Tailored Anion‐Enriched Solvation Sheath Design Enables Wide Temperature Range Performance of Lithium Metal Batteries †

Comprehensive Summary Conventional lithium‐ion batteries that utilize high melting point ethylene carbonate (EC) solvent and graphite anodes exhibit a narrow operating temperature range, which is insufficient to meet the wide‐temperature requirements of electric vehicle power batteries. Herein, a novel electrolyte featuring an anion‐enriched solvation structure is developed by incorporating ethyl difluoroacetate (DFAE), a fluorinated solvent with wide liquid range and weak solvation capability, which enables the stable operation of lithium metal batteries (LMBs) over a broad temperature range (–50 °C to 60 °C). The anion‐enrich solvation structure facilitates rapid desolvation and enables the formation of inorganic‐dominated interphases on both the cathode and anode surfaces. NMC811||DEF||Li cells exhibit a high specific capacity of 194.7 mAh·g –1 at a 2 C rate and room temperature, retaining 77.16% capacity after 400 cycles. The pouch cell using DEF electrolyte successfully powered an LED panel at –50 °C, demonstrating practical viability. This innovative strategy provides a promising pathway for the development of next generation wide‐temperature LMBs.