An Artificial Lithium Protective Layer that Enables the Use of Acetonitrile‐Based Electrolytes in Lithium Metal Batteries

The resurgence of the lithium metal battery requires innovations in technology, including the use of non‐conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (−3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile‐based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF6 in acetonitrile. You shall not pass: An artificial protective film is formed spontaneously on lithium metal in contact with pure fluoroethylene carbonate. This artificial solid electrolyte interface prevents acetonitrile from decomposing on the lithium anode, allowing its use as a solvent for the preparation of highly conductive electrolytes for lithium metal batteries. Such treated electrodes were cycled for 700 h without any sign of parasitic reaction.