Micro Area Interface Wetting Structure with Tailored Li⁺-Solvation and Fast Transport Properties in Composite Polymer...

To satisfy the demand for high safety and energy density in energy storage devices, all-solid-state lithium metal batteries with solid polymer electrolytes (SPE) replacing traditional liquid electrolytes and separators have been proposed and are increasingly regarded as one of the most promising candidates as next-generation energy storage systems. In this study, poly(vinylidene fluoride)-hexafluoropropylene/lignosulfonic acid (PVDF-HFP/LSA) composite polymer electrolyte (CPE) membranes with a micro area interface wetting structure were successfully prepared by incorporating LSA into the PVDF-HFP polymer matrix. The enhanced interaction between the polar functional group in LSA and the C═O in N-methylpyrrolidone (NMP) hinders the evaporation of solvent NMP, thus creating a micro area wetting structure, which offers a flexible region for the chain segment movement and enlarging the area of the amorphous zone in PVDF-HFP. From the results of IR and Raman spectroscopy, it was found that the presence of LSA induced unique ion transport channels created by the massive aggregated ion pair (AGG) and contact ion pair (CIP) of ion cluster structures composed of Li⁺ and multiple TFSI^- and, at the same time, effectively reduced the crystallinity of the polymer electrolyte, hence further contributing to the Li⁺ diffusion. As a result, at a rate of 2 C, the Li|CPE-15|LiFePO₄ solid-state battery delivers an initial discharge-specific capacity of 134.9 mAh g^-1 and maintains stability with a retention of 84% during 400 charge-discharge cycles while the Li|CPE-0|LiFePO₄ battery fails after only a few cycles at the same rate.