氧化锆复合Bi2O3-BaO-SiO2-RxOy玻璃封接材料性能研究

doi:10.3724/SP.J.1077.2010.01058

无机材料学报 ›› 2010, Vol. 25 ›› Issue (10): 1058-1064.DOI: 10.3724/SP.J.1077.2010.01058 CSTR: 32189.14.SP.J.1077.2010.01058

氧化锆复合Bi₂O₃-BaO-SiO₂-R_xO_y玻璃封接材料性能研究

韩敏芳, 杜俊平, 于立安

(中国矿业大学(北京) 煤气化燃料电池研究中心, 化学与环境工程学院, 北京 100083)

收稿日期:2010-01-22 修回日期:2010-03-10 出版日期:2010-10-20 网络出版日期:2010-09-26
基金资助:
国家自然科学基金(508 2150, 50730004); 高等学校学科创新引智计划(111计划)(B08010)

Properties of Bi₂O₃-BaO-SiO₂-R_xO_y Glass with ZrO₂-filler Composite Sealant

HAN Min-Fang, DU Jun-Ping, Yu Li-An

(Union Research Center of Fuel Cell, School of Chemical & Environment Engineering, China University of Mining & Technology (CUMTB), Beijing 100083, China)

Received:2010-01-22 Revised:2010-03-10 Published:2010-10-20 Online:2010-09-26
Supported by:
National Nature Science Foundation of China (50872150, 50730004), Programme of Introducing Talents of Discipline to University (B08010)

摘要/Abstract

摘要： 在玻璃中复合脊性骨料是固体氧化物燃料电池(SOFC)封接材料研究热点. 实验选定在Bi₂O₃-BaO-SiO₂-R_xO_y (简记为BiBaSi)玻璃体系中复合10wt%~30wt%的ZrO₂颗粒来改善玻璃在高温下的封接性能.结果表明, ZrO₂复合BiBaSi玻璃后, 复合体系热膨胀系数略有增大; 随着ZrO₂含量增多, 复合封料适宜使用温度逐渐提高, 从基体BiBaSi玻璃的720℃到BiBaSi-10Zr、BiBaSi-20Zr、BiBaSi-30Zr的780、860和900℃; 氧化锆加入到基体玻璃中, 一部分作为脊性骨料存在于玻璃相中, 维持了高温封接要求的形状和尺寸; 另一部分逐渐进入了玻璃网络中, 促进玻璃结晶生成新的物相Bi₄Si₃O₁₂; 两种晶体相共存于玻璃相中, 提高了复合体系封接的稳定性. 通过改变氧化锆加入量, 可以有效调控封接材料相关性能, 满足SOFC封接要求.

关键词: 固体氧化物燃料电池, Bi₂O₃-BaO-SiO₂玻璃, 氧化锆骨料, 复合封接材料, 封接性能

Abstract: It is research focus that composite materials including glass and skeletal structure are used as sealant in solid oxide fuel cell (SOFC). The composite sealant with 10wt%-30wt% ZrO₂-filler in the Bi₂O₃-BaO-SiO₂(BiBaSi) glass were researched in order to improve sealing properties at high temperature. As a result, the coefficients of thermal expansion of the composite sealants were increased than that of basic glass. The suitable sealing temperatures of composite sealant vary from the 720℃ of base glass to 780℃, 860℃ and 900℃ of BiBaSi-10Zr, BiBaSi-20Zr, BiBaSi-30Zr, respectively. ZrO₂-fillers in base glass have two roles: Parts of ZrO₂-fillers as skeletal structure materials always exist in base glass, which help to maintain the required shape and size of sealant. The other ZrO₂-fillers can also drop into the network of the BiBaSi glass and therefore form a new phase Bi₄Si₃O₁₂. Two kinds of crystal phase of ZrO₂and Bi₄Si₃O₁₂ coexist in the composite sealant to improve the stability of composite system in high temperature. The properties of sealing materials could be easily controlled in SOFC sealant by changing the amount of ZrO₂-fillers in composite materials.

