Synergy of Weakly Solvated Electrolyte and LiF-Reinforced Interphase Enables Long-Term Operation of Li-Metal Batteries at Low Temperatures

Hindered by the high diffusion energy barrier of Li + in graphite anode layers, the low-temperature application of traditional Li-ion batteries is limited. Lithium metal without intercalation and with excellent specific capacity is expected to support battery operation at low temperatures. However, due to the low conductivity, high freezing point, and strong solvation energy of traditional carbonate electrolytes, the application of lithium–metal batteries at low temperatures remains challenged. In this paper, an all-ester-based ternary solvent electrolyte based on fluorinated carbonate and methyl acetate is developed to improve the cyclic efficiency of the Li-metal anode at subzero temperatures. Methyl acetate, with low viscosity and low freezing point, endows Li + with efficient transfer in the bulk phase at low temperatures. Fluorinated cosolvent regulates the solvation structure, thereby facilitating Li + desolvation while forming a LiF-rich solid electrolyte interphase. The electrolyte exhibits good compatibility with the Li-metal anode, as confirmed by the significantly reduced kinetic barrier of Li + diffusion at the interface. The theoretical calculations suggest that anions occupy the dominant positions within the inner solvation sheath. The in situ/ex situ characterizations provide straightforward evidence of a dendrite-free Li-metal electrode during cycling. As a result, the symmetric Li||Li cell is able to cycle stably for thousands of hours at current densities of 0.5 mA cm –2 and 1 mAh cm –2 . When paired with a LiFePO 4 cathode, the battery at 0.2 C (1 C = 170 mA g –1 ) has a capacity retention of 95.4% after 200 cycles at −15 °C and 92.6% after 100 cycles at −20 °C, respectively.