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In the present study, poly(ethylene oxide) (PEO) and poly(vinylidene fluoride) (PVDF) blend based composite polymer electrolytes (CPEs) had been prepared by using a different content of nano-sized BaTiO₃ filler, in order to examine the filler addition effect on the structural modification and electrochemical properties. The crystallinity and thermal stability of the CPEs was evaluated using differential scanning calorimeter (DSC), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The electrochemical properties of CPEs were measured by the AC impedance method and cyclic voltammetry (CV). As a result, Both DSC and XRD results indicated that the CPE showed reduced crystallinity after the introduction of BaTiO₃ filler. From the ionic conductivity results, the CPE containing BaTiO₃ filler 15wt.% showed the highest ionic conductivity (1.2×10⁻⁴S/cm) with a wide electrochemical stability window and an …