Key words: solid oxide fuel cell, Bi₂O₃-BaO-SiO₂ glass, ZrO₂-filler, composite sealant, sealing properties

中图分类号:

TQ171

韩敏芳, 杜俊平, 于立安. 氧化锆复合Bi₂O₃-BaO-SiO₂-R_xO_y玻璃封接材料性能研究[J]. 无机材料学报, 2010, 25(10): 1058-1064.

HAN Min-Fang, DU Jun-Ping, Yu Li-An. Properties of Bi₂O₃-BaO-SiO₂-R_xO_y Glass with ZrO₂-filler Composite Sealant[J]. Journal of Inorganic Materials, 2010, 25(10): 1058-1064.

参考文献

[1] 韩敏芳, 彭苏萍. 固体氧化物燃料电池材料与制备. 北京: 科技出版社, 2004. [2] Subhash C.Singhal(编), 韩敏芳(译). 高温固体氧化物燃料电池-原理、设计和应用. 北京: 科学出版社, 2006: 27. [3] Nielsen K A, Solvang M, Nielsen S B L, et al. Glass composite seals for SOFC application. Journal of the European Ceramic Society, 2007, 27(2): 1817-1822. [4] Haanappel V A C, Shemet V, Vinke I C, et al. A novel method to evaluate the suitability of glass sealant–alloy combinations under SOFC stack conditions. Journal of Power Sources, 2005, 141(1): 102-107. [5] Zheng R, Wang S R, Nie H W, et al. SiO2-CaO-B2O3-Al2O3 ceramic glaze as sealant for planar ITSOFC. Journal of Power Sources, 2004, 128(2): 165-172. [6] Lara C, Pascual M J, Prado M O, et al. Sintering of glasses in the system RO-Al2O3-BaO-SiO2 (R=Ca, Mg, Zn) studied by hot-stage microscopy. Solid State Ionics, 2004, 170(3): 201-208. [7] Larsen P H, Poulsen F W, Berg R W. The influence of SiO2 addition to 2MgO-Al2O3-3.3P2O5 glass. Journal of Non-Crystalline Solids, 1999, 244(1): 16-24. [8] Lara C, Pascual M J, Duran A. Glass-forming ability, sinterability and thermal properties in the systems RO-BaO-SiO2 (R = Mg, Zn). Journal of Non-Crystalline Solids, 2004, 348: 149-155. [9] Laorodphan N, Namwong P, Thiemsorn W, et al. A low silica, barium borate glass–ceramic for use as seals in planar SOFCs. Journal of Non-Crystalline Solids, 2009, 355(1): 38-44. [10] Xue Liang A, Yamanis James, Lear Gregory, et al. Composite Sealant for Solid Oxide Fuel Cells. United States Patent, US6271158B1, 2001.08.07. [11] Donald I W, Metcalfe B L, Gerrard L A, et al. The influence of Ta2O5 additions on the thermal properties and crystallization kinetics of a lithium zinc silicate glass. Journal of Non-Crystalline Solids, 2008, 354(2): 301-310. [12] Gross S M, Koppitz T, Remmel J, et al. Glass–ceramic composite as a new sealing material for SOFCs. In Proceedings of the IX ECS on Solid Oxide Fuel Cells, ed. S. C. Singhal and J. Mizusaki, 2005: 1924. [13] Yang Z, Meinhardt K D, Stevenson J W. Chemical compatibility of barium–calcium–aluminosilicate-based sealing glasses with the ferritic stainless steel interconnect in SOFCs. J. Electrochem. Soc., 2003, 150(8): A1095-A1101. [14] Yang Z, Weil K S, Paxton D