Unlocking the Potential of Lithium Metal Batteries With a Sulfite‐Based Electrolyte

Abstract Lithium metal batteries (LMBs) have the potential to significantly increase the energy density of advanced batteries in the future. Nonetheless, the dendritic lithium structures and low Coulombic efficiency (CE) of LMBs currently impede their applied implementation. Herein, a sulfite‐based electrolyte (SBE/FEC), including 1.0 m lithium bis(fluorosulfonyl)imide in a blend of ethylene sulfite and diethyl sulfite, and 5 wt% fluoroethylene carbonate is proposed. SBE/FEC is a highly efficient inhibitor against the growth of lithium dendrites through the formation of robust solid electrolyte interphase (SEI) layer. Raman spectroscopy and theoretical calculation indicate that in SBE/FEC, a significant portion of FSI − exists in associated complexes, playing a vital role in the creation of LiF‐rich passivation. Besides, the sulfite solvents decompose and yield polysulfide complexes in the SEI layer. A direct correlation between the proportion of cation–anion complexes and the contact angle between electrolyte and separator is elucidated through molecular dynamics simulations. The SBE/FEC system exhibits high CEs (98.3%) with Li||Cu cells, along with a steady discharge capacity of ≈137 mA h g −1 in Li||LiFePO 4 cell. This study presents an effective approach for enhancing LMBs with sulfite‐based electrolytes, which can lead to high‐energy‐density next‐generation rechargeable batteries.