Superior long-term cycling of high-voltage lithium-ion batteries enabled by single-solvent electrolyte

Highlights: • Introduce a new single-solvent electrolyte system comprising LiFSI and TFPMS for very stable cycling of high-voltage LIBs. • Unlike α-fluorinated sulfone, LiFSI-TFPMS system at normal salt concentration is compatible with the graphite anode. • The LiFSI-TFPMS electrolyte enables the formation of a robust SEI by the sacrificial decomposition of LiFSI. • The LiFSI-TFPMS system outperformed many reported electrolytes for high-voltage lithium-ion system. A new single-solvent electrolyte system comprising lithium bis(fluorosuflonyl) imide (LiFSI) and β-fluorinated sulfone (TFPMS) was designed to enable very stable long-term cycling of high-voltage lithium-ion batteries. Compared to other fluorinated solvents such as α-fluorinated sulfone (FMES) and fluorinated carbonate (FEMC), which are prone to reduction on the graphite anode, the LiFSI-TFPMS system displayed outstanding compatibility with graphite. While regular carbonate and sulfone from the LiFSI electrolyte system are compatible with the graphite anode, their high solvating power not only induces severe corrosion on the aluminum cathode current collector at high voltage, but also renders a low aggregation level at a normal salt concentration (about 1.0 M), resulting in the formation of an unstable solid-electrolyte interphase (SEI) on the graphite anode. Owing to the low solvating power of TFPMS, the aggregation level of the LiFSI-TFPMS system is relatively high even at normal salt concentration, which not only facilitates the formation of a robust SEI by the sacrificial decomposition of LiFSI, but also suppresses the aluminum corrosion of the LiFSI electrolyte system at high voltage. Together with the high intrinsic anodic stability of TFPMS, the superior cycling performance of graphite||LiNi_0.6Co_0.2Mn_0.2O₂ cells was achieved by employing the non-flammable LiFSI-TFPMS single-solvent electrolyte system.