Na2O对固体氧化物燃料电池用透辉石封接微晶玻璃性能的影响

硅酸盐通报 ›› 2023, Vol. 42 ›› Issue (8): 2922-2927.

Na₂O对固体氧化物燃料电池用透辉石封接微晶玻璃性能的影响

谭金奇¹, 信彩丽², 屠恒勇³, 韩壮壮¹, 刘冰¹, 袁坚^1,2

1.武汉理工大学硅酸盐建筑材料国家重点实验室,武汉 430070;
2.河北省沙河玻璃技术研究院,沙河 054100;
3.上海交通大学机械与动力学院燃料电池所,上海 200240

收稿日期:2023-02-21 修订日期:2023-05-16 发布日期:2023-08-18
通信作者: 袁坚,博士,教授。E-mail:janeyuan@whut.edu.cn
作者简介:谭金奇(1997—),男,硕士研究生。主要从事高温封接微晶玻璃的研究。E-mail:2317672244@qq.com

Effect of Na₂O on Properties of Diopside-Based Sealing Glass-Ceramics for Solid Oxide Fuel Cell

TAN Jinqi¹, XIN Caili², TU Hengyong³, HAN Zhuangzhuang¹, LIU Bing¹, YUAN Jian^1,2

1. State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China;
2. Hebei Shahe Glass Technology Research Institute, Shahe 054100, China;
3. School of Mechanical Power and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2023-02-21 Revised:2023-05-16 Published:2023-08-18

摘要/Abstract

摘要： 本文设计和制备了以透辉石为主晶相的R₂O-RO-Al₂O₃-B₂O₃-SiO₂系封接微晶玻璃,用于固体氧化物燃料电池(SOFC)的封接,研究了Na₂O含量(0%～10%,摩尔分数)对封接玻璃热膨胀系数(CTE)、析晶与烧结润湿特性的影响,表征了封接件在高温长时间热处理后玻璃与SUS403不锈钢的封接界面。结果表明,Na₂O可以显著改善玻璃的热性能,所制备的玻璃样品在封接温度范围内经热处理后可获得主晶相为透辉石(CaMgSi₂O₆) 的微晶玻璃。随着Na₂O含量增加,主晶相透辉石的晶相含量不同,微晶玻璃的热膨胀系数由未晶化前的8.22×10^-6 K^-1提升至11.79×10^-6 K^-1,能够满足SOFC封装的热膨胀匹配。当Na₂O含量大于等于8%(摩尔分数)时,玻璃中析出高膨胀钙镁黄长石(Ca₂MgSi₂O₇)晶相,不利于封接。将4%(摩尔分数)玻璃试样与SUS403高温封接后于850 ℃保温100 h,封接界面致密牢固无气孔,界面处存在Cr₂O₃层以及比封接玻璃本体更致密的透辉石薄层,这些致密层的存在有利于限制封接玻璃中Na⁺向界面扩散。

关键词: 氧化钠, 透辉石, 高温封接微晶玻璃, 固体氧化物燃料电池, 热膨胀系数, 封接界面

Abstract: In this paper, R₂O-RO-Al₂O₃-B₂O₃-SiO₂ based sealing glass-ceramics with diopside as main crystalline phase was designed and prepared for the sealing of solid oxide fuel cell (SOFC). The effect of Na₂O content (0%～10%, mole fraction) on coefficient of thermal expansion (CTE), crystallization and sintering wetting property of sealing glass was analyzed, and the sealing interface between glass and SUS403 stainless steel after high temperature and long time heat treatment was characterized. The results show that Na₂O can significantly improve the thermal properties of glass, the prepared glass samples can be obtained as glass-ceramics with main crystalline phase of diopside (CaMgSi₂O₆) after heat treatment in sealing temperature range. With the increase of Na₂O content, the crystal phase content of main crystal phase diopside is different, and coefficient of thermal expansion of glass-ceramics increases from 8.22×10^-6 K^-1 before crystallization to 11.79×10^-6 K^-1, which can meet the thermal expansion match of SOFC sealing. When the Na₂O content is greater than or equal to 8% (mole fraction), the crystalline phase of high expansion calcium akermanite (Ca₂MgSi₂O₇) is precipitated in glass, which is not conducive to sealing. After sealing 4% (mole fraction) glass sample with SUS403 at high temperature for 100 h at 850 ℃, the sealing interface is dense and firm without air pores. There is a Cr₂O₃ layer at the interface and a thin layer of diopside which is denser than glass sealing body. The existence of these dense layers is beneficial to limit the diffusion of Na⁺ from sealing glass to interface.

Key words: sodium oxide, diopside, high temperature sealing glass-ceramics, solid oxide fuel cell, coefficient of thermal expansion, sealing interface

中图分类号:

TQ171

谭金奇, 信彩丽, 屠恒勇, 韩壮壮, 刘冰, 袁坚. Na₂O对固体氧化物燃料电池用透辉石封接微晶玻璃性能的影响[J]. 硅酸盐通报, 2023, 42(8): 2922-2927.

TAN Jinqi, XIN Caili, TU Hengyong, HAN Zhuangzhuang, LIU Bing, YUAN Jian. Effect of Na₂O on Properties of Diopside-Based Sealing Glass-Ceramics for Solid Oxide Fuel Cell[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(8): 2922-2927.

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Na₂O对固体氧化物燃料电池用透辉石封接微晶玻璃性能的影响

Effect of Na₂O on Properties of Diopside-Based Sealing Glass-Ceramics for Solid Oxide Fuel Cell

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