Anchored Fluoro‐Shielded Solvation for Lithium Metal Batteries

ABSTRACT Polyvinylidene fluoride (PVDF)‐based polymer electrolytes are promising candidates for solid‐state lithium metal batteries owing to their favorable overall electrochemical properties. However, conventional PVDF‐based polymer electrolytes suffer from uneven solvation distribution, discontinuous ion‐transport pathways, and unstable electrode/electrolyte interfaces caused by residual solvents and porous PVDF frameworks. Herein, we report an anchored fluoro‐shielded solvation strategy to construct a high‐performance PVDF‐based polymer electrolyte. By integrating polyanionic anchoring sites with fluorinated shielding segments, the optimized electrolyte enables spatially distributed anion‐rich solvation pathways, homogeneous Li + transport, and robust LiF‐rich solid electrolyte interphase (SEI). The polymer electrolyte delivers a high ionic conductivity of 1.26×10 −3 S cm −1 , a Li + transference number of 0.69, an oxidative onset potential of 5.27 V, and a critical current density of 6.4 mA cm −2 . Spectroscopic and interfacial analyses reveal that the anchored fluoro‐shielded solvation structure promotes LiF‐rich SEI formation and suppresses solvent decomposition. Consequently, Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 batteries retain 80.2% capacity after 2000 cycles under high‐voltage and high‐rate conditions of 4.5 V and 5 C. This work highlights anchored fluoro‐shielded solvation as an effective molecular design principle for advanced polymer electrolytes toward practical high‐voltage and high‐rate solid‐state Li metal batteries.