Amphiphobic Solvent‐Mediated Relay Push‐Escape Strategy for Highly Efficient Lithium‐Metal Batteries

Lithium‐metal batteries promise high‐energy‐density, wide operating temperature ranges, and fast charging. However, integrating these attributes remains a formidable challenge, as it necessitates an electrolyte that concurrently delivers high ionic conductivity, low solvation energy, low melting point, and the ability to form a stable electrode–electrolyte interphase (EEI), a feat elusive to conventional formulations. Here, we successfully address this challenge with a “relay push‐escape” strategy using amphiphobic hexafluoroisopropyl methyl ether. Its anion‐repulsive Coulombic field and steric hindrance transform conventional 1 M LiFSI‐DME electrolyte into L4DF electrolyte, triggers a novel mechanism that drives anions into the inner Li⁺ solvation sheaths, displacing DME solvents to form a contacted ion‐pair and aggregative ion‐pair‐dominated structure. The resulting L4DF electrolyte facilitates rapid Li⁺ desolvation and fosters the formation of a stable, anion‐derived LiF‐rich EEI. As a result, the L4DF electrolyte demonstrates exceptional compatibility with lithium‐metal, showing high Coulombic efficiency of 99.7%. The LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li half‐cell achieves 91.2% capacity retention after 1000 cycles and outstanding performance under 5 C fast‐charging and low‐temperature conditions. Remarkably, a 5.52 Ah pouch‐cell reaches an energy density of 502.3 Wh kg −1 while retaining 87.6% of its capacity for 260 cycles. This work paves the way for the precise design of electrolytes for advanced batteries.