During the manufacturing and thermal cycles of advanced contemporary large sized sodium sulfur (NaS) batteries, thermally driven stresses can be applied to the glass sealing joints, which may result in catastrophic cell failure. To minimize the thermal stresses at the joints, there is a need to develop a method to properly estimate the maximum thermal stresses by varying the materials properties and shapes of the sealing area, and thereby determine the properties and shapes of sealing material at the joints. In the present study, the optimum coefficient of thermal expansion (CTE) of the glass sealant and end shape of the glass sealing area (i.e., concave, flat, and convex shapes) have been determined using the finite-element analysis (FEA) computation technique. The results showed that the CTE value of 7.8 × 10−6 K−1 with a convex end shape would have the lowest stress concentration in the vicinity of glass sealing joints for the prototype tubular NaS cell design adopted in this work.