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无钴钙钛矿空气电极中的简易缺陷工程实现质子陶瓷燃料电池性能增强

Facile Deficiency Engineering in a Cobalt-Free Perovskite Air Electrode to Achieve Enhanced Performance for Protonic Ceramic Fuel Cells.

作者信息

Ye Qirui, Ye Huaqing, Ma Zilin, Lin Haoqing, Zhao Bote, Yang Guangming, Dong Feifei, Ni Meng, Lin Zhan, Zhang Shanqing

机构信息

Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou Higher Education Mega Center, Guangzhou, 510006, P. R. China.

School of Environment and Energy, South China University of Technology, Guangzhou, 510006, P. R. China.

出版信息

Small. 2024 Jul;20(28):e2307900. doi: 10.1002/smll.202307900. Epub 2024 Feb 9.

Abstract

As a crucial component responsible for the oxygen reduction reaction (ORR), cobalt-rich perovskite-type cathode materials have been extensively investigated in protonic ceramic fuel cell (PCFC). However, their widespread application at a commercial scale is considerably hindered by the high cost and inadequate stability. In response to these weaknesses, the study presents a novel cobalt-free perovskite oxide, BaLa(FeZn)O (BLFZ0.95), with the triple-conducting (H|O|e) property as an active and robust air electrode for PCFC. The B-site deficiency state contributes significantly to the optimization of crystal and electronic structure, as well as the increase in oxygen vacancy concentration, thus in turn favoring the catalytic capacity. As a result, the as-obtained BLFZ0.95 electrode demonstrates exceptional electrochemical performance at 700 °C, representing extremely low area-specific resistance of 0.04 Ω cm in humid air (3 vol.% HO), extraordinarily high peak power density of 1114 mW cm, and improved resistance against CO poisoning. Furthermore, the outstanding long-term durability is achieved without visible deterioration in both symmetrical and single cell modes. This study presents a simple but crucial case for rational design of cobalt-free perovskite cathode materials with appreciable performance via B-site deficiency regulation.

摘要

作为负责氧还原反应(ORR)的关键组件,富钴钙钛矿型阴极材料已在质子陶瓷燃料电池(PCFC)中得到广泛研究。然而,其高成本和稳定性不足严重阻碍了它们在商业规模上的广泛应用。针对这些弱点,该研究提出了一种新型无钴钙钛矿氧化物BaLa(FeZn)O(BLFZ0.95),它具有三重传导(H|O|e)特性,可作为PCFC的活性且坚固的空气电极。B位缺陷状态对晶体和电子结构的优化以及氧空位浓度的增加有显著贡献,进而有利于催化能力。结果,所制备的BLFZ0.95电极在700°C下表现出优异的电化学性能,在潮湿空气中(3 vol.% H₂O)具有极低的面积比电阻0.04 Ω cm²,极高的峰值功率密度1114 mW cm⁻²,以及对CO中毒的抗性提高。此外,在对称和单电池模式下均实现了出色的长期耐久性,且无明显劣化。该研究通过B位缺陷调控为合理设计具有可观性能的无钴钙钛矿阴极材料提供了一个简单但关键的案例。

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