Solvation-Protection-Enabled High-Voltage Electrolyte for Lithium Metal Batteries

Abstract To facilitate the practical application of lithium metal batteries (LMBs), stable interfaces between the electrolyte and the lithium metal must be achieved. Herein, we introduce a solvation protection strategy for designing a functional electrolyte for high-voltage LMBs. Fluoroethylene carbonate (FEC) was introduced as a solvation protection solvent for the difluoroethylene carbonate (DFEC)/trifluoroethyl methyl carbonate (FEMC) electrolyte system to enable the cycling of lithium metal anode. The addition of FEC alters the structures of lithium complexes in solution because of its relatively high solvating power. Through the precise control of the solvation number (> 1) of fluorinated cyclic carbonate (i.e., FEC:DFEC > critical ratio), lithium complexes with Li+ solvated solely by FEMC, which decompose on the lithium surface to form detrimental by-products, can be effectively eliminated. The new ternary FEC/DFEC/FEMC system not only maintains the beneficial effect of DFEC in forming a robust solid-electrolyte interphase on the lithium anode, but also confers outstanding anodic stability provided by FEMC, while eliminating detrimental FEMC decomposition through the solvation protection effect of FEC. Clearly, this ternary system outperforms the FEC/FEMC and DFEC/FEMC binary systems in facilitating the stable cycling of LMBs.