Deciphering and Integrating Functionalized Side Chains for High Ion‐Conductive Elastic Ternary Copolymer Solid‐State Electrolytes for Safe Lithium Metal Batteries

A critical challenge in solid polymer lithium batteries is developing a polymer matrix that can harmonize ionic transportation, electrochemical stability, and mechanical durability. We introduce a novel polymer matrix design by deciphering the structure‐function relationships of polymer side chains. Leveraging the molecular orbital‐polarity‐spatial freedom design strategy, a high ion‐conductive hyperelastic ternary copolymer electrolyte (CPE) is synthesized, incorporating three functionalized side chains of poly‐2,2,2‐Trifluoroethyl acrylate (PTFEA), poly(vinylene carbonate) (PVC), and polyethylene glycol monomethyl ether acrylate (PEGMEA). It is revealed that fluorine‐rich side chain (PTFEA) contributes to improved stability and interfacial compatibility; the highly polar side chain (PVC) facilitates the efficient dissociation and migration of ions; the flexible side chain (PEGMEA) with high spatial freedom promotes segmental motion and interchain ion exchanges. The resulting CPE demonstrates an ionic conductivity of 2.19 × 10‐3 S cm‐1 (30 °C), oxidation resistance voltage of 4.97 V, excellent elasticity (2700%), and non‐flammability. The outer elastic CPE and the inner organic‐inorganic hybrid SEI buffer intense volume fluctuation and enable uniform Li+ deposition. As a result, symmetric Li cells realize a high CCD of 2.55 mA cm‐2 and the CPE‐based Li||NCM811 full cell exhibits a high‐capacity retention (~90%, 0.5 C) after 200 cycles.