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

doi:10.15541/jim20250105

无机材料学报 ›› 2026, Vol. 41 ›› Issue (1): 70-78.DOI: 10.15541/jim20250105 CSTR: 32189.14.10.15541/jim20250105

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.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 出版日期:2026-01-20 网络出版日期:2025-05-22
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(1996-), 男, 博士后. E-mail: tbh371@cumt.edu.cn
基金资助:
国家自然科学基金(22279025);国家自然科学基金(21773048);江苏省杰出青年基金(BK20240109);中央高校基础研究基金(2023FRFK06005);中央高校基础研究基金(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 Fangjun¹, LÜ Zhe², LING Yihan¹()

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 Published:2026-01-20 Online:2025-05-22
Contact: WEI Bo, professor. E-mail: bowei@hit.edu.cn;
LING Yihan, professor. E-mail: lyhyy@cumt.edu.cn
About author:GAO Yuan (1996-), male, post doctor. E-mail: tbh371@cumt.edu.cn
Supported by:
National Natural Science Foundation of China(22279025);National Natural Science Foundation of China(21773048);Natural Science Foundation of Jiangsu Province(BK20240109);Fundamental Research Funds for the Central Universities(2023FRFK06005);Fundamental Research Funds for the Central Universities(HIT.NSRIF202204);China Postdoctoral Science Foundation(2024M753513)

摘要/Abstract

摘要： 铬中毒现象是制约固体氧化物燃料电池(SOFCs)阴极实际应用的重要因素。尤其是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SrCo_0.9Ta_0.1O_3-_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, Sr_0.9Ag_0.1Co_0.9Ta_0.1O_3-_δ(SACT10)阴极的极化电阻为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, 增强了材料的耐铬能力。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 cell (SOFC) 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 SrCo_0.9Ta_0.1O_3-_δ (SCT) was regulated by Ag doping, whose conductivity, catalytic activity, surface morphology, and composition were then 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 ℃, polarization resistance (R_p) of Sr_0.9Ag_0.1Co_0.9Ta_0.1O_3-_δ (SACT10) cathode is 0.0176 Ω·cm², 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 further increases the relative acidity and improves the Cr resistance. After operating in Cr-containing atmosphere for 22 h, R_p of SACT10 cathode is 0.205 Ω·cm², significantly lower than that of SCT cathode (0.964 Ω·cm²), and fewer inert secondary phases are observed on the surface of SACT10 cathode after testing. All 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 SOFC cathode material.

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

中图分类号:

TQ174

高源, 魏波, 金芳军, 吕喆, 凌意瀚. 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[J]. 无机材料学报, 2026, 41(1): 70-78.

GAO Yuan, WEI Bo, JIN Fangjun, LÜ Zhe, LING Yihan. Ag Doping Modulating Cathode Acidic Sites to Enhance Chromium Resistance for Intermediate Temperature Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2026, 41(1): 70-78.

图/表 12

图1 合成后样品的(a) XRD图谱和(b)局部放大图

Fig. 1 (a) XRD patterns and (b) local enlargements of the as-prepared samples

图2 SCT、SACT5及SACT10材料在空气中的(a)电导率及(b)相应的阿伦尼乌斯曲线

Fig. 2 (a) Electrical conductivities of SCT, SACT5 and SACT10 samples in air and (b) their corresponding Arrhenius plots

图3 SCT、SACT5和SACT10材料在(a) 700, (b) 650和(c) 600 ℃的ECR曲线以及(d) kchem

Fig. 3 ECR curves at (a) 700, (b) 650 and (c) 600 ℃ of SCT, SACT5 and SACT10, and (d) their kchem

图4 SCT、SACT5和SACT10阴极在(a) 700和(b) 650 ℃的EIS谱图、(c) Rp和(d)相应的阿伦尼乌斯曲线

Fig. 4 EIS spectra of SCT, SACT5 and SACT10 cathodes at (a) 700 and (b) 650 ℃, and their (c) Rp and (d) corresponding Arrhenius plots Inset in (a): equivalent circuit

图5 (a~e)不同阴极在700 ℃含铬气氛下运行不同时间的EIS谱图; (f) SACT10阴极EIS谱图相应的DRT分析; (g, h)运行后不同阴极的(g) EIS谱图和(h)相应的DRT分析

Fig. 5 (a-e) EIS spectra of different cathodes at 700 ℃ under Cr-containing atmosphere for different operating times; (f) DRT analysis of the corresponding EIS spectra of SACT10 cathode; (g) EIS spectra for different cathodes after operating, and (h) their corresponding DRT analysis (a) SCT; (b) S0.95CT; (c) S0.9CT; (d) SACT5; (e) SACT10

图6 700 ℃含铬气氛中处理22 h前后(a) SCT、(b) Cr-SCT、(c) Cr-S0.95CT、(d) Cr-S0.9CT、(e) Cr-SACT5和(f) Cr-SACT10致密样品片的SEM照片

Fig. 6 SEM images of (a) SCT, (b) Cr-SCT, (c) Cr-S0.95CT, (d) Cr-S0.9CT, (e) Cr-SACT5, and (f) Cr-SACT10 dense pellets before and after treatment at 700 ℃ under Cr-containing atmosphere for 22 h

图7 700 ℃含铬气氛中运行22 h前后(a) SCT、(b) Cr-SCT、(c) Cr-SACT5和(d) Cr-SACT10阴极的SEM照片

Fig. 7 SEM images of (a) SCT, (b) Cr-SCT, (c) Cr-SACT5, and (d) Cr-SACT10 cathodes before and after operating at 700 ℃ under Cr-containing atmosphere for 22 h

图8 700 ℃含铬气氛处理前后SACT10样品的XPS谱图

Fig. 8 XPS spectra of SACT10 before and after treatment under Cr-containing atmosphere at 700 ℃ (a) Sr3d; (b) Co2p; (c) O1s; (d) Cr2p; (e) Ag3d; (f) Ta4f. Colorful figures are available on website

图S1 在880 ℃下烧结5 h后得到的前驱体粉末的XRD图谱

Fig. S1 XRD patterns of precursor powders sintered at 880 ℃ for 5 h

图S2 SACT10样品片的SEM-EDS元素分布图

Fig. S2 SEM-EDS elemental mappings of SACT10 pellet

图S3 含铬气氛处理后样品的Raman图谱

Fig. S3 Raman spectra of samples treated in the Cr-containing atmosphere

图S4 700 ℃含铬气氛下处理22 h前后致密样品片(a) Cr-SCT、(b) Cr-S0.95CT、(c) Cr-S0.9CT、(d) Cr-SACT5和(e) Cr-SACT10表面二次相的粒径分布图

Fig. S4 Particle size distributions of the secondary phases on the surface of dense pellets (a) Cr-SCT, (b) Cr-S0.95CT, (c) Cr-S0.9CT, (d) Cr-SACT5, and (e) Cr-SACT10 before and after treatment at 700 ℃ under Cr-containing atmosphere for 22 h

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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

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

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