Locking Active Li Metal through Localized Redistribution of Fluoride Enabling Stable Li‐Metal Batteries

The creation of fluorinated interphase has emerged as an effective strategy for improving Li-metal anodes for rechargeable high-energy batteries. In contrast to the introduction of fluorine-containing species through widely adopted electrolyte engineering, a Li-metal composite design is reported in which LiF can locally redistribute on the Li-metal surface in liquid electrolytes via a dissolution-reprecipitation mechanism, and enable the formation of a high-fluorine-content solid electrolyte interphase (SEI). For validation, a Li/Li₂₂ Sn₅ /LiF ternary composite is investigated, where the as-formed LiF-rich SEI locks the active Li metal from corrosive electrolyte. The Li/Li₂₂ Sn₅ /LiF anode displays an impressive average Coulombic efficiency (ACE, ≈99.2%) at 1 mA cm^-2 and 1 mAh cm^-2 in a carbonate electrolyte and a remarkable cycling life of over 1600 h at 1 mA cm^-2 and 2 mAh cm^-2 . Applied to a LiCoO₂ full cell with a high cathode areal capacity of 4.0 mAh cm^-2 , a high capacity retention of ≈91.1% is realized for 100 cycles at 0.5 C between 2.8 to 4.5 V with a low negative/positive (N/P) ratio of 2:1. This design is conceptually different from the design employing the widely used fluorine-containing electrolyte additive and provides an alternative approach to realize reliable Li-metal batteries.