Impact of fluorination on Li+ solvation and dynamics in ionic liquid-hydrofluoroether locally concentrated electrolytes

The thermal, physical, structural, and transport properties of ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide [PYR14][TFSI] and Li-salts of lithium (nonafluorobutane)(trