Directing Fluorinated Solid Electrolyte Interphase by Solubilizing Crystal Lithium Fluoride in Aprotic Electrolyte for Lithium Metal Batteries

Abstract Lithium fluoride (LiF) facilitates robust and fast‐ion‐transport solid electrolyte interphase (SEI) in lithium metal batteries. Fluorinated solvents/salts are ubiquitously employed to introduce LiF into SEI through electrochemical decomposition, but this approach is usually at the expense of their continuous consumption. A direct approach to fluorinate SEI that employs crystal LiF is limited by its poor solubility in the current battery electrolyte formulation. Dissolving crystal LiF in high‐dielectric‐constant solvents, like ethylene carbonate (EC) is nearly neglected. Herein, the feasibility of directly fluorinating SEI by the addition of crystal LiF in aprotic electrolyte with the assistance of EC is verified, and its mechanisms in fluorination of SEI and anti‐acidification of electrolyte are explored. The dissolved LiF is encapsulated by solvent‐/salt‐derived organic skins to promote the fluorinated SEI. Meanwhile, the presence of LiF in electrolyte alters hazardous thermodynamic equilibrium, suppressing the production of acid species to mitigate electrolyte acidification and SEI degradation. Such collective benefits yield a capacity retention ratio of ≈88% after 150 cycles at a high areal capacity (4.5 mAh cm −2 ) in Li||NCM622 cells. This facile and effective fluorination of SEI contributes to an in‐depth understanding of SEI formation and rational design of well‐performing lithium metal batteries.