Tailoring the Preformed Solid Electrolyte Interphase in Lithium Metal Batteries: Impact of Fluoroethylene Carbonate

[Image: see text] The film-forming electrolyte additive/co-solvent fluoroethylene carbonate (FEC) can play a crucial role in enabling high-energy-density lithium metal batteries (LMBs). Its beneficial impact on homogeneous and compact lithium (Li) deposition morphology leads to improved Coulombic efficiency (CE) of the resulting cell chemistry during galvanostatic cycling and consequently an extended cell lifetime. Herein, the impact of this promising additive/co-solvent on selected properties of LMBs is systematically investigated by utilizing an in-house developed lithium pretreatment method. The results reveal that as long as FEC is present in the organic carbonate-based electrolyte, a dense mosaic-like lithium morphology of Li deposits with a reduced polarization of only 20 mV combined with a prolonged cycle life is achieved. When the pretreated Li electrodes with an FEC-derived preformed SEI (pSEI) are galvanostatically cycled with the FEC-free electrolyte, the described benefits induced by the additive are not observable. These results underline that the favorable properties of the FEC-derived SEI are beneficial only if there is unreacted FEC in the electrolyte formulation left to constantly reform the interphase layer, which is especially important for anodes with high-volume changes and dynamic surfaces like lithium metal and lithiated silicon.