Ion–Dipole-Interaction-Induced Encapsulation of Free Residual Solvent for Long-Cycle Solid-State Lithium Metal Batteries

Owing to high ionic conductivity and mechanical strength, poly(vinylidene fluoride) (PVDF) electrolytes have attracted increasing attention for solid-state lithium batteries, but highly reactive residual solvents severely plague cycling stability. Herein, we report a free-solvent-capturing strategy triggered by reinforced ion–dipole interactions between Li+ and residual solvent molecules. Lithium difluoro(oxalato)borate (LiDFOB) salt additive with electron-withdrawing capability serves as a redistributor of the Li+ electropositive state, which offers more binding sites for residual solvents. Benefiting from the modified coordination environment, the kinetically stable anion-derived interphases are preferentially formed, effectively mitigating the interfacial side reactions between the electrodes and electrolytes. As a result, the assembled solid-state battery shows a lifetime of over 2000 cycles with an average Coulombic efficiency of 99.9% and capacity retention of 80%. Our discovery sheds fresh light on the targeted regulation of the reactive residual solvent to extend the cycle life of solid-state batteries.