M, et al. Selection and evaluation of heat-resistant alloys for SOFC interconnect applications. J. Electrochem. Soc., 2003, 150(9): A1188-A1201. [15] H¨oland W, Beall G. Glass–ceramic Technology. The American Ceramic Society, Westerville, OH, 2002. [16] Lahl N, Singh K, Singheiser L, et al. Crystallisation kinetics in AO-Al2O3-SiO2-B2O3 glasses (A:Ba, Ca, Mg). J. Mater. Sci., 2000, 35(12): 3089-3096. [17] Gross Sonja M, Koppitz Thomas, Remmel Josef, et al. Joining properties of a composite glass-ceramic sealant. Fuel Cells Bulletin, 2006(9): 12-15. [18] Lara C, Pascual M J, Prado M O, et al. Sintering of glasses in the system RO-Al2O3-BaO-SiO2(R=Ca,Mg,Zn) studied by hot-stage microscopy. Solid State Ionics, 2004, 170(3/4): 201-208. [19] Eichler K, Solow G, Otschik P, et al. BAS (BaO·Al2O3·SiO2)- glasses for high temperature applications. Journal of the European Ceramic Society, 1999, 19(6/7): 1101-1104. [20] Hwang Shiang-Po, Wu Jenn-Ming. Effect of composition on microstructural development in MgO-Al2O3-SiO2 glass-ceramics. Journal of the American Ceramic Society, 2001, 84(5): 1108-1112. [21] Ghosh Saswati, Sharma AD, Kundu P, Mahanty S, et al. Development and characterizations of BaO-CaO-Al2O3-SiO2 glass-ceramic sealants for intermediate temperature solid oxide fuel cell application. Journal of Non-Crystalline Solids, 2008, 354(34): 4081-4088. [22] Han Min-Fang, Wang Huan, Wang Qi. Research of the Composite BiO2-SiO2-RxOy(R=K, Ca, Ba, Zn and Al) Glass used for SOFC sealing Materials. (MP3-2007), Beijing, China, 2007. [23] Han Minfang, Wang Zhongli, Wang Yuqian. Study on the sealing materials for SOFC. Key Engineering Materials, 2007, 336-338: 452-454. [24] Werner Vogel, 著. 谢于深, 译. 玻璃化学. 北京: 轻工业出版社, 1988: 221. [25] 赵彦钊, 殷海荣.玻璃工艺学. 化学工业出版社, 2006. [26] Fergus J W. Sealants for solid oxide fuel cells. Journal of Power Sources, 2005, 147(1): 46-57. [27] 彭练, 朱庆山, 谢朝晖, 等(PENG Lian, et al). 中温SOFC密封玻璃热稳定性研究. 无机材料学报(Journal of Inorganic Materials), 2006, 21(4): 867-872. [28] Fei Y T, Fan S J, Sun R Y, et al. Study on phase diagram of Bi2O3-2SiO2 system for Bridgman growth of Bi4Si3O12 single crystal. Progress in Crystal Growth and Characterization of Materials, 2000, 40(124): 183-188. [29] Zhereb V P, Skorikov V M. Metastable states in bismuth-containing oxide systems. Inorganic Material, 2003, 39(2): 121-145. [30] 费一汀, 范世 (FEI Yi-Ting, et al). Bi2O3-2SiO2系统的相关系和析晶行为的研究进展. 无机材料学报(Journal of Inorganic Materials), 1997, 12(4): 469-476. [31] 费一汀, 范世, 孙仁英, 等(FEI Yi-Ting, et al). Bi2SiO5的亚稳定相平衡的研究. 硅酸盐学报(Journal of the Chinese Ceramic Society), 1999, 27(2): 230-236.

