固態氧化物燃料電池玻璃密封材料SiO2-Al2O3-Y2O3-ZnO-MxOy之研發

Development of SiO2-Al2O3-Y2O3-ZnO-MxOy glass sealants for solid oxide fuel cell

謝岳錡(Yueh-Chi Hsieh)

指導教授 ： 王錫福 ； 徐永富

國立臺北科技大學/工程學院/材料科學與工程研究所/碩士(2014年)

摘要

本研究目的為開發出無添加B2O3及鹼金/鹼土族的封裝玻璃SiO2-Al2O3-Y2O3-ZnO-MxOy系統，在此玻璃系統中添加La2O3、Nd2O3、Co3O4及NiO以進一步改善其封裝效果，應用於固態氧化物燃料電池。添加La2O3相較於Nd2O3有助於提升熱膨脹係數，玻璃配方之Tg點在721°C至767°C之間，熱膨脹係數(CTE)最高達到8.64×10-6/°C。添加少量的NiO可以提高玻璃的結晶溫度Tc點，使得黏合溫度提高到800和850°C依然沒有其他結晶相產生，保有原來的玻璃相，YASZLN1甚至在操作溫度經歷500小時仍然還是保持非晶態。而在玻璃與不鏽鋼(SUS430)的黏合測試中，YASZLN1、YASZLN4、YZLN1-Z6、YZLN1-Y6、YASZLC1及YASN1六個玻璃配比皆可與SUS430不鏽鋼黏合。各玻璃與不鏽鋼間並沒有發生任何互擴散情形。其中熱膨脹係數較高的YASZLN1及YZLN1-Y6玻璃在溫度700°C、荷重1 psi及進氣壓力1 psi通入He氣經過500小時量測YASZLN1漏氣率維持在0.012 sccm/cm以下，而YZLN1-Y6維持在0.021 sccm/cm以下。YASZLN1配比經30 vol% LaCoO3 (LCO)陶瓷粉複合，熱膨脹係數由原來的8.35?10-6/°C提升至9.23?10-6/°C。通入He氣經過500小時漏氣率測試中維持在0.023 sccm/cm以下，與純玻璃YASZLN1結果變化並不大。

關鍵字

固態氧化物燃料電池 ； 封裝材料 ； 漏氣率 ； 玻璃膏

並列摘要

SiO2-Al2O3-Y2O3-ZnO-MxOy glass sealants free of alkaline earth metals and B2O3 were prepared in this study. In order to improve the seal glass adhesion to other cell components for SOFC, various dopants including La2O3, Nd2O3, Co3O4 and NiO were added in the glass. Adding La2O3 shown a better effect than that of Nd2O3 on increasing the glass coefficient of thermal expansion (CTE). The Tg fell in the range of 721°C and 767°C. The highest CTE is 8.64×10-6/°C. Trace amounts of NiO dopant could raise the crystallization temperature, no recrystallization occurred in the glass when heated to the sealing temperature range between 800 and 850°C, indicating a fine thermal stability of the glass. YASZLN1 glass could maintain amorphous after been soaked at working temperature for 500 hours. In this study, the glasses YASZLN1, YASZLN4 YZLN1-Z6, YZLN1-Y6, YASZLC1 and YASN1 possessed good wettability and could effectively bound with stainless steel (SUS430), no detectable inter-diffusion across the interface was found. YASZLN1 appeared that a low leak rates of 0.012 sccm/cm was obtained at a He pressure of 1 psi with a compressive stress of 1 psi and unchanged as the system was soaked at 700°C for 500 h, YZLN1-Y6 glass the leak rate was 0.021 sccm/cm. The CTE of the YASZLN1 glass escalated from 7.01 to 9.30?10-6/°C with 30 vol% LaCoO3 (LCO) fillers. It appeared that a low leak rate of 0.023 sccm/cm was obtained and unchanged at the same condition.

並列關鍵字

Solid oxide fuel cell ； Sealing materials ； Leak test ； Glass sealant

參考文獻

1. Sea-Fue Wang, Yung-Fu Hsu, Hsi-Chuan Lu, Shih-Chieh Lo and Chieh-Sheng Cheng, "B2O3-free SiO2-Al2O3-SrO-La2O3-ZnO-TiO2 glass sealants for intermediate temperature solid oxide fuel cell applications," International Journal of Hydrogen Energy, vol. 37, 2012, pp. 5901-5913.

3. K. Lu and M.K. Mahapatra, "Glass-based seals for solid oxide fuel and electrolyzer cells - A review," Materials Science and Engineering, vol. 67, 2010, pp. 65-85.

4. J. Pu, Y. Ye, D. Yan, X. Wang, B. Chi and J. Li, "Development of novel glass-based composite seals for planar intermediate temperature solid oxide fuel cells," International Journal of Hydrogen energy, vol. 37, 2012, pp. 1710-1716.

5. S.F. Wang, Y.R. Wang, Y.F. Hsu and C.C. Chuang, "Effect of additives on the thermal properties and sealing characteristic of BaO-Al2O3-B2O3-SiO2 glass-ceramic for solid oxide fuel cell application," International Journal of Hydrogen Energy, vol. 34, 2009, pp. 8235-8244.

6. S. Ghosh, A.D. Sharma, P. Kundu and R.N. Basu, "Glass-Ceramic Sealants for Planar IT-SOFC: A Bilayered Approach for Joining Electrolyte and Metallic Interconnect," Journal of the Electrochemical Society, vol. 155, 2008, pp. B476-B478.