Electrical conduction mechanism in NaCl complexed PEO/PVP polymer blend electrolytes

► Suppression of crystallinity of the complexed samples is confirmed by XRD analysis. ► Interaction of salt with host and its miscibility is demonstrated by FTIR studies. ► Ionic motion obeyed Jonscher's power law. The dc conductivity increased with salt. ► Rise of dielectric constant with salt, represents fractional increase in charges. ► Non‐Debye nature of samples is observed by modulus spectra.