硅酸盐学报

平板式固体氧化物燃料电池密封材料研究进展

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王显玉 ¹ , 杜志鸿 ¹^,² , 王捷 ¹^,² , 赵海雷 ¹^,²

硅酸盐学报 | 青年视角 2025,53(7): 2066-2078

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硅酸盐学报 |青年视角 2025 , 53 (7) : 2066 -2078

平板式固体氧化物燃料电池密封材料研究进展

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王显玉¹, 杜志鸿¹^,², 王捷¹^,², 赵海雷¹^,²

作者信息

^1．北京科技大学材料科学与工程学院，北京 100083

^2．新能源材料与技术北京市重点实验室，北京 100083

通讯作者:

赵海雷（1966—），女，博士，教授；

杜志鸿（1986—），男，博士，副教授。

作者简介:

王显玉（1997—），女，博士研究生。

Progress on Sealing Materials for Planar Solid Oxide Fuel Cells

Xianyu WANG¹, Zhihong DU¹^,², Jie WANG¹^,², Hailei ZHAO¹^,²

Affiliations

^1.School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

^2.Beijing Municipal Key Lab for Advanced Energy Materials and Technologies, Beijing 100083, China

Corresponding Author:

ZHAO Hailei (1966-), female, Ph.D., Professor. E-mail: hlzhao@ustb.edu.cn;

DU Zhihong (1986-), male, Ph.D., Associate Professor. zhihongdu@ustb.edu.cn

WANG Xianyu (1997-), female, Doctoral candidate. E-mail: wangxianyuustb@163.com

出版时间: 2025-07-20 doi: 10.14062/j.issn.0454-5648.20240798

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摘要

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平板式固体氧化物燃料电池（SOFC）具有功率密度高、制备工艺简单、电堆紧凑性高等优点，是目前的主流构型。平板式SOFC需经高温密封方能正常运行，密封技术直接影响电池的效率、寿命和安全性，是保障SOFC安全高效稳定运行的关键环节。密封材料是SOFC密封技术的核心，密封材料的性能直接影响电堆的密封特性，进而影响电堆的发电性能和运行稳定性。本文针对压密封和刚性密封两种不同密封方式，分别综述了韧性金属基材料、云母基材料、陶瓷基材料、玻璃和玻璃-陶瓷基材料以及金属钎焊材料等多种密封材料的研究现状，分析了密封失效的主要原因以及对应的改进措施，最后对平板式SOFC密封材料的发展趋势进行了展望。

关键词

固体氧化物燃料电池 / 密封材料 / 压密封 / 刚性密封

Abstract

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Planar solid oxide fuel cells (SOFCs) offer several advantages, i.e., high power density, simplified fabrication processes, and excellent stack compactness, thus making them the predominant architecture in SOFC technology. However, high-temperature sealing remains a major challenge for planar SOFC stacks. Sealing technology is critical in determining the safety, efficiency, and overall stability of SOFC systems. The sealing material as the core component of this technology directly affects the stack hermeticity, thereby impacting its power output and long-term operational reliability.

Planar solid oxide fuel cells (SOFCs) utilize two primary sealing methods, i.e., compressive and rigid sealing, which are distinguished via the application of compressive load during the sealing process. Compressive sealing materials suitable for planar SOFCs include metal, mica-based, and ceramic-based compressive seals, each offering unique properties such as excellent deformability, high stability, and superior high-temperature resistance. 1) Metal Compressive Seals: Silver (Ag) is the most widely used metal compressive sealing material due to its outstanding ductility, chemical stability, and lower cost, compared to platinum and gold. However, Ag also has several drawbacks, including temperature sensitivity, low mechanical strength, and limited chemical stability under both oxidizing and reducing atmospheres, hindering its suitability for commercial SOFC applications. 2) Mica-based Compressive Seals: Mica-based compressive sealing materials feature a distinctive layered structure, with adjacent layers held together by weak K⁺ interactions. This unique arrangement enables an interlayer sliding under compressive stress, enhancing their adaptability as sealing materials. The main gas leakage pathways in mica-based compressive sealing materials occur through the mica itself and the contact interfaces between mica and adjacent components. These leakage pathways can be mitigated via introducing an intermediate layer or infiltrating with wetting materials. Thermiculite® 866 is one of the most commercially advanced mica-based compressive sealing materials. It is based upon the mineral vermiculite and contains no organic binder or any other organic component. Thermiculite® 866 is soft and highly conformable, allowing for both macro- and micro-sealing to be readily achieved. In addition, it also maintains its sealing properties without relaxation or creep, even under high-temperature conditions. 3) Ceramic-based Compressive Seals: Ceramic-based materials with a great thermal and chemical stability are challenging to use directly as compressive sealing materials for SOFCs, considering their ductility, thermal expansion coefficient (TEC), and chemical compatibility. However, it is feasible to modify the morphology, optimize the manufacturing process or incorporate metallic components to improve their deformability, making them suitable for seals. In summary, the development and optimization of compressive sealing materials are crucial for enhancing the performance and durability of planar SOFCs. Each type of sealing material presents distinct advantages and challenges, necessitating ongoing research to address these issues and improve SOFC technology.

