Inhibiting Residual Solvent Induced Side Reactions in Vinylidene Fluoride‐Based Polymer Electrolytes Enables Ultra‐Stable Solid‐State Lithium Metal Batteries

Abstract Residual solvents in vinylidene fluoride (VDF)‐based solid polymer electrolytes (SPEs) have been recognized as responsible for their high ionic conductivity. However, side reactions by the residual solvents with the lithium (Li) metal induce poor stability, which has been long neglected. This study proposes a strategy to achieve a delicate equilibrium between ion conduction and electrode stability for VDF‐based SPEs. Specifically, 2,2,2‐trifluoro‐ N , N ‐dimethylacetamide (FDMA) is developed as the nonside reaction solvent for poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVHF)‐based SPEs, achieving both high ionic conductivity and significantly improved electrochemical stability. The developed FDMA solvent fosters the formation of a stable solid electrolyte interphase (SEI) through interface reactions with Li metal, effectively mitigating side reactions and dendrite growth on the Li metal electrode. Consequently, the Li||Li symmetric cells and Li||LiFePO 4 cells demonstrate excellent cycling performance, even under limited Li (20 µm thick) supply and high‐loading cathodes (>10 mg cm −2 , capacity >1 mAh cm −2 ) conditions. The stable Li||LiCoO 2 cells operation with a cutoff voltage of 4.48 V indicates the high‐voltage stability of the developed SPE. This study offers valuable insights into the development of advanced VDF‐based SPEs for enhanced lithium metal battery performance and longevity.