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用于固体氧化物电池的钴基钙钛矿空气电极的热膨胀失配最小化。

Minimized thermal expansion mismatch of cobalt-based perovskite air electrodes for solid oxide cells.

作者信息

Li Zhishan, Peng Meilan, Zhao Yingru, Li Jianhui, Sun Yifei

机构信息

College of Energy, Xiamen University, Xiamen, Fujian, 361102, China.

National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, China.

出版信息

Nanoscale. 2021 Dec 13;13(47):20299-20308. doi: 10.1039/d1nr06845h.

Abstract

The mismatch of thermal expansion coefficients (TECs) between cobalt-containing perovskite air electrodes and electrolytes is a great challenge for the development of thermo-mechanically durable solid oxide cells (SOCs). In this work, we propose a facile design principle to directly grow highly dispersed Co reactive sites onto ion-conducting scaffolds and confine the dimension of active centres within nanoscale. As a representative, the Co-socketed BaCeZrYO perovskite (denoted as R-BCZY-Co) was constructed a consecutive sol-gel and exsolution approach. Combined XRD, H-TPR, SEM and TEM results confirm the emergence of Co nanoparticles on a BCZY matrix without the segregation of a secondary Co-rich phase. The symmetric half-cell measurement suggests that R-BCZY-Co air electrode with the optimal Co content of 10 mol% exhibits a 7-fold promoted oxygen activation performance with a polarization resistance of ∼0.17 Ω cm at 750 °C. The TEC mismatch between fabricated R-BCZY-Co electrodes and BCZY electrolytes is minimized down to only ∼11.4%, which is significantly lower than that of other representative counterparts. Moreover, the detailed XPS result proves that the architecture of exsolved Co on BCZY possesses a higher concentration of surface oxygen vacancy, which further benefits the kinetics of ion diffusion and oxygen absorption.

摘要

含钴钙钛矿空气电极与电解质之间热膨胀系数(TECs)的不匹配是热机械耐用型固体氧化物电池(SOCs)发展面临的巨大挑战。在这项工作中,我们提出了一种简便的设计原则,将高度分散的钴活性位点直接生长在离子导电支架上,并将活性中心的尺寸限制在纳米尺度内。作为一个例子,通过连续的溶胶-凝胶和析出现象构建了套接钴的BaCeZrYO钙钛矿(表示为R-BCZY-Co)。结合XRD、H-TPR、SEM和TEM结果证实了在BCZY基体上出现了钴纳米颗粒,而没有富钴第二相的偏析。对称半电池测量表明,钴含量为10 mol%的最佳R-BCZY-Co空气电极在750℃时表现出7倍提升的氧活化性能,极化电阻约为0.17Ω·cm。制备的R-BCZY-Co电极与BCZY电解质之间的TEC不匹配最小化至仅约11.4%,这明显低于其他代表性对应物。此外,详细的XPS结果证明,BCZY上析出钴的结构具有更高浓度的表面氧空位,这进一步有利于离子扩散和氧吸收的动力学。

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