PVDF-HFP via Localized Iodization as Interface Layer for All-Solid–State Lithium Batteries with Li₆PS₅Cl Films

All-solid lithium (Li) metal batteries (ASSLBs) with sulfide-based solid electrolyte (SEs) films exhibit excellent electrochemical performance, rendering them capable of satisfying the growing demand for energy storage systems. However, challenges persist in the application of SEs film owing to their reactivity with Li metal and uncontrolled formation of lithium dendrites. In this study, iodine-doped poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP) as an interlayer (PHI) to establish a stable interphase between Li metal and Li₆PS₅Cl (LPSCl) films is investigated. The release of I ions and PVDF-HFP produces LiI and LiF, effectively suppressing lithium dendrite growth. Density functional theory calculations show that the synthesized interlayer layer exhibits high interfacial energy. Results show that the PHI@Li/LPSCl film/PHI@Li symmetrical cells can cycle for more than 650 h at 0.1 mA cm⁻². The PHI@Li/LPSCl film/NCM622 cell exhibits a distinct enhancement in capacity retention of ≈26% when using LiNi_0.6Mn_0.2Co_0.2O₂ (NCM622) as the cathode, compared to pristine Li metal as the anode. This study presents a feasible method for producing next-generation dendrite-free SEs films, promoting their practical use in ASSLBs.