A Fast Na‐Ion Conduction Polymer Electrolyte via Triangular Synergy Strategy for Quasi‐Solid‐State Batteries

Polymer electrolytes provide a visible pathway for the construction of high-safety quasi-solid-state batteries due to their high interface compatibility and processability. Nevertheless, sluggish ion transfer at room temperature seriously limits their applications. Herein, a triangular synergy strategy is proposed to accelerate Na-ion conduction via the cooperation of polymer-salt, ionic liquid, and electron-rich additive. Especially, PVDF-HFP and NaTFSI salt acted as the framework to stably accommodate all the ingredients. An ionic liquid (Emim⁺ -FSI^- ) softened the polymer chains through a weakening molecule force and offered additional liquid pathways for ion transport. Physicochemical characterizations and theoretical calculations demonstrated that electron-rich Nerolin with π-cation interaction facilitated the dissociation of NaTFSI and effectively restrained the competitive migration of large cations from EmimFSI, thus lowering the energy barrier for ion transport. The strategy resulted in a thin F-rich interphase dominated by NaTFSI salt's decomposition, enabling rapid Na⁺ transmission across the interface. These combined effects resulted in a polymer electrolyte with high ionic conductivity (1.37×10^-3 S cm^-1 ) and t_Na+ (0.79) at 25 °C. The assembled cells delivered reliable rate capability and stability (200 cycles, 99.2 %, 0.5 C) with a good safety performance.