构型熵工程增强双钙钛矿型氧电极抗Cr中毒能力

doi:10.15541/jim20240542

摘要/Abstract

摘要： 固体氧化物燃料电池(SOFC)作为一种高效清洁的发电装置,其阴极性能对于电池的商业化应用来说至关重要。其中阴极表面的阳离子偏析会对电池的性能和稳定性产生不利影响。双钙钛矿氧化物PrBa_0.8Ca_0.2Co₂O₅₊_δ(PBCC)是一种高活性阴极,但其依然存在偏析显著和Cr耐受力不足问题。为提高阴极稳定性,本研究设计了由PBCC衍生的A位中熵双钙钛矿阴极材料Pr_0.6La_0.1Nd_0.1Sm_0.1Gd_0.1Ba_0.8Ca_0.2Co₂O₅₊_δ(ME-PBCC),并系统探究了其在含Cr气氛下的偏析情况及耐Cr性能。与传统PBCC阴极相比,ME-PBCC材料表面的BaCrO₄和Co₃O₄偏析得到了显著抑制,这归因于其具有较高的构型熵值。电导弛豫(ECR)和电化学交流阻抗谱(EIS)结果表明ME-PBCC阴极的电化学稳定性得到了明显提高。中熵阴极在Cr沉积48 h后的氧表面交换系数k_chem从4.4×10^-4 cm·s^-1降至1.8×10^-4 cm·s^-1,其k_chem减小量明显低于PBC (从7.3×10^-4 cm·s^-1降至1.2×10^-4 cm·s^-1)。此外,在700 ℃含Cr空气中处理48 h后的EIS结果显示,中熵ME-PBCC的极化电阻仅为0.07 Ω·cm²,明显低于PBCC的0.11 Ω·cm²,证实了中熵阴极的运行稳定性与耐Cr能力显著提高。本研究提供了一种具有应用前景的SOFCs阴极材料。

关键词: 固体氧化物燃料电池, 双钙钛矿阴极, 构型熵, 阳离子偏析, 耐Cr性

Abstract: Solid oxide fuel cells (SOFCs) as a highly efficient and clean power generation device, where the performance of the cathode is critically important for the commercial application of the entire cell. Cation segregation on the surface of cathodes significantly affects the performance and operational stability. The double perovskite oxide PrBa_0.8Ca_0.2Co₂O₅₊_δ(PBCC), a highly active cathode, still suffers from serious surface segregation and insufficient Cr-tolerance ability. In order to improve the stability of cathode, a A-site medium-entropy double perovskite oxide Pr_0.6La_0.1Nd_0.1Sm_0.1Gd_0.1Ba_0.8Ca_0.2Co₂O₅₊_δ ( ME-PBCC ) derived from PBCC was prepared, and its segregation behavior in Cr-containing atmosphere was systematically investigated. Compared with the traditional PBCC cathode, the segregation of BaCrO₄ and Co₃O₄ on the surface of ME-PBCC is significantly suppressed, which is attributed to its higher configurational entropy. Electrical conductivity relaxation (ECR) and electrochemical impedance spectroscopy (EIS) results indicate that the electrochemical stability of the ME-PBCC cathode have been significantly improved. For example, after Cr deposition for 48 h, the oxygen surface exchange coefficient k_chem of the medium-entropy cathode decreases from 4.4×10^-4 cm·s^-1 to 1.8×10^-4 cm·s^-1, with the reduction of k_chem being significantly lower than that of PBC (which decreases from 7.3×10^-4 cm·s^-1 to 1.2×10^-4 cm·s^-1). Furthermore, the EIS results after treatment in Cr-containing air at 700 ℃ for 48 h show that the polarization resistance (R_p) of ME-PBCC is only 0.07 Ω·cm², which is lower than 0.11 Ω·cm² of PBCC, confirming that the medium-entropy cathode has significantly improved operational stability and Cr resistance. This study provides a promising cathode material for SOFCs.

Key words: solid oxide fuel cell, double perovskite cathode, configuration entropy, cation segregation, chromium tolerance

中图分类号:

TQ174

王哲, 郝鸿儒, 吴宗辉, 徐玲玲, 吕喆, 魏波. 构型熵工程增强双钙钛矿型氧电极抗Cr中毒能力[J]. 无机材料学报, DOI: 10.15541/jim20240542.

WANG Zhe, HAO Hongru, WU Zonghui, XU Lingling, LÜ Zhe, WEI Bo. Enhancing Cr-tolerance Ability of Double Perovskite Cathodes through Configuration Entropy Engineering[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20240542.

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