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原位电化学回收:基于LaSrCoFeO的氧电极的可逆固体氧化物电池中铬中毒下的沉积物转变

In Situ Electrochemical Recovery: Sediment Transformation under Chromium Poisoning in Reversible Solid Oxide Cells with LaSrCoFeO-Based Oxygen Electrodes.

作者信息

Liu Xucong, Li Xuanliang, Chi Bo, Pu Jian, Xiong Chunyan

机构信息

Center for Fuel Cell Innovation, School of Materials Science and Engineering, Huazhong University of Science & Technology, Wuhan, Hubei 430074, China.

Hubei Provincial Research Centre of Engineering & Technology for New Energy Materials, Hubei Key Lab of Novel Reactor & Green Chemical Technology, Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China.

出版信息

ACS Appl Mater Interfaces. 2024 Aug 28;16(34):44889-44899. doi: 10.1021/acsami.4c09441. Epub 2024 Aug 13.

Abstract

Reversible solid oxide cells (RSOCs) are an all-solid-state electrochemical device, which can convert H into electricity in the fuel cell (SOFC) mode and electrolyze HO into fuel gas in the electrolytic cell (SOEC) mode, exhibiting good application prospect in the development of carbon neutrality. However, the degradation of the air electrode caused by Cr-containing steel interconnects is a major obstacle that limits the broader application of RSOCs. Herein, the Cr poisoning effect on LaSrCoFeO (LSCF)-based oxygen electrodes under the electrolysis mode was systematically investigated. The phase transition of the sediment during the chromium poisoning process was captured and monitored. When tested under the presence of Fe-Cr interconnects at 800 °C for 40 h, SrCrO on the surface of LSCF was clearly identified through XRD and Raman analysis as the main deposition, and with the prolonged operating time, LaCrO slowly emerged. Due to the much higher electrical conductivity of LaCrO compared to SrCrO, the negative effect induced by Cr poisoning was offset along with test progressing due to the deposition transition phenomenon. Inspired by the interesting discoveries, transition from SrCrO to LaCrO can be artificially facilitated by switching the operating mode to the SOEC mode, which can partially recover the dramatic degradation caused by the Cr poisoning effect under the SOFC mode. The feasibility of the in situ electrochemical recovery method was also verified by the experimental results. The peak power density of the cells decreased from 0.829 to 0.505 W/cm when operating under the SOFC mode with an Fe-Cr metal connector, and after in situ electrochemical recovery in the SOEC mode, the peak power density recovered to 0.630 W/cm. This study provides a new strategy for achieving high performance and stability of RSOCs.

摘要

可逆固体氧化物电池(RSOCs)是一种全固态电化学装置,它在燃料电池(SOFC)模式下能将氢气转化为电能,在电解池(SOEC)模式下能将水电解为燃料气体,在碳中性发展方面展现出良好的应用前景。然而,含铬钢互连件导致的空气电极降解是限制RSOCs更广泛应用的主要障碍。在此,系统研究了电解模式下铬中毒对基于LaSrCoFeO(LSCF)的氧电极的影响。捕获并监测了铬中毒过程中沉积物的相变。当在800℃下于Fe-Cr互连件存在的情况下测试40小时时,通过XRD和拉曼分析明确鉴定出LSCF表面的SrCrO为主要沉积物,并且随着运行时间的延长,LaCrO缓慢出现。由于LaCrO的电导率比SrCrO高得多,由于沉积转变现象,随着测试的进行,铬中毒引起的负面影响被抵消。受这些有趣发现的启发,通过将运行模式切换到SOEC模式可以人为促进从SrCrO到LaCrO的转变,这可以部分恢复SOFC模式下由铬中毒效应引起的显著降解。实验结果也验证了原位电化学恢复方法的可行性。当在带有Fe-Cr金属连接器的SOFC模式下运行时,电池的峰值功率密度从0.829降至0.505 W/cm²,在SOEC模式下进行原位电化学恢复后,峰值功率密度恢复到0.630 W/cm²。本研究为实现RSOCs的高性能和稳定性提供了一种新策略。

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