High Performance Low‐Temperature Lithium Metal Batteries Enabled by Tailored Electrolyte Solvation Structure

Abstract The electrochemical performances of lithium metal batteries are determined by the kinetics of interfacial de‐solvation and ion transport, especially at low‐temperature environments. Here, a novel electrolyte that easily de‐solvated and conducive to interfacial film formation is designed for low‐temperature lithium metal batteries. A fluorinated carboxylic ester, diethyl fluoromalonate (DEFM), and a fluorinated carbonate, fluoroethylene carbonate (FEC) are used as solvents, while high concentrated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is served as the solute. Through tailoring the electrolyte formulation, the lithium ions in the high concentrated fluorinated carboxylic ester electrolyte are mainly combined with anions, which weakens the bonding strength of lithium ions and solvent molecules in the solvation structure, beneficial to the de‐solvation process at low temperature. The fluorinated carboxylic ester (FCE) electrolyte enables the LiFePO 4 (LFP) | Li half‐cell achieves a high capacity of 91.9 mAh g −1 at −30 °C, with high F content in the interface. With optimized de‐solvation kinetics, the LFP | Li full cell remains over 100 mAh g −1 at 0 °C after cycling 100 cycles. Building new solvents with outstanding low‐temperature properties and weaker solvation to match with Li metal anode, this work brings new possibilities of realizing high energy density and low temperature energy storage batteries.