中温固体氧化物燃料电池BaO-CaO-Al_2O_3-B_2O_3-SiO_2玻璃合成工艺的优化
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摘要
利用传统工艺成功制备出BaO-CaO-Al_2O_3-B_2O_3-SiO_2封接玻璃并通过改善熔融工艺对玻璃性能进行优化,这三种工艺条件分别为:1300℃保温1 h(工艺A)、1400℃保温1 h(工艺B)和1400℃保温3 h(工艺C),分别得到A、B、C三种样品。利用热膨胀系数、粘度、高温显微镜等测试方法来比较分析三种样品的性能变化,测试结果表明B样品在20-558℃的热膨胀系数为10.3×10~(-6) K~(-1);样品B的粘度值(107.5 dPa·s)在封接材料所需的范围之内(10~6-10~9 dPa·s),同时样品B的润湿角表明其能够在适当的压力下对电解质进行良好地封接;通过扫描电子显微镜(SEM)和能谱分析(EDS)对样品B在750℃下保温100 h后的界面结合性能的表征,发现两者间界面结合性能良好且无明显的元素扩散。从整体上而言,样品B的性能最符合封接玻璃材料的应用要求。
The BaO-CaO-Al_2O_3-B_2O_3-SiO_2 sealing glass was successfully prepared by the traditional process and the glass properties were optimized by improving the melting process. The three process conditions were: 1300 ℃ for 1 h(process A), 1400 °C for 1 h(process B) and 1400 ℃ for 3 h(process C), and samples A, B and C were obtained respectively. The test methods of thermal expansion coefficient, viscosity,and high temperature microscope were used to compare and analyze the performance changes of the three samples. The results show that the thermal expansion coefficient of sample B at 20-558 °C was 10.3 × 10~(-6) K~(-1). The viscosity value of the glass sample B at the sealing temperature(850 ℃) was 107.5 dPa·s and it was within the required range of the sealing material(10~6-10~9 dPa·s). The wetting angle of sample B also indicates that it can seal the electrolyte well under appropriate pressure. The characterization by the scanning electron microscopy(SEM)and energy dispersivespectrometer(EDS) of the interfacial bonding between glass sample B and YSZ at 750 ℃ for 100 h found that the interfacial bonding performance was excellent and there was no obvious elemental diffusion. Overall, the performance of Sample B is most consistent with the application requirements of the sealing glass material.
The BaO-CaO-Al_2O_3-B_2O_3-SiO_2 sealing glass was successfully prepared by the traditional process and the glass properties were optimized by improving the melting process. The three process conditions were: 1300 ℃ for 1 h(process A), 1400 °C for 1 h(process B) and 1400 ℃ for 3 h(process C), and samples A, B and C were obtained respectively. The test methods of thermal expansion coefficient, viscosity,and high temperature microscope were used to compare and analyze the performance changes of the three samples. The results show that the thermal expansion coefficient of sample B at 20-558 °C was 10.3 × 10~(-6) K~(-1). The viscosity value of the glass sample B at the sealing temperature(850 ℃) was 107.5 dPa·s and it was within the required range of the sealing material(10~6-10~9 dPa·s). The wetting angle of sample B also indicates that it can seal the electrolyte well under appropriate pressure. The characterization by the scanning electron microscopy(SEM)and energy dispersivespectrometer(EDS) of the interfacial bonding between glass sample B and YSZ at 750 ℃ for 100 h found that the interfacial bonding performance was excellent and there was no obvious elemental diffusion. Overall, the performance of Sample B is most consistent with the application requirements of the sealing glass material.
引文
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[13]刘亮光,罗凌虹,程亮,等.基于热重差热分析研究玻璃熔制过程中碳酸钡的分解规律[J].硅酸盐通报,2018,37(3):805-809.LIU L G,LUO L H,CHENG L,et al.Bulletin of the Chinese Ceramic Society,2018,37(3):805-809.
[14]胡志强.无机材料科学基础教程[M](第二版).北京:化学工业出版社,2015:86-89.
[15]MOTT N F,GURNEY R W.Recent theories of the liquid state[J].Reports on Progress in Physics,1938,5(1):46-63.
[16]WANG R,LU Z,LIU C,et al.Characteristics of a SiO2-B2O3-Al2O3-BaO-PbO2-ZnO glass-ceramic sealant for SOFCs[J].Journal of Alloys Compounds,2007,432(1-2):189-193.
