Stable LiF‐Rich Electrode–Electrolyte Interface toward High‐Voltage and High‐Energy‐Density Lithium Metal Solid Batteries

Abstract Lithium‐rich layered oxide (LRLO) materials have attracted significant attention due to their high specific capacity, low cost, and environmental friendliness. However, owing to its unique capacity activation mechanism, the release of lattice oxygen during the first charge process leads to a series of problems, such as severe voltage decay, poor cycle stability, and poor rate performance. Herein, a fluorinated quasi‐solid‐state electrolyte (QSSE) via a simple thermal polymerization method toward lithium metal batteries with LRLO materials is reported. The well‐designed QSSE exhibits an ionic conductivity of 6.4 × 10 −4 S cm −1 at 30 °C and a wide electrochemical stable window up to 5.6 V. Most importantly, XPS spectra demonstrate the generation of a LiF‐rich electrode–electrolyte interface (EEI), where the in situ generated LiF provides strong protection against the structural degradation of LRLO materials and directs the uniform plating/stripping behaviors of lithium‐ions to inhibit the formation of lithium dendrites. As a result, LRLO/QSSE/Li batteries exhibit excellent rate performance and demonstrate a large initial capacity for 209.7 mA h g −1 with a capacity retention of 80.8% after 200 cycles at 0.5C. This work provides a new insight for the LiF‐rich EEI design of safe, high‐performance quasi‐solid‐state lithium metal batteries.