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Ag掺杂调控中温固体氧化物燃料电池阴极酸性位点增强耐铬能力

高源1,2, 魏波2, 金芳军1, 吕喆2, 凌意瀚1   

  1. 1.中国矿业大学 材料与物理学院,徐州 221000;
    2.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 150000
  • 收稿日期:2025-03-11 修回日期:2025-05-05
  • 通讯作者: 魏 波, 教授. E-mail: bowei@hit.edu.cn;凌意瀚, 教授. E-mail: lyhyy@cumt.edu.cn
  • 作者简介:高 源, 博士. E-mail: tbh371@cumt.edu.cn
  • 基金资助:
    国家自然科学基金 (22279025, 21773048); 江苏省杰出青年基金 (BK20240109); 中央高校基础研究基金 (2023FRFK06005, HIT.NSRIF202204); 中国博士后科学基金(2024M753513)

Ag Doping Modulating Cathode Acidic Sites to Enhance Chromium Resistance for Intermediate Temperature Solid Oxide Fuel Cells

GAO Yuan1,2, WEI Bo2, JIN Fanjun1, LÜ Zhe2, LING Yihan1   

  1. 1. School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221000, China;
    2. Heilongjiang Provincial Key Laboratory of Advanced Quantum Functional Materials and Sensor devices, School of Physics, Harbin Institute of Technology, Harbin 150000, China
  • Received:2025-03-11 Revised:2025-05-05
  • Contact: WEI Bo, professor. E-mail: bowei@hit.edu.cn; LING Yihan, professor. E-mail: lyhyy@cumt.edu.cn
  • About author:GAO Yuan, PhD. E-mail: tbh371@cumt.edu.cn
  • Supported by:
    National Natural Science Foundation of China (22279025, 21773048); Natural Science Foundation of Jiangsu Province (BK20240109); Fundamental Research Funds for the Central Universities (2023FRFK06005, HIT.NSRIF202204); The China Postdoctoral Science Foundation(2024M753513)

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摘要： 铬中毒现象是制约固体氧化物燃料电池阴极实际应用的重要因素。尤其富碱土元素的钙钛矿氧化物阴极在高温下易发生离子偏析和杂质中毒,进而导致阴极性能显著降低。为提高阴极耐铬能力,本研究采取Ag掺杂策略,调控阴极材料SrCo0.9Ta0.1O3-δ(SCT)的酸性位点,并系统探究材料的电导率、催化活性和表面微观形貌及组分。结果表明,Ag掺杂使材料的电导率提升,且掺杂后的材料具有更大的氧表面交换系数,有利于提高其阴极催化活性。700 ℃时,Sr0.9Ag0.1Co0.9Ta0.1O3-δ(SACT10)阴极的极化电阻(Rp)为0.0176 Ω·cm2,明显低于SCT阴极(0.0366 Ω·cm2)。此外,由于掺入Ag,SACT10材料中Co的平均价态升高,使其相对酸度提高,提高了材料的耐铬能力。在含铬气氛中运行22 h后,SACT10阴极的极化电阻为0.205 Ω·cm2,明显低于SCT阴极(0.964 Ω·cm2),这是因为SACT10阴极表面观察到更少的惰性二次相。以上结果证实在材料中掺杂Ag可以有效增加酸性位点,提高活性,增强耐铬能力。制备的SACT10有望成为具有应用前景的中温SOFCs阴极材料。

关键词: 固体氧化物燃料电池, 耐铬能力, 酸性位点, 碱土离子, 表面偏析

Abstract: Cr poisoning is an important factor restricting the practical application of solid oxide fuel cells (SOFCs) cathodes. In particular, the alkaline earth rich perovskite oxide cathodes are prone to cation segregation and impurity poisoning at high temperatures, which can significantly reduce the cathode performance. To improve the Cr resistance of the cathode, the acid site of SrCo0.9Ta0.1O3-δ (SCT) was regulated by Ag doping, and the conductivity, catalytic activity, surface morphology and composition of materials were systematically investigated. The results show that Ag doping enhances the conductivity of the material, and the doped material exhibits higher oxygen surface exchange coefficient, which is conducive to improving its cathodic catalytic activity. At 700 ℃, the polarization resistance (Rp) of Sr0.9Ag0.1Co0.9Ta0.1O3-δ (SACT10) cathode is 0.0176 Ω·cm2, which is significantly lower than that of SCT cathode (0.0366 Ω·cm2). In addition, due to the Ag doping strategy, the average valence state of Co in SACT10 material increases, which increases the relative acidity and improves the Cr resistance. After operating in Cr-containing atmosphere for 22 h, Rp of SACT10 cathode is 0.205 Ω·cm2, significantly lower than that of SCT cathode (0.964 Ω·cm2), and less inert secondary phases are observed on the surface of SACT10 cathode after testing. The above results confirm that Ag doping can effectively increase acid sites, improve activity and enhance Cr resistance. SACT10 obtained in this work is expected to be a promising medium temperature SOFCs cathode material.

Key words: solid oxide fuel cell, chromium resistance, acidic site, alkaline earth cation, surface segregation

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