Temperature-dependent interphase formation and Li⁺ transport in lithium metal batteries

High-performance Li-ion/metal batteries working at a low temperature (i.e., <-20 °C) are desired but hindered by the sluggish kinetics associated with Li⁺ transport and charge transfer. Herein, the temperature-dependent Li⁺ behavior during Li plating is profiled by various characterization techniques, suggesting that Li⁺ diffusion through the solid electrolyte interface (SEI) layer is the key rate-determining step. Lowering the temperature not only slows down Li⁺ transport, but also alters the thermodynamic reaction of electrolyte decomposition, resulting in different reaction pathways and forming an SEI layer consisting of intermediate products rich in organic species. Such an SEI layer is metastable and unsuitable for efficient Li⁺ transport. By tuning the solvation structure of the electrolyte with a lower lowest unoccupied molecular orbital (LUMO) energy level and polar groups, such as fluorinated electrolytes like 1 mol L^-1 lithium bis(fluorosulfonyl)imide (LiFSI) in methyl trifluoroacetate (MTFA): fluoroethylene carbonate (FEC) (8:2, weight ratio), an inorganic-rich SEI layer more readily forms, which exhibits enhanced tolerance to a change of working temperature (thermodynamics) and improved Li⁺ transport (kinetics). Our findings uncover the kinetic bottleneck for Li⁺ transport at low temperature and provide directions to enhance the reaction kinetics/thermodynamics and low-temperature performance by constructing inorganic-rich interphases.