal	May 2016
High-Entropy Perovskite Oxide: A New Opportunity for Developing Highly Active and Durable Air Electrode for Reversible Protonic Ceramic Electrochemical Cells Liu, Zuoqing; Tang, Zhengjie; Song, Yufei Nano-Micro Letters, Vol. 14, Issue 1 https://doi.org/10.1007/s40820-022-00967-6	journal	November 2022
Medium-Entropy perovskites Sr(FeαTiβCoγMnζ)O3- as promising cathodes for intermediate temperature solid oxide fuel cell Shen, Leyu; Du, Zhihong; Zhang, Yang Applied Catalysis B: Environmental, Vol. 295 https://doi.org/10.1016/j.apcatb.2021.120264	journal	October 2021
Constructing an active and stable oxygen electrode surface for reversible protonic ceramic electrochemical cells Pei, Kai; Luo, Shunrui; He, Fan Applied Catalysis B: Environmental, Vol. 330 https://doi.org/10.1016/j.apcatb.2023.122601	journal	August 2023
Electrochemical analysis of high-performance protonic ceramic fuel cells based on a columnar-structured thin electrolyte Choi, Sung Min; An, Hyegsoon; Yoon, Kyung Joong Applied Energy, Vol. 233-234 https://doi.org/10.1016/j.apenergy.2018.10.043	journal	January 2019
Electrochemical performance and stability of the cathode for solid oxide fuel cells: V. high performance and stable Pr2NiO4 as the cathode for solid oxide fuel cells Zhou, X. -D.; Templeton, J. W.; Nie, Z. Electrochimica Acta, Vol. 71 https://doi.org/10.1016/j.electacta.2012.03.067	journal	June 2012
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
Self-Assembled Triple-Conducting Nanocomposite as a Superior Protonic Ceramic Fuel Cell Cathode Song, Yufei; Chen, Yubo; Wang, Wei Joule, Vol. 3, Issue 11 https://doi.org/10.1016/j.joule.2019.07.004	journal	November 2019
Cathode reaction models and performance analysis of Sm0.5Sr0.5CoO3−δ–BaCe0.8Sm0.2O3−δ composite cathode for solid oxide fuel cells with proton conducting electrolyte He, Fei; Wu, Tianzhi; Peng, Ranran Journal of Power Sources, Vol. 194, Issue 1 https://doi.org/10.1016/j.jpowsour.2009.04.053	journal	October 2009
A reversible perovskite air electrode for active and durable oxygen reduction and evolution reactions via the A-site entropy engineering He, Fan; Zhu, Feng; Liu, Dongliang Materials Today, Vol. 63 https://doi.org/10.1016/j.mattod.2023.02.006	journal	March 2023
High-entropy ceramics: Review of principles, production and applications Akrami, Saeid; Edalati, Parisa; Fuji, Masayoshi Materials Science and Engineering: R: Reports, Vol. 146 https://doi.org/10.1016/j.mser.2021.100644	journal	October 2021
Hybrid-solid oxide electrolysis cell: A new strategy for efficient hydrogen production Kim, Junyoung; Jun, Areum; Gwon, Ohhun Nano Energy, Vol. 44 https://doi.org/10.1016/j.nanoen.2017.11.074	journal	February 2018
In situ/operando regulation of the reaction activities on hetero-structured electrodes for solid oxide cells Hu, Tong; He, Fan; Liu, Meilin Progress in Materials Science, Vol. 133 https://doi.org/10.1016/j.pmatsci.2022.101050	journal	March 2023
Fe-Based High-Entropy Perovskite Oxide: A Strategy to Suppress Sr Segregation and Performance Evaluation as an Electrode Material for SOFCs Salman, Muhammad; Saleem, Sumaiya; Ling, Yihan ACS Applied Energy Materials, Vol. 7, Issue 19 https://doi.org/10.1021/acsaem.4c01614	journal	September 2024
Template Synthesis and Photocatalytic Properties of Porous Metal Oxide Spheres Formed by Nanoparticle Infiltration Shchukin, Dmitry G.; Caruso, Rachel A. Chemistry of Materials, Vol. 16, Issue 11 https://doi.org/10.1021/cm0497780	journal	May 2004
Cation Size Mismatch and Charge Interactions Drive Dopant Segregation at the Surfaces of Manganite Perovskites Lee, Wonyoung; Han, Jeong Woo; Chen, Yan Journal of the American Chemical Society, Vol. 135, Issue 21 https://doi.org/10.1021/ja3125349	journal	May 2013
Materials for fuel-cell technologies Steele, Brian C. H.; Heinzel, Angelika Nature, Vol. 414, Issue 6861, p. 345-352 https://doi.org/10.1038/35104620	journal	November 2001
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
Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin Nature Materials, Vol. 15, Issue 9 https://doi.org/10.1038/nmat4659	journal	June 2016
High entropy oxides for reversible energy storage Sarkar, Abhishek; Velasco, Leonardo; Wang, Di Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05774-5	journal	August 2018
Self-sustainable protonic ceramic electrochemical cells using a triple conducting electrode for hydrogen and power production Ding, Hanping; Wu, Wei; Jiang, Chao Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15677-z	journal	April 2020
Surface restructuring of a perovskite-type air electrode for reversible protonic ceramic electrochemical cells Pei, Kai; Zhou, Yucun; Xu, Kang Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-29866-5	journal	April 2022
