A PVDF‐Based Suspension Carbonate Electrolyte Drives Solvation‐Sheath Regulation for Stable Lithium‐Metal Batteries

Lithium‐metal batteries (LMBs) are promising candidates for next‐generation high‐energy‐density energy storage systems, but their practical application is limited by unstable Li‐metal interfaces and poor compatibility of conventional carbonate electrolytes with high‐voltage cathodes. Here, we report a poly(vinylidene fluoride) (PVDF)‐based suspension carbonate electrolyte as an effective electrolyte‐modification strategy, which improves the electrochemical stability of LMBs by enabling more uniform Li deposition and better oxidative stability. Molecular dynamics simulations combined with spectroscopic analyses reveal that fluorine‐rich PVDF particle/electrolyte interfaces locally regulate Li + coordination by weakening solvent‐dominated solvation and enhancing anion participation around PVDF particles, thereby increasing contact ion pairs and aggregates. This promotes the formation of a gradient interphase with a fluorinated/organic‐rich outer region and an inorganic inner region, while the intrinsically higher oxidation resistance of PVDF helps suppress parasitic reactions under high‐voltage conditions. As a result, the suspension electrolyte delivers a Li + transference number of 0.611, an oxidative stability window up to 4.7 V, and stable Li plating/stripping for over 2500 h in symmetric cells, while also improving the cycling stability and rate capability of Li||LiFePO 4 and Li||NCM811 cells. This work provides a practical strategy for interfacial stabilization in carbonate electrolytes.