Abstract(#br)The solid polymer electrolyte (SPE) films comprise poly(vinylidene fluoride) (PVDF)/poly(ethylene oxide) (PEO) blend (75/25 wt/wt%) as host polymer matrix with lithium perchlorate (LiClO 4 ) as ionic dopant for different salt concentrations (i.e., 5, 10, 15, 20, 25, and 30 wt%), and also varying compositional weight ratio PVDF/PEO blends (i.e., 75/25, 50/50, 25/75, and 10/90 wt/wt%) with 25 wt% concentration of LiClO 4 were prepared by solution casting at 70 °C. The results obtained from X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy revealed that there is enormous alteration in the α- and β-phase crystals of the PVDF and the size and content of the PEO crystallites, and also the degree of crystallinity of these SPE materials with the variation of... salt concentration and the polymer blend composition. Dielectric relaxation spectroscopy (DRS) was employed over the frequency range from 20 Hz to 1 MHz, at 27 °C for the study of the complex impedance, dielectric permittivity, dielectric loss tangent, ac electrical conductivity, and electric modulus spectra of the SPE films. All these spectra were analyzed separately and simultaneously by a novel ‘master curve representation’ procedure to unveil the contribution of various dielectric polarization processes (i.e., electrode, interfacial, molecular (dipolar), and the ionic) and their relaxations which are exhibited with increasing order of frequency and have substantial overlapping with the adjacent processes in these heterogeneous ion conducting materials. The loss tangent spectra of these materials manifest prominent dielectric relaxation peaks which attribute to the cation coordinated polymer chain segmental dynamics. The high frequencies ac electrical conductivity data of all these materials obey the power law, whereas the Nyquist plots of impedance data exhibit reasonably distinguishable bulk and electrode polarization frequency regions for the electrolytes having salt concentration ≥20 wt%. The inverse correlation observed between the relaxation time and the dc ionic conductivity establishes that the transportation of ions is predominantly coupled to the polymer chain segmental motion which assists the hopping between favourable conduction sites in the ion-dipole complexes. The SPE films are comparatively stiffer and have a slightly higher degree of crystallinity when the salt concentration is ≤ 15 wt% and they exhibit distinct dielectric, dc ionic conductivity, and relaxation behaviour as compared to that of the softer and lower crystallinity films having salt concentration ≥20 wt%. These SPE films possess good electrochemical performance and close-to-unity total ion transference numbers. Among these two sets of the SPE films, the maximum dc ionic conductivity was noted 2.01 × 10 −5 S/cm at 27 °C for the 75PVDF/25PEO–30 wt% LiClO 4 film from the set of different salt concentrations, and 5.61 × 10 −6 S/cm for 25PVDF/75PEO–25 wt% LiClO 4 film from the set of varying compositions of the polymer blend matrix. The considerable ionic conductivity values of these SPE films at ambient temperature and also their promising electrochemical performance corroborate them as novel ion conductors suitable for the development of solid-state rechargeable lithium-ion batteries.