Decoupling Li + Transport in Self‐Healing Polymer Dual‐Salt Electrolytes for Room Temperature Lithium Metal Batteries

Gel polymer electrolytes (GPEs) stand as leading candidates for advancing high‐energy‐density lithium metal batteries toward next‐generation applications. However, the inherent crystallinity of conventional polymer matrices severely limits ionic conductivity (IC) and Li + transference number (t Li + ), while imposing large interfacial resistance and uncontrollable lithium dendrite growth—critical bottlenecks hindering practical room‐temperature application. Herein, we report a dual‐salt incorporation strategy within a self‐curing polymer framework to overcome these challenges. The anion‐anion interactions of the dual‐salt system within the polymer network immobilize the anions, thereby liberating a greater number Li + ions. Additionally, the salt‐polymer interactions alter the polymer energy levels, cooperatively enhancing the IC to 2.23 mS cm −1 and the t Li + to 0.55. The electrolyte sustains stable Li||Li symmetric cycling for over 2000 h. When integrated with a LiFePO 4 cathode, the full cell delivers 133 mAh g 1 at 1C with 75% capacity retention over 700 cycles, while the NMC811||Li cell achieves 135 mAh g −1 , retaining 72% of its initial capacity over 250 cycles. Additionally, the electrolyte exhibits inherent flame retardancy and uniform Li + plating‐stripping, effectively suppressing dendrite penetration. This design strategy provides a viable route to ambient‐temperature, self‐curing GPEs that enhance battery safety and suppress dead lithium.