The electrochemical behavior of lithium-sulfur batteries was investigated by means of electrochemical impedance spectroscopy (EIS). Films of NCPEs (PEO+LiCF3SO3+BaTiO3-g-GO) were cast using a novel hot-press technique. The addition of filler in fractional amount to the solid polymer matrix at room temperature further enhances the ionic conductivity. The membranes were subjected to cycling, FT-IR and Raman spectroscopic analyses. The occurrence of ion-ion pairs interaction has been identified using FT-IR and Raman analysis. Cells with this electrolyte have a high coulombic efficiency of 98% and a high cycling stability.