In situ Construction of Robust Biphasic Surface Layers on Lithium Metal for Lithium–Sulfide Batteries with Long Cycle Life

Abstract Lithium–sulfur (Li‐S) batteries have potential in high energy density battery systems. However, intermediates of lithium polysulfides (LiPSs) can easily shuttle to the Li anode and react with Li metal to deplete the active materials and cause rapid failure of the battery. A facile solution pretreatment method for Li anodes involving a solution of metal fluorides/dimethylsulfoxide was developed to construct robust biphasic surface layers (BSLs) in situ. The BSLs consist of lithiophilic alloy (Li x M) and LiF phases on Li metal, which inhibit the shuttle effect and increase the cycle life of Li‐S batteries. The BSLs allow Li + transport and they inhibit dendrite growth and shield the Li anodes from corrosive reaction with LiPSs. Li‐S batteries containing BSLs‐Li anodes demonstrate excellent cycling over 1000 cycles at 1 C and simultaneously maintain a high coulombic efficiency of 98.2 %. Based on our experimental and theoretical results, we propose a strategy for inhibition of the shuttle effect that produces high stability Li‐S batteries.