Incorporating high acidity cations in Co-free BiFeO3-based air electrodes for enhancing their electrocatalytic activity and durability in reversible solid oxide cells†

IF 10.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL
Shun Wang, Wen Jiang and Yifeng Zheng
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引用次数: 0

Abstract

Developing air electrodes with high catalytic activity and outstanding durability for the oxygen reduction and evolution reactions (ORR and OER) is crucial for the commercialization of reversible solid oxide cells (RSOCs). Co-free BiFeO3−δ-based perovskite oxides are considered promising air electrode materials owing to the high polarizability of Bi3+ and low oxygen-vacancy migration energy. In this work, we report the synthesis of Bi0.8Ca0.2Fe1−xTixO3−δ (BCFTix, x = 0, 0.05, 0.1 and 0.15) perovskites as efficient air electrodes for RSOCs via A-/B-site co-doping engineering. Ca and Ti co-doping significantly improved the electrochemical performance and operational stability of BiFeO3-based air electrodes. Bi0.8Ca0.2Fe0.9Ti0.1O3−δ (BCFTi0.1) exhibited the highest electrocatalytic activity with a polarization resistance of 0.064 Ω cm2 in air at 700 °C in symmetrical cells, with a decrease of approximately 48% compared to BCF (0.123 Ω cm2). In addition, BCFTi0.1 possessed excellent CO2 tolerance and exhibited stable electroactivity in 3% CO2-air at 700 °C for 100 h. A fuel electrode-supported single cell with the BCFTi0.1 air electrode demonstrated remarkable performance at 700 °C, achieving a power density of 1.03 W cm−2 in fuel cell mode, which was about 88% higher than that of BCF (0.6 W cm−2). In electrolysis mode, a current density of 0.9 A cm−2 was obtained at 700 °C and 1.3 V with 70% H2O–30% H2. The single cell with the BCFTi0.1 air electrode demonstrated good cycling durability under humidified H2 (10% H2O). The reduced activation energy for oxygen-ion migration and increased oxygen-vacancy concentration via Ca and Ti co-doping promoted surface oxygen exchange and bulk-transport kinetics, leading to enhanced electrocatalytic activity. At the same time, the high acidity of Ti4+ and large average bonding energy enhanced the CO2 tolerance of BCFTi0.1. This study provides a collaborative strategy for the regulation of A/B-site cations to design novel air electrodes with high activity and chemical stability for RSOCs.

Abstract Image

在无co的bifeo3基空气电极上加入高酸性阳离子以增强可逆固体氧化物电池的电催化活性和耐久性
开发高催化活性和高耐久性的氧反应和进化反应(ORR和OER)空气电极是可逆固体氧化物电池(rsoc)商业化的关键。无co - BiFeO3-δ基钙钛矿氧化物由于其高极化率和低氧空位迁移能而被认为是一种很有前途的空气电极材料。在这项工作中,我们提出Bi0.8Ca0.2Fe1-xTixO3-δ (BCFTix, x= 0,0.05, 0.1和0.15)钙钛矿通过a / b位共掺杂工程作为rsoc的高效空气电极。Ca和Ti共掺杂显著提高了bifeo3基空气电极的电化学性能和工作稳定性。bi0.8 ca0.2 fe0.9 ti0.1 -δ (BCFTi0.1)表现出最好的电催化活性,在700℃空气中对称电池中极化电阻为0.064 Ω cm2,比BCF (0.123 Ω cm2)降低了约48%。此外,BCFTi0.1具有优异的CO2耐受性,在700℃下3% CO2-空气条件下保持100 h的稳定电活性。使用BCFTi0.1空气电极的燃料电极负载单体电池在700℃下表现出优异的性能,燃料电池模式下功率密度为1.03 W cm-2,比使用BCF (0.6 W cm-2)的电池功率密度提高约88%。在电解模式下,在700℃,1.3 V, 70%H2O-30%H2条件下,电流密度为0.9 a cm-2。采用BCFTi0.1空气电极的单体电池在加湿H2 (10% H2O)条件下具有良好的循环耐久性。Ca和Ti共掺杂降低了氧离子迁移活化能,增加了氧空位浓度,促进了表面氧交换和体输运动力学,从而提高了电催化活性。同时,Ti4+的高酸性和大的平均键能增强了BCFTi0.1的CO2耐受性。本研究提供了a / b位阳离子调控的协同策略,为rsoc设计具有高活性和化学稳定性的新型空气电极。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Journal of Materials Chemistry A
Journal of Materials Chemistry A CHEMISTRY, PHYSICAL-ENERGY & FUELS
CiteScore
19.50
自引率
5.00%
发文量
1892
审稿时长
1.5 months
期刊介绍: The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.
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