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

• In-MOF as a multifunctional promoter enables PVH-IM composite solid polymer electrolyte to achieve high ionic conductivity of 1.23 × 10−3 S cm−1 and excellent electrochemical stability against Li anodes. • In-MOF adsorbs and converts free residual solvents into bonded states, preventing side reactions with Li anodes while maintaining Li+ transport. • In-MOF induces inorganic-rich solid electrolyte interphase layers, preventing PVH from reacting with lithium anodes and promoting uniform lithium deposition without dendrite growth. • Li|PVH-IM|Li symmetric cells maintain stable cycling for 5550 h at 0.2 mA cm−2, and all-solid-state LFP|PVH-IM|Li full cells deliver 80.0% capacity retention after 280 cycles at 0.5C at 25 °C.