Thermally activated batteries have good stability, reliability and long shelf life. Due to these characteristics and operational mechanism, thermal batteries are usually applied to military power sources. Especially, Li/$FeS_2$ thermal batteries, which are used mostly in these days, use LiCl-KCl and LiBr-LiCl-LiF as electrolytes. The electrochemistry of thermal batteries have been researched for long time, however, electrochemical study using impedance spectroscopy was not published so much. Through this research, microscopic electrochemical research was investigated with electrochemical impedance spectroscopy(E.I.S). Electrolyte effects on Li/$FeS_2$ thermal battery was researched changing electrolytes, LiCl-KCl and LiBr-LiCl-LiF. Additionally, the salts, which are added to electrolytes, effects on thermal battery were researched. It is expected that the impedance spectroscopy analysis is applicable to not only thermal battery electrochemical study effectively, but also, thermal battery developments.