硅酸盐学报

Mn-Co涂层对SUS441不锈钢面比电阻及其阴极侧界面电阻的影响

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冯仰光 ¹ , 林科迪 ¹ , 张旸 ² , 林王林 ³ , 官万兵 ²

硅酸盐学报 | 固体氧化物电池表界面专题—研究论文 2025,53(10): 3013-3021

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硅酸盐学报 |固体氧化物电池表界面专题—研究论文 2025 , 53 (10) : 3013 -3021

Mn-Co涂层对SUS441不锈钢面比电阻及其阴极侧界面电阻的影响

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冯仰光¹, 林科迪¹, 张旸², 林王林³, 官万兵²

作者信息

^1．浙江启明电力集团有限公司，浙江舟山 316000

^2．中国科学院宁波材料技术与工程研究所，全省先进燃料电池与电解池技术重点实验室，浙江宁波 315201

^3．浙江大学海洋学院，浙江舟山 316021

通讯作者:

张旸（1991—），男，博士，助理研究员。

作者简介:

冯仰光（1983—），男，硕士，高级工程师。

Influence of Mn-Co Coating on Area Specific Resistance of SUS441 and Cathode Side Interfacial Resistance

Yangguang FENG¹, Kedi LIN¹, Yang ZHANG², Wanglin LIN³, Wanbing GUAN²

Affiliations

^1.Zhejiang Qiming Electric Power Group Co., Ltd., Zhoushan 316000, Zhejiang, China

^2.Zhejiang Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

^3.College of Oceanography, Zhejiang University, Zhoushan 316021, Zhejiang, China

Corresponding Author:

ZHANG Yang (1991-), male, Ph.D., Assistant Professor. E-mail: zhangyang@nimte.ac.cn

FENG Yangguang (1983-), male, Master, Senior Engineer. E-mail: 285080321@qq.com

出版时间: 2025-10-20 doi: 10.14062/j.issn.0454-5648.20240780

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摘要

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固体氧化物燃料电池（SOFC）电堆是实现大规模应用的基础，金属连接体是衔接各单体电池的核心部件，而其阴极侧的防护及其界面电阻是影响SOFC电堆性能的关键。本工作以SUS441不锈钢为基体，在表面制备Mn-Co涂层，深入探究该涂层对连接体氧化行为及由此影响界面电阻性能的作用效果。结果显示，经800 h测试，含Mn-Co涂层的连接体面比电阻为11.97 mΩ·cm²，为无防护涂层的47%；含有涂层样品也展现出与阴极良好的界面接触，800 h测试后其界面电阻为7.99 mΩ·cm²，约为无防护涂层的55%。结果表明，Mn-Co涂层有效抑制了SUS441不锈钢基体的氧化，并显著降低了界面电阻，为SOFC电堆的性能优化提供了可行的技术方案。

关键词

连接体 / SUS441不锈钢 / 尖晶石涂层 / 界面电阻 / 固体氧化物燃料电池

Abstract

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Introduction

Solid oxide fuel cell (SOFC) stacks depend on metallic interconnects to ensure the performance with cathode-side protection and interfacial resistance as key determinants. The existing coatings like perovskite, active element oxides and spinel all have drawbacks. For instance, perovskite coatings fail to inhibit oxygen ion diffusion, while active element oxides are typically thin and porous. In contrast, spinel coatings have a promise due to their lower densification temperature and ability to suppress chromium volatility. However, there is little work on the contact resistance. In this work, a Mn-Co spinel coating was applied to SUS441 stainless steel to reduce both oxidation and interfacial resistance. This approach could offer a viable solution for optimizing the performance of SOFC stacks.

Methods

SUS441 was chosen as an interconnect substrate material, and all the samples were cut to small pieces with the dimensions of 10.0 mm × 10.0 mm × 1.5 mm. Manganese nitrate and cobalt nitrate (AR, Sinopharm Group Co., Ltd., China) were dispersed in ethanol solvent, with dispersant, binder, and defoamer added to prepare a precursor solution. A wet-spray device was used to deposit Mn_1.5Co_1.5O₄ coating on the SUS441 substrate (coated SUS441), which was then dried in air and calcined at 850 ℃ for 10 h.

The area-specific resistance (ASR) of the samples was measured by a four-terminal method with a CHI760e electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd., China), with a voltage range of -1 to 1 V. The interfacial contact resistance was calculated based on the ASR values.

The thermal expansion behavior was characterized by a model DIL402C dilatometer (Netzsch Co., Germany) at a heating rate of 5 ℃/min. The microstructures were determined by a model S4800 scanning electron microscope (Hitachi Co., Japan). The oxidation mass gain was monitored by a model FA2104 electronic balance (Shanghai Shunyu Hengping Scientific Instruments Co., Ltd., China). A three-dimensional surface profile was obtained by a model LSM700 laser confocal microscope (Zeiss Co., Germany).

