Tunable PVDF/PVA/Li Polymeric Composites: A Path Toward Solid Electrolytes

The development of safe, cost‐effective solid electrolytes is essential for overcoming the limitations of liquid electrolytes in lithium‐ion batteries. In this work, poly(vinylidene fluoride)/poly(vinyl alcohol)/lithium hydroxide (PVDF/PVA/LiOH) polymeric composites were synthesized via solvent casting and characterized by XRD, FTIR, TGA, DSC, and CIS to assess the influence of polymer blend composition on their properties. The optimized formulation—comprising a PVDF/LiOH matrix modified with PVA—exhibited an electrical resistance of 1.3 × 10 5 Ω at room temperature, nearly three orders of magnitude lower than that of the base PVDF/LiOH composition (10 8 Ω), while maintaining thermal stability up to 270°C. XRD analysis revealed the coexistence of α ‐ and β ‐phases of PVDF with increased peak broadening, indicative of enhanced amorphization and improved ion‐transport pathways. FTIR spectra confirmed strong polymer–salt interactions through shifts in OH and CO bands, correlating with improved Li + mobility. Although the ionic conductivity remained moderate (9.79 × 10 −8 S/cm), the combination of tunable composition, reduced resistance, and high thermal stability highlights the potential of PVDF/PVA/LiOH blends as robust candidates for next‐generation solid‐state batteries.