金属连接体涂层材料MnCo2O4尖晶石的氧化动力学行为和电性能*

doi:10.11900/0412.1961.2015.00449

金属学报

2016, Vol. 52

Issue (3): 355-360 DOI: 10.11900/0412.1961.2015.00449

论文

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金属连接体涂层材料MnCo₂O₄尖晶石的氧化动力学行为和电性能^*

张文颖¹(

),李俊²,周波¹

1 中国地质大学机械与电子信息学院, 武汉 430074
2 华中科技大学材料科学与工程学院材料成型与模具技术重点实验室, 武汉 430074

OXIDATION KINETICS BEHAVIOR AND ELECTRICAL PROPERTY OF MnCO₂O₄ SPINEL AS A COATING MATERIAL FOR METALLIC INTERCONNECTS

Wenying ZHANG¹(

),Jun LI²,Bo ZHOU¹

1 School of Mechanical Engineering and Electronic Information, China University of Geosciences, Wuhan 430074, China
2 State Key Laboratory of Materials Processing and Die&Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

引用本文:

张文颖, 李俊, 周波. 金属连接体涂层材料MnCo₂O₄尖晶石的氧化动力学行为和电性能^*[J]. 金属学报, 2016, 52(3): 355-360.
Wenying ZHANG, Jun LI, Bo ZHOU. OXIDATION KINETICS BEHAVIOR AND ELECTRICAL PROPERTY OF MnCO₂O₄ SPINEL AS A COATING MATERIAL FOR METALLIC INTERCONNECTS[J]. Acta Metall Sin, 2016, 52(3): 355-360.

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摘要:

采用溶胶-凝胶法在SUS 430合金表面制备MnCo₂O₄尖晶石涂层, 研究在固体氧化物燃料电池(SOFCs)阴极气氛下涂层对于SUS 430合金氧化动力学行为和电性能的效用. 利用XRD, EDS和SEM对合金表面氧化物的相结构,表面和截面形貌以及成分进行表征, 并采用四探针直流技术测量表面氧化物的面比电阻(ASR). 结果表明, 涂层合金在750 ℃空气中氧化1000 h形成2 μm氧化物层, 其主要由内层Mn-Cr尖晶石和外层掺杂的Mn-Co尖晶石构成; Cr₂O₃和Fe₂O₃的形成受到了抑制. 氧化动力学曲线遵循抛物线规律, 2段氧化速率常数分别为3.74×10^-15g²/(cm⁴s) (0~200 h)和7.06×10^-15g²/(cm⁴·s) (200~1000 h), 与无涂层SUS 430合金相比降低了1个数量级. 在600~800 ℃范围内, 氧化物层的ASR介于5.21~22.65 mΩcm²范围内. MnCo₂O₄涂层有效地增强了SUS 430合金的抗氧化能力和电性能.

关键词 ：固体氧化物燃料电池, 金属连接体, MnCo2O4 尖晶石, 氧化动力学, 面比电阻

Abstract：

MnCo₂O₄spinel was coated on the surface of SUS 430 alloy by using the sol-gel method. The oxidation kinetics behavior and electrical property of coated SUS 430 alloy in solid oxide fuel cells (SOFCs) cathode atmosphere were investigated. XRD, EDS and SEM were used to characterize the phase structure, surface and cross-section morphology, and composition of the surface oxides; the area specific resistance (ASR) of the surface oxides was measured by using the four-probe direct current technique. The result shows that a 2 μm thick oxide scale, mainly consisting of an inner layer of Mn-Cr spinel and an outer layer of doped Mn-Co spinel, was formed during cyclic oxidation at 750 ℃ in air for 1000 h. The growth of Cr₂O₃ and Fe₂O₃ was depressed. The oxidation kinetics obeys the parabolic law with two rate constants 3.74×10^-15g²/(cm⁴s)(0~200 h) and 7.06×10^-15g²/(cm⁴s) (200~1000 h), respectively, which is 1 order of magnitude lower than that of the SUS 430 alloy without coating. The ASR is in the range of 5.21~22.65 mΩcm²at 600~800 ℃. MnCo₂O₄ coating was proved to be effective in enhancing the oxidation resistance and electrical property of SUS 430 alloy.

Key words： solid oxide fuel cell metallic interconnect spinel MnCo2O4 oxidation kinetics area specific resistance

收稿日期: 2015-08-21

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https://www.ams.org.cn/CN/10.11900/0412.1961.2015.00449 或 https://www.ams.org.cn/CN/Y2016/V52/I3/355

表1 图2中不同区域的EDS分析结果

图1 涂覆MnCo2O4涂层的SUS 430合金在750 ℃空气中氧化1000 h前后的XRD谱

图2 MnCo2O4涂层在750 ℃空气中氧化1000 h前后的表面形貌

图3 MnCo2O4涂层在750 ℃空气中氧化1000 h后的截面形貌和EDS线扫描分析

图4 涂覆MnCo2O4涂层的SUS 430合金在750 ℃空气中氧化时氧化增重的平方与氧化时间的关系

图5 MnCo2O4涂层在750 ℃空气中氧化1000 h后面比电阻ASR与测试温度的关系

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