Results and discussion

The coated SUS441 exhibits an uneven surface but a dense cross-section free of cracks or bubbles, indicating a robust adhesion between the coating and substrate. The Mn-Co spinel coating substantially reduces the interconnect's resistance of 0.47 mΩ·cm², compared to 3.29 mΩ·cm² for uncoated SUS441. Also, the coating enhances the activation energy (E_a) for electrical conductivity from 0.59 eV to 0.91 eV, thereby slowing electron migration and reducing the oxidation rate.

The results of long-term testing at 750 ℃ show that the ASR of uncoated SUS441 increases from 26.07 mΩ·cm² to 52.41 mΩ·cm² after 720 h, then gradually decreases and stabilizes at 25.54 mΩ·cm². This may result from the maturation and reconstruction of the oxide layer, which lowers the resistance. In contrast, the coated SUS441 has an initial ASR of 3.96 mΩ·cm², which increases to 16.38 mΩ·cm² after 300 h and then slowly declines to 11.97 mΩ·cm² at 820 h. These findings demonstrate that the Mn-Co coating significantly enhances the high-temperature oxidation resistance of SUS441.

The oxidation mass gain is a key indicator of interconnect oxidation resistance. The coated and uncoated SUS441 interconnects both exhibit a rapid mass gain in the first 200 h. After 200 h, the mass gain rate of the coated SUS441 slows and stabilizes, whereas the uncoated SUS441 further increases. The dense Mn-Co coating effectively blocks oxygen penetration and metal ion migration, thereby slowing oxidation and enhancing resistance. The relationship between the square of oxidation mass gain and time indicates a change in oxidation behavior after approximately 200 h, likely due to the thickening of the oxide layer hindering further oxidation. As the oxide layer thickens, the internal mass transfer becomes more difficult, slowing the oxidation rate. The K_p value decreases by one order of magnitude during the slow oxidation phase, compared to the initial rapid stage.

The coating has a limited impact on the thermal expansion of the interconnect but brings the expansion coefficient of SUS441 closer to that of the La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) cathode, thus improving the thermal compatibility. The initial interfacial contact resistance between SUS441 and LSCF is 3.54 mΩ·cm², stabilizing at 14.57 mΩ·cm². For coated SUS441 and LSCF, the initial interfacial contact resistance decreases from 20.78 mΩ·cm² to 7.99 mΩ·cm². The Mn-Co coating likely improves the interface microstructure, reducing defects and roughness, and enhancing electron transfer. The analysis of laser confocal microscopy indicates that the roughness matching value between SUS441 and LSCF is 0.605, and it is 1.156 for coated SUS441, indicating better surface compatibility and contact with LSCF.

Conclusions

The Mn-Co spinel coating was coated on the surface of SUS441 interconnect, and its effect on suppressing the interconnect's oxidation behavior and reducing interfacial resistance were investigated. The results showed that the coating significantly reduced the ASR of SUS441 from 3.29 mΩ·cm² to 0.47 mΩ·cm² at 800 ℃, maintaining a relatively low ASR of 11.97 mΩ·cm² after 800 h oxidation. The results of oxidation mass gain tests indicated that the coating effectively reduced the oxidation rate of coated SUS441, which was only 43% of that of the uncoated sample. For the interfacial properties, the contact resistance between the Mn-Co coated SUS441 and the LSCF cathode was 7.99 mΩ·cm², which was just 55% of that of the uncoated sample, with improved interfacial roughness matching. These findings could demonstrate that the Mn-Co spinel coating effectively mitigated the oxidation rate and interfacial resistance of SUS441, thereby enhancing its high-temperature oxidation resistance.

Key words

interconnect / SUS441 stainless steel / spinel coating / interfacial resistance / solid oxide fuel cell

引用本文

冯仰光, 林科迪, 张旸, 林王林, 官万兵. Mn-Co涂层对SUS441不锈钢面比电阻及其阴极侧界面电阻的影响. 硅酸盐学报, 2025 , 53 (10) : 3013 -3021 . DOI: 10.14062/j.issn.0454-5648.20240780

Yangguang FENG, Kedi LIN, Yang ZHANG, Wanglin LIN, Wanbing GUAN. Influence of Mn-Co Coating on Area Specific Resistance of SUS441 and Cathode Side Interfacial Resistance[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (10) : 3013 -3021 . DOI: 10.14062/j.issn.0454-5648.20240780

基金

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国家重点研发计划(2021YFB2500402)
宁波市重点研发计划(2023z103)
宁波市自然基金(2023J355)
浙江启明电力集团有限公司(CF059108002021002)

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2025年第53卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240780

接收时间：2024-12-06
首发时间：2026-10-21
出版时间：2025-10-20

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出版历史

收稿日期：2024-12-06
修回日期：2024-12-16

基金

国家重点研发计划(2021YFB2500402)

宁波市重点研发计划(2023z103)

宁波市自然基金(2023J355)

浙江启明电力集团有限公司(CF059108002021002)

作者信息

^1．浙江启明电力集团有限公司，浙江舟山 316000

^2．中国科学院宁波材料技术与工程研究所，全省先进燃料电池与电解池技术重点实验室，浙江宁波 315201

^3．浙江大学海洋学院，浙江舟山 316021

通讯作者:

张旸（1991—），男，博士，助理研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240780

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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