铁基钙钛矿La0.25M0.75FeO3-δ (M= Ba, Sr, Ca)的制备及其作为固体氧化物燃料电池阴极材料的性能研究

doi:10.15541/jim20240500

摘要/Abstract

摘要： 固体氧化物燃料电池(SOFC)的性能受阴极氧还原反应(ORR)的制约,对整个电池性能至关重要。本研究通过容限因子和结构特征设计合成了La_0.25M_0.75FeO_3-_δ (M=Ba, Sr, Ca,标记为LBF、LSF、LCF)钙钛矿阴极,研究了Ba、Sr、Ca元素取代的特性及对阴极电化学性能的影响。不同的碱土元素对晶体结构有显著影响,LBF为Pm-3m立方相, LSF为R-3c菱方相,而LCF为P21ma正交和Pcmn菱方的复合相。晶体结构的差异也导致了不同的材料热膨胀系数(TEC)和电导率,LCF具有最小的TEC (13.8×10^-6 K^-1),LSF具有最高的电导率,其电导率在550 ℃达到404.4 S·cm^-1。三种Fe基阴极在空气和CO₂气氛下都体现了优异的稳定性,以及与电解质的化学兼容性。此外,不同的碱土元素也影响着材料的催化活性,LSF和LBF具有低的面比电阻(ASR),在800 ℃时ASR仅为0.022和0.027 Ω·cm²,优于LCF的0.351 Ω·cm²。较高的氧还原活性归因于其晶体结构,以及氧的吸附和解离能力。鉴于Ba²⁺、Sr²⁺、Ca²⁺在在阴极性能上各有优缺点,未来可以在A位有效引入中高熵设计,充分发挥各自的优势获得综合性能优异的SOFC阴极。

关键词: 固体氧化物燃料电池, 钙钛矿, 无钴阴极, 电化学性能

Abstract: Solid Oxide Fuel Cell (SOFC) performance is mainly constrained by the cathode's oxygen reduction reaction (ORR), which is crucial for overall cell efficiency. This study synthesized La_0.25M_0.75FeO_3-_δ (M=Ca, Sr, Ba, abbreviated as LCF, LSF, LBF) perovskite cathodes based on tolerance factors and structural design to examine the effects of Ba, Sr, and Ca doping on electrochemical performance. Different alkaline earth elements have a significant effect on the crystal structure. LBF is Pm-3m cubic phase, LSF is R-3c rhombohedral phase, and LCF is a composite phase of P21ma orthogonal and Pcmn rhombohedral. The difference of crystal structure also leads to various thermal expansion coefficient (TEC) and electrical conductivity. LCF possesses the smallest TEC (1.38 × 10^-56 K^-1), while LSF possesses the highest conductivity, which reaches 404.4 S·cm^-1 at 550 °C. All of three Fe-based cathodes exhibit excellent stability in air and CO₂ atmospheres, as well as chemical compatibility with electrolytes. In addition, different alkaline earth elements also affect the catalytic activity of the material. LSF and LBF have low area specific resistance (ASR). At 800 °C, their ASR are only 0.022 and 0.027 Ω·cm² which are better than 0.351 Ω·cm² of LCF. The higher oxygen reduction activity is attributed to its crystal structure, oxygen adsorption and dissociation ability. In view of the advantages and disadvantages of Ba²⁺, Sr²⁺ and Ca²⁺ in cathode performance, medium/high-entropy design can be effectively introduced in A-site in the future to give full play to their respective advantages to obtain SOFC cathode with excellent comprehensive performance.

Key words: solid oxide fuel cell, perovskite, cobalt-free cathode, electrochemical performance

中图分类号:

TM911

杨恒强, 张馨月, 马义初, 周青军. 铁基钙钛矿La_0.25M_0.75FeO_3-_δ (M= Ba, Sr, Ca)的制备及其作为固体氧化物燃料电池阴极材料的性能研究[J]. 无机材料学报, DOI: 10.15541/jim20240500.

YANG Hengqiang, ZHANG Xinyue, MA Yichu, ZHOU Qingjun. Iron-based Perovskite Material La_0.25M_0.75FeO_3-_δ (M= Ca, Sr, Ba): Preparation and Performance as Cathode for Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20240500.

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