Indium-MOF as Multifunctional Promoter to Remove Ionic Conductivity and Electrochemical Stability Constraints on Fluoropolymer Electrolytes for All-Solid-State Lithium Metal Battery

Abstract Fluoropolymers promise all-solid-state lithium metal batteries (ASLMBs) but suffer from two critical challenges. The first is the trade-off between ionic conductivity ( σ ) and lithium anode reactions, closely related to high-content residual solvents. The second, usually consciously overlooked, is the fluoropolymer’s inherent instability against alkaline lithium anodes. Here, we propose indium-based metal–organic frameworks (In-MOFs) as a multifunctional promoter to simultaneously address these two challenges, using poly(vinylidene fluoride–hexafluoropropylene) (PVH) as the typical fluoropolymer. In-MOF plays a trio: (1) adsorbing and converting free residual solvents into bonded states to prevent their side reactions with lithium anodes while retaining their advantages on Li + transport; (2) forming inorganic-rich solid electrolyte interphase layers to prevent PVH from reacting with lithium anodes and promote uniform lithium deposition without dendrite growth; (3) reducing PVH crystallinity and promoting Li-salt dissociation. Therefore, the resulting PVH/In-MOF (PVH-IM) showcases excellent electrochemical stability against lithium anodes, delivering a 5550 h cycling at 0.2 mA cm −2 with a remarkable cumulative lithium deposition capacity of 1110 mAh cm −2 . It also exhibits an ultrahigh σ of 1.23 × 10 −3 S cm −1 at 25 °C. Moreover, all-solid-state LiFePO 4 |PVH-IM|Li full cells show outstanding rate capability and cyclability (80.0% capacity retention after 280 cycles at 0.5C), demonstrating high potential for practical ASLMBs.