Chemical Stability of Lithium 2‑Trifluoromethyl-4,5-dicyanoimidazolide, an Electrolyte Salt for Li-Ion Cells

Lithium hexafluorophosphate (LiPF₆) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reduced on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in light of recent spectroscopic studies. We demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate, and lithium bis­(oxalato)­borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs Li/Li⁺, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode