In Situ Construction of a LiF-Enriched Interface for Stable All-Solid-State Batteries and its Origin Revealed by Cryo-TEM

The application of solid polymer electrolytes (SPEs) is still inherently limited by the unstable lithium (Li)/electrolyte interface, despite the advantages of security, flexibility, and workability of SPEs. Herein, the Li/electrolyte interface is modified by introducing Li₂S additive to harvest stable all-solid-state lithium metal batteries (LMBs). Cryo-transmission electron microscopy (cryo-TEM) results demonstrate a mosaic interface between poly(ethylene oxide) (PEO) electrolytes and Li metal anodes, in which abundant crystalline grains of Li, Li₂O, LiOH, and Li₂CO₃ are randomly distributed. Besides, cryo-TEM visualization, combined with molecular dynamics simulations, reveals that the introduction of Li₂S accelerates the decomposition of N(CF₃SO₂)₂^? and consequently promotes the formation of abundant LiF nanocrystals in the Li/PEO interface. The generated LiF is further verified to inhibit the breakage of C? O bonds in the polymer chains and prevents the continuous interface reaction between Li and PEO. Therefore, the all-solid-state LMBs with the LiF-enriched interface exhibit improved cycling capability and stability in a cell configuration with an ultralong lifespan over 1800 h. This work is believed to open up a new avenue for rational design of high-performance all-solid-state LMBs.