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Sodium ion conducting gel polymer electrolytes based on polyacrylonitrile (PAN) with ethylene carbonate and dimethyl formamide as plasticizing solvents are prepared by the solution cast technique. These electrolyte films are free standing, transparent and dimensionally stable. Na ? ions are derived from NaI. The structural properties of pure and complex formations have been examined by X-ray diffraction, Fourier transform infrared spectroscopic studies and differential scanning calorimetric studies. The variation of the conductivity with salt concentration ranging from 10 to 40 wt% is studied. The sample containing 30 wt% of NaI exhibits the highest conductivity of 2.35 9 10 -4 S cm -1 at room temperature (303 K) and 1 9 10 -3 S cm -1 at 373 K. The conductivity-temperature dependence of polymer electrolyte films obeys Arrhenius behavior with activation energy in the range of 0.25-0.46 eV. The transport numbers both electronic (t e ) and ionic (t i ) are evaluated using Wagner's polarization technique. It is revealed that the conducting species are predominantly due to ions. The ionic transport number of highest conducting film is found to be 0.991. Solid-state battery with configuration Na/(PAN ? NaI)/(I 2 ? C ? electrolyte) is developed using the highest conducting gel polymer electrolyte system and the discharge characteristics of the cell are evaluated over the load of 100 KX.