This paper presents the research and development of β″-Al2O3 ceramic electrolytes for sodium sulfur battery applications in the Shanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS). The process to prepare large size β″-Al2O3 ceramic tubes is described. Composite electrolytes with ZrO2 as second phase additives are introduced. The strengthening and toughening effects of the second phase are significant. The results show that high quality β″-Al2O3 ceramic electrolytes with diameter as large as 60mm and length of 500mm are successfully produced. The composite of β″-Al2O3 and tetragonal ZrO2 displayed much better mechanical properties than the pristine β″-Al2O3 ceramics.