Exceptional power density and stability at intermediate temperatures in protonic ceramic fuel cells Choi, Sihyuk; Kucharczyk, Chris J.; Liang, Yangang Nature Energy, Vol. 3, Issue 3 https://doi.org/10.1038/s41560-017-0085-9	journal	February 2018
Highly efficient reversible protonic ceramic electrochemical cells for power generation and fuel production Duan, Chuancheng; Kee, Robert; Zhu, Huayang Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-019-0333-2	journal	March 2019
A combined ionic Lewis acid descriptor and machine-learning approach to prediction of efficient oxygen reduction electrodes for ceramic fuel cells Zhai, Shuo; Xie, Heping; Cui, Peng Nature Energy, Vol. 7, Issue 9 https://doi.org/10.1038/s41560-022-01098-3	journal	September 2022
Lowering the operating temperature of protonic ceramic electrochemical cells to <450 °C Liu, Fan; Deng, Hao; Diercks, David Nature Energy, Vol. 8, Issue 10 https://doi.org/10.1038/s41560-023-01350-4	journal	September 2023
Highly durable, coking and sulfur tolerant, fuel-flexible protonic ceramic fuel cells Duan, Chuancheng; Kee, Robert J.; Zhu, Huayang Nature, Vol. 557, Issue 7704 https://doi.org/10.1038/s41586-018-0082-6	journal	May 2018
Revitalizing interface in protonic ceramic cells by acid etch Bian, Wenjuan; Wu, Wei; Wang, Baoming Nature, Vol. 604, Issue 7906 https://doi.org/10.1038/s41586-022-04457-y	journal	April 2022
A highly active, CO ₂ -tolerant electrode for the oxygen reduction reaction Chen, Yu; Yoo, Seonyoung; Choi, YongMan Energy & Environmental Science, Vol. 11, Issue 9 https://doi.org/10.1039/C8EE01140K	journal	January 2018
Protonic ceramic electrochemical cells for hydrogen production and electricity generation: exceptional reversibility, stability, and demonstrated faradaic efficiency Choi, Sihyuk; Davenport, Timothy C.; Haile, Sossina M. Energy & Environmental Science, Vol. 12, Issue 1 https://doi.org/10.1039/C8EE02865F	journal	January 2019
Transition from perovskite to misfit-layered structure materials: a highly oxygen deficient and stable oxygen electrode catalyst Saqib, Muhammad; Choi, In-Gyu; Bae, Hohan Energy & Environmental Science, Vol. 14, Issue 4 https://doi.org/10.1039/D0EE02799E	journal	January 2021
Promotion of oxygen reduction reaction on a double perovskite electrode by a water-induced surface modification Kim, Jun Hyuk; Yoo, Seonyoung; Murphy, Ryan Energy & Environmental Science, Vol. 14, Issue 3 https://doi.org/10.1039/D0EE03283B	journal	January 2021
Water as a hole-predatory instrument to create metal nanoparticles on triple-conducting oxides Kim, Jun Hyuk; Hong, Jaewoon; Lim, Dae-Kwang Energy & Environmental Science, Vol. 15, Issue 3 https://doi.org/10.1039/D1EE03046A	journal	January 2022
Critical role of acceptor dopants in designing highly stable and compatible proton-conducting electrolytes for reversible solid oxide cells Luo, Zheyu; Zhou, Yucun; Hu, Xueyu Energy & Environmental Science, Vol. 15, Issue 7 https://doi.org/10.1039/D2EE01104B	journal	January 2022
An universal oxygen electrode for reversible solid oxide electrochemical cells at reduced temperatures Kim, Jun Hyuk; Kim, Dongyeon; Ahn, Sejong Energy & Environmental Science, Vol. 16, Issue 9 https://doi.org/10.1039/D2EE04108A	journal	January 2023
Water-mediated exsolution of nanoparticles in alkali metal-doped perovskite structured triple-conducting oxygen electrocatalysts for reversible cells Park, Kwangho; Saqib, Muhammad; Lee, Hyungwoo Energy & Environmental Science, Vol. 17, Issue 3, p. 1175-1188 https://doi.org/10.1039/D3EE03510G	journal	January 2024
Phase segregation of a composite air electrode unlocks the high performance of reversible protonic ceramic electrochemical cells He, Fan; Hou, Mingyang; Liu, Dongliang Energy & Environmental Science, Vol. 17, Issue 11 https://doi.org/10.1039/D4EE01608D	journal	January 2024
Steam-promoted symmetry optimizations of perovskite electrodes for protonic ceramic cells Zhu, Feng; Hou, Mingyang; Du, Zhiwei Energy & Environmental Science, Vol. 17, Issue 20 https://doi.org/10.1039/D4EE02233E	journal	January 2024
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
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
Proton-conducting oxides for energy conversion and storage Duan, Chuancheng; Huang, Jake; Sullivan, Neal Applied Physics Reviews, Vol. 7, Issue 1 https://doi.org/10.1063/1.5135319	journal	March 2020
An Octane-Fueled Solid Oxide Fuel Cell Zhan, Z. Science, Vol. 308, Issue 5723 https://doi.org/10.1126/science.1109213	journal	May 2005
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
Readily processed protonic ceramic fuel cells with high performance at low temperatures Duan, C.; Tong, J.; Shang, M. Science, Vol. 349, Issue 6254 https://doi.org/10.1126/science.aab3987	journal	July 2015

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