In the present work, the effect of different nanofiller (BaTiO3, CeO2, Er2O3 or TiO2) on blend solid polymer electrolyte comprising of PEO and PVC complexed with bulky LiPF6 have been explored. The XRD analysis confirms the polymer nanocomposite formation. FTIR provides evidence of interaction among the functional groups of the polymer with the ions and the nanofiller in terms of shifting and changing peak profile. The highest ionic conductivity is ~2.3×10 -5 S cm -1 with a wide electrochemical stability window of ~3.5 V for 10 wt. % Er2O3. The real and imaginary part of dielectric permittivity follows the identical trend of the decreasing value with increase in the frequency. The particle size and the dielectric constant shows an abnormal trend with different nanofiller. The ac conductivity follows the universal power law. An effective mechanism has been proposed to understand the nanofiller interaction with cation coordinated polymer in the investigated system. storage/conversion devices must have (a) high ionic conductivity; (b) electrochemical stability window (>4 V); (c) low melting point; (d) high boiling point; (e) high chemical stability; (f) nontoxicity; (g) low cost and good compatibility with electrodes. Solid polymer electrolyte (SPEs) plays a dual role as an electrolyte as well as a separator which keeps both electrodes separate and avoids the user from using a spacer as in liquid electrolyte system. The first report on ionic conduction was given by P. V. Wright [5] and Fenton et al [6] in 1973 and it was concluded that polymer host dissolved with an alkali metal salt results in an ionic conductive system. The first application of novel polymer electrolyte in batteries was announced by Armand and his co-workers in 1978 [7]. Most devices are based on liquid/gel polymer electrolytes due to their high ionic conductivity (10 -3 -10 -2 Scm -1 ) and compatible with electrodes. But poor mechanical strength, freezing at low temperature, leakage and flammable nature limits their application in commercial use. This motivates the researchers toward better replacement of liquid polymer electrolyte with a solvent free polymer electrolyte having high ionic conductivity, leak proof, flexibility, wide electrochemical window, good mechanical strength, light weight and ease of preparation [8-10]. Solid polymer electrolytes (SPEs) fulfill all above requirements and have attracted researchers globally towards development for their potential application in portable electronics and electrochemical devices [11]. The commonly used host polymer for preparation of polymer nanocomposite films (PNCs) is PEO [12], PAN [13], PMMA [14], PEMA [15] and PVC [16]. Out of aforesaid host polymers, polyethylene oxide (PEO) is undoubtedly the best host polymer used as SPEs with strong, unstrained C-O, C-C, C-H bonds and it has high dielectric constant, easy availability, and high ionic conductivity in amorphous phase, low glass transition temperature, high flexibility, and good dimensional and chemical stability. But PEO possesses low ion...

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