[17]BEAMAN R G.Relation between(apparent)second-order transition temperature and melting point[J].Journal of Polymer Science,2010,9(5):470-472.
[18]SAKKA S,MACKENZIE J D.Relation between apparent glass transition temperature and liquids temperature for inorganic glasses[J].Journal of Non-crystalline Solids,1971,6(2):145-162.
[2]罗凌虹,刘亮光,王乐莹,等.ZrO2/TiO2/ZrO2+TiO2三种添加剂对CaO-BaO-SiO2-B2O3封接玻璃析晶及抗折强度的影响[J].陶瓷学报,2018,39(4):482-486.LUO L H,LIU L G,WANG L Y,et al.Journal of Ceramics,2018,39(4):482-486.
[3]LIN C K,LIN K L,YEH J H,et al.Aging effects on hightemperature creep properties of a solid oxide fuel cell glassceramic sealant[J].Journal of Power Sources,2013,241(1):12-19.
[4]王琳琳,何峰,王立格,等.BaO对硅酸盐SOFC封接玻璃结构与性能的影响[J].硅酸盐通报,2016,35(01):267-274.WANG L L,HE F,WANG L G,et al.Bulletin of the Chinese Ceramic Society,2016,35(01):267-274.
[5]WANG S F,LU H C,LIU Y X,et al.Characteristics of glass sealants forintermediate-temperature solid oxide fuel cell applications[J].Ceramics International,2017,43(1):S613-S620.
[6]MAHAPATRA M K,LU K.Seal glass for solid oxide fuel cells[J].Journal of Power Sources,2010,195(21):7129-7139.
[7]MAHAPATRA M K,LU K.Glass-based seals for solid oxide fuel and electrolyzer cells:A review[J].Materials Science and Engineering R,2009,67(5-6):65-85.
[8]HEYDARI F,MAGHSOUDIPOUR A,HAMNABARD Z,et al.Evaluation on properties of CaO-BaO-B2O3-Al2O3-Si O2 glassceramic sealants for intermediate temperature solid oxide fuel cells[J].Journal of Materials Science and Technology,2013,29(01):49-54.
[9]LUO Linghong,LIN Youchen,HUANG Zuzhi,et al.Application of BaO-CaO-Al2O3-B2O3-SiO2 glass-ceramic seals in large size planar IT-SOFC[J].Ceramics International,2015,41(8):9239-9243.
[10]CHOU Y S,STEVENSON J W,HARDY J,et al.Material degradation during isothermal ageing and thermal cycling of hybrid mica seals under solid oxide fuel cell exposure conditions[J].Journal of Power Sources,2006,157(1):260-270.
[11]EICHLER K,SOLOW G,OTSCHIK P,et al.BAS(BaO·Al2O3·SiO2)-glasses for hightemperature applications[J].Journal of the European Ceramic Society,1999,19(6):1101-1104.
[12]GHOSH S,SHARMA A D,KUNDU P,et al.Development and characterizations of BaO-CaO-Al2O3-SiO2 glassceramic sealants for intermediate temperature solid oxide fuel cell application[J].Journal of Non-crystalline Solids,2008,354(34):4081-4088.
[13]刘亮光,罗凌虹,程亮,等.基于热重差热分析研究玻璃熔制过程中碳酸钡的分解规律[J].硅酸盐通报,2018,37(3):805-809.LIU L G,LUO L H,CHENG L,et al.Bulletin of the Chinese Ceramic Society,2018,37(3):805-809.
[14]胡志强.无机材料科学基础教程[M](第二版).北京:化学工业出版社,2015:86-89.
[15]MOTT N F,GURNEY R W.Recent theories of the liquid state[J].Reports on Progress in Physics,1938,5(1):46-63.
[16]WANG R,LU Z,LIU C,et al.Characteristics of a SiO2-B2O3-Al2O3-BaO-PbO2-ZnO glass-ceramic sealant for SOFCs[J].Journal of Alloys Compounds,2007,432(1-2):189-193.
[17]BEAMAN R G.Relation between(apparent)second-order transition temperature and melting point[J].Journal of Polymer Science,2010,9(5):470-472.
[18]SAKKA S,MACKENZIE J D.Relation between apparent glass transition temperature and liquids temperature for inorganic glasses[J].Journal of Non-crystalline Solids,1971,6(2):145-162.