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

无机材料学报 ›› 2025, Vol. 40 ›› Issue (12): 1341-1348.DOI: 10.15541/jim20240542

• 专栏：高温燃料电池关键材料(客座编辑：凌意瀚) • 上一篇下一篇

构型熵工程增强双钙钛矿型氧电极抗Cr中毒能力

王哲¹(), 郝鸿儒¹, 吴宗辉¹, 徐玲玲², 吕喆¹, 魏波¹()

1.哈尔滨工业大学物理学院, 黑龙江省先进量子功能材料与传感器件重点实验室, 哈尔滨 150001
2.哈尔滨师范大学物理与电子工程学院, 哈尔滨 150025

收稿日期:2024-12-27 修回日期:2025-02-02 出版日期:2025-03-06 网络出版日期:2025-03-06
通讯作者: 魏波, 教授. E-mail: bowei@hit.edu.cn
作者简介:王哲(1998-), 男, 博士研究生. E-mail: 1020881070@qq.com
基金资助:
国家自然科学基金(22279025);国家自然科学基金(21773048);国家自然科学基金(52472195);中央高校基础研究基金(2023FRFK06005);中央高校基础研究基金(HIT.NSRIF202204)

Enhancing Cr-tolerance Ability of Double Perovskite Cathodes through Configuration Entropy Engineering

WANG Zhe¹(), HAO Hongru¹, WU Zonghui¹, XU Lingling², LÜ Zhe¹, WEI Bo¹()

1. Heilongjiang Provincial Key Laboratory of Advanced Quantum Functional Materials and Sensor Devices, School of Physics, Harbin Institute of Technology, Harbin 150001, China
2. School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, China

Received:2024-12-27 Revised:2025-02-02 Published:2025-03-06 Online:2025-03-06
Contact: WEI Bo, professor. E-mail: bowei@hit.edu.cn
About author:WANG Zhe (1998-), male, PhD candidate. E-mail: 1020881070@qq.com
Supported by:
National Natural Science Foundation of China(22279025);National Natural Science Foundation of China(21773048);National Natural Science Foundation of China(52472195);Fundamental Research Funds for the Central Universities(2023FRFK06005);Fundamental Research Funds for the Central Universities(HIT.NSRIF202204)

摘要/Abstract

摘要：

固体氧化物燃料电池(SOFCs)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。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PBCC(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, ME-PBCC的极化电阻(R_p)仅为0.07 Ω·cm², 明显小于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) are a kind of highly efficient and clean power generation devices whose cathode performance 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, an 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 traditional PBCC cathode, 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 electrochemical stability of the ME-PBCC cathode has been significantly improved. Among the improvements, 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 significantly lower than that of PBCC (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 demonstrates that ME-PBCC is 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, 2025, 40(12): 1341-1348.

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, 2025, 40(12): 1341-1348.

图/表 11

图1 PBCC和ME-PBCC的晶体结构和XRD图谱

Fig. 1 Crystal structures and XRD patterns of PBCC and ME-PBCC (a) Schematic demonstrations of structures and (b) XRD patterns for PBCC and ME-PBCC; (c) Rietveld XRD pattern for ME-PBCC

图2 PBCC和ME-PBCC片体在不同处理条件下的SEM照片

Fig. 2 SEM images of PBCC and ME-PBCC pellets treated under different conditions (a-c) SEM images of PBCC after (a) polishing and heat treatment in dry Cr-containing air at (b) 700 and (c) 800 ℃ for 12 h; (d-f) SEM images of ME-PBCC after (d) polishing and heat treatment in dry Cr-containing air at (e) 700 and (f) 800 ℃ for 12 h. Inserts in (b, e): corresponding distributions of particle sizes

图3 在800 ℃含Cr空气条件下处理12 h后PBCC样品表面的(a) SEM照片及(b) EDS元素分析

Fig. 3 (a) SEM image and (b) corresponding EDS elemental analysis of the surface of PBCC sample after treatment in Cr-containing air for 12 h at 800 ℃

图4 (a, c) PBCC和(b, d) ME-PBCC表面的(a, b) SEM-EDS元素分布及(c, d)相关谱图

Fig. 4 (a, b) SEM-EDS elemental mappings and (c, d) corresponding spectra for the surface of (a, c) PBCC and (b, d) ME-PBCC

图5 在800 ℃ Cr毒化12 h后(a) PBCC和(b) ME-PBCC样品片上Co3O4和CrO42-的拉曼映射和相应谱图

Fig. 5 Raman mappings and corresponding spectra from marked points of Co3O4 and CrO42- for (a) PBCC and (b) ME-PBCC pellets after Cr-poisoning at 800 ℃ for 12 h Colorful figures are available on website

图6 ECR曲线及氧表面交换系数(kchem)和体相扩散系数(Dchem)结果

Fig. 6 ECR curves, oxygen surface exchange coefficients (kchem) and bulk diffusion coefficients (Dchem) (a, b) ECR curves for (a) PBCC and (b) ME-PBCC before and after Cr deposition at 700 ℃; (c, d) Results for (c) kchem and (d) Dchem

图7 PBCC与ME-PBCC的EIS谱图及相应的DRT分析

Fig. 7 EIS spectra and corresponding DRT analysis of PBCC and ME-PBCC (a) Variation curves of Rp with time at 700 ℃ in Cr-containing air; (b, c) EIS spectra of (b) PBCC and (c) ME-PBCC; (d, e) DRT curves of (d) PBCC and (e) ME-PBCC

图S1 PBCC的Rietveld精修的XRD图谱

Fig. S1 Rietveld refined XRD pattern of PBCC

图S2 PBCC和ME-PBCC初始样品片的EDS元素分析

Fig. S2 EDS elemental analysis of initial PBCC and ME- PBCC pellets

表S1 PBCC和ME-PBCC精修后的晶胞参数

Table S1 Results of the refined cell parameters of PBCC and ME-PBCC

Sample	Space group	a/Å	b/Å	c/Å	Volume/Å³
PBCC	P4/mmm	3.878	3.878	7.628	114.72
ME-PBCC	P4/mmm	3.877	3.877	7.606	114.33

图S3 (a) PBCC和(b) ME-PBCC的SEM照片与除Pr、Ba、Co和Cr元素以外的EDS元素分布图

Fig. S3 SEM images and EDS elemental distribution mappings excluding Pr, Ba, Co, and Cr elements of (a) PBCC and (b) ME-PBCC

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构型熵工程增强双钙钛矿型氧电极抗Cr中毒能力

Enhancing Cr-tolerance Ability of Double Perovskite Cathodes through Configuration Entropy Engineering

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