氧化锆复合Bi₂O₃-BaO-SiO₂-R_xO_y玻璃封接材料性能研究

Properties of Bi₂O₃-BaO-SiO₂-R_xO_y Glass with ZrO₂-filler Composite Sealant

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	潘建隆, 马官军, 宋乐美, 郇宇, 魏涛. 燃料还原法原位制备高稳定性/催化活性SOFC钴基钙钛矿阳极[J]. 无机材料学报, 2024, 39(8): 911-919.
[2]	叶梓滨, 邹高昌, 吴琪雯, 颜晓敏, 周明扬, 刘江. 阳极支撑型锥管串接式直接碳固体氧化物燃料电池组的制备及性能[J]. 无机材料学报, 2024, 39(7): 819-827.
[3]	张琨, 王宇, 朱腾龙, 孙凯华, 韩敏芳, 钟秦. LaNi_0.6Fe_0.4O₃阴极接触材料导电特性调控及其对SOFC电化学性能的影响[J]. 无机材料学报, 2024, 39(4): 367-373.
[4]	陈正鹏, 金芳军, 李明飞, 董江波, 许仁辞, 徐韩昭, 熊凯, 饶睦敏, 陈创庭, 李晓伟, 凌意瀚. 双钙钛矿Sr₂CoFeO₅₊_δ阴极材料的制备及其中温固体氧化物燃料电池性能研究[J]. 无机材料学报, 2024, 39(3): 337-344.
[5]	薛顶喜, 伊炳尧, 李国君, 马帅, 刘克勤. 功能梯度阳极固体氧化物燃料电池热应力数值模拟研究[J]. 无机材料学报, 2024, 39(11): 1189-1196.
[6]	郭天民, 董江波, 陈正鹏, 饶睦敏, 李明飞, 李田, 凌意瀚. 中温固体氧化物燃料电池的高熵双钙钛矿阴极材料: 兼容性与活性研究[J]. 无机材料学报, 2023, 38(6): 693-700.
[7]	樊帅, 金天, 张山林, 雒晓涛, 李成新, 李长久. Li₂O烧结助剂对固体氧化物燃料电池LSGM电解质烧结特性及离子电导率的影响[J]. 无机材料学报, 2022, 37(10): 1087-1092.
[8]	曹丹,周明扬,刘志军,颜晓敏,刘江. 阳极支撑质子导体电解质固体氧化物燃料电池的制备及其性能研究[J]. 无机材料学报, 2020, 35(9): 1047-1052.
[9]	夏天, 孟燮, 骆婷, 占忠亮. 固体氧化物燃料电池La_xSr_2-3_x_/2Fe_1.5Ni_0.1Mo_0.4O_6-_δ阳极性能研究[J]. 无机材料学报, 2020, 35(5): 617-622.
[10]	李凯, 李霄, 李箭, 谢佳苗. 基于应力分析Ni-Fe合金支撑固体氧化物燃料电池结构稳定性研究[J]. 无机材料学报, 2019, 34(6): 611-617.
[11]	汪维, 苑莉莉, 丘倩媛, 周明扬, 刘美林, 刘江. 流延法制备单片式直接碳固体氧化物燃料电池组及其性能研究[J]. 无机材料学报, 2019, 34(5): 509-514.
[12]	夏天, 孟燮, 骆婷, 占忠亮. Ca掺杂Sr₂Fe_1.5Mo_0.5O_6-_δ材料的合成与作为对称固体氧化物燃料电池电极催化剂的性能研究[J]. 无机材料学报, 2019, 34(10): 1109-1114.
[13]	李斯琳, 屠恒勇, 于立军. 中温固体氧化物燃料电池Nd₂NiO₄₊_δ-Ce_0.8Gd_0.2O_2-_δ复合阴极性能研究[J]. 无机材料学报, 2017, 32(5): 469-475.
[14]	徐红梅, 张华, 李恒, 简耀永, 谢武, 王一平, 徐铭泽. 纳米结构LSCF-SDC复合阴极的制备及其氧还原机理研究[J]. 无机材料学报, 2017, 32(4): 379-385.
[15]	谢佳苗, 王峰会. 基于热应力分析的固体氧化物燃料电池阳极功能层优化设计[J]. 无机材料学报, 2017, 32(4): 400-406.