Rigid sealing materials generally provide a superior gas tightness, compared to compressive seals, making them a focal point in the development of planar solid oxide fuel cells (SOFCs). These rigid seals primarily encompass glass, glass-ceramic, and metal brazing techniques. 1) Glass and Glass-ceramic Seals: Glass and glass-ceramic materials are among the most commonly used sealing materials in planar SOFCs. Adjusting the phase composition or controlling the crystallization process of these materials allows for tailoring their TEC, effectively minimizing thermal expansion mismatches with adjacent cell components. However, solely designing the composition of glass sealants to meet comprehensive performance requirements, such as glass transition temperature (T_g), softening temperature (T_s), TEC, thermal stability, and mechanical strength, poses some challenges. Incorporating ceramics, mica, or glass fibers into glass sealants can significantly enhance their overall properties. A research indicates that glasses and particularly glass-ceramics are ideal sealant candidates due to their properties, including thermal expansion, can be tailored to be compatible with other fuel cell materials. 2) Metal Brazing: Brazing is a high-temperature joining technique wherein a molten metal filler material fills the gap between metal and ceramic components, interacting with the substrates and solidifying upon cooling to form a robust, hermetic joint. Brazing techniques are primarily categorized into active metal brazing (AMB) and air reaction brazing (RAB). AMB is typically conducted under vacuum or a protective gas atmosphere, leading to higher production costs, compared to RAB. The Ag-CuO system as one of the most preferred RAB materials faces several challenges, i.e., high TEC, poor chemical stability, and low mechanical strength, significantly hindering its long-term stability in SOFC applications. In summary, while rigid sealing materials offer superior gas tightness essential for the efficient operation of planar SOFCs, some challenges remain in optimizing their properties to ensure long-term stability and compatibility with other cell components. Ongoing research and development efforts focus on addressing these challenges to enhance the performance and durability of SOFC systems.

Solid oxide fuel cells (SOFCs) hold a significant promise for efficient energy conversion, however, some challenges associated with sealing materials impede their widespread commercialization. Two primary causes of sealing failure are identified:

1) Thermal Expansion Mismatch: Differences in the thermal expansion coefficients (TEC) between sealing materials and adjacent SOFC components can induce thermal stresses at high operating temperatures. These stresses may lead to the formation of pores and cracks, compromising the mechanical integrity of the seal and resulting in gas leakage.

2) Decomposition and Interfacial Reactions: Exposure to high temperatures and environments with both oxidizing and reducing conditions can cause decomposition of sealing materials. In addition, chemical reactions at the interfaces between seals and SOFC components can also occur, ultimately leading to a sealing failure.

Addressing these issues is crucial for the commercial application of SOFCs. Future research should focus on:

1) Enhancing high-temperature stability and chemical compatibility: Developing materials that remain stable and chemically inert under SOFC operating conditions.

2) Improving TEC matching: Tailoring the TEC of sealing materials to closely align with those of adjacent components to minimize thermal stresses.

3) Enhancing resistance to chemical corrosion and oxidation: Creating seals that can withstand corrosive environments and resist oxidation over prolonged periods.

4) Optimizing glass-ceramic formulations: Adjusting compositions to reduce crystallization tendencies, thereby improving mechanical properties and durability.

5) Developing self-healing materials: Innovating materials capable of autonomously repairing minor damages, extending the operational lifespan of seals.

6) Advancing cost-effective solutions: Streamlining manufacturing processes to reduce costs without compromising quality.

7) Promoting environmentally friendly technologies: Ensuring that new sealing materials and processes with a minimal environmental impact, aligning with sustainable development goals.

Summary and prospects

Advancements in sealing materials are pivotal for the progression of solid oxide fuel cell (SOFC) technology. These materials must maintain a long-term stability under extreme operating conditions, i.e., high temperatures, elevated pressures, and chemically aggressive environments. In addition, they also require excellent thermal expansion compatibility and gas impermeability to ensure the structural integrity and operational longevity of SOFC stacks. Future developments in SOFC sealing materials should focus on glass-ceramic composites, offering superior chemical stability, tailored thermal expansion behavior, and robust mechanical properties at elevated temperatures. These characteristics make them well-suited for ensuring the long-term stability of SOFC systems. The microstructure of these composites can be engineered to enhance gas tightness, self-healing capabilities, and overall durability via optimizing the composition of glass and ceramic phases, as well as refining heat treatment processes. The development of high-performance glass-ceramic composite sealing materials will address the critical challenges associated with the existing SOFC sealing technologies, providing some essential solutions for the commercialization and large-scale deployment of SOFC systems. Advancements in this field will facilitate a widespread adoption of clean energy technologies, contributing to the global transition toward a low-carbon economy and sustainable energy infrastructure.

Key words

solid oxide fuel cell / sealing material / compressive sealing / rigid sealing

引用本文

王显玉, 杜志鸿, 王捷, 赵海雷. 平板式固体氧化物燃料电池密封材料研究进展. 硅酸盐学报, 2025 , 53 (7) : 2066 -2078 . DOI: 10.14062/j.issn.0454-5648.20240798

Xianyu WANG, Zhihong DU, Jie WANG, Hailei ZHAO. Progress on Sealing Materials for Planar Solid Oxide Fuel Cells[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (7) : 2066 -2078 . DOI: 10.14062/j.issn.0454-5648.20240798

基金

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国家重点研发计划(2023YFE0119500)

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2025年第53卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240798

接收时间：2024-12-16
首发时间：2026-10-21
出版时间：2025-07-20

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收稿日期：2024-12-16
修回日期：2025-01-12

基金

国家重点研发计划(2023YFE0119500)

作者信息

^1．北京科技大学材料科学与工程学院，北京 100083

^2．新能源材料与技术北京市重点实验室，北京 100083

通讯作者:

赵海雷（1966—），女，博士，教授；

杜志鸿（1986—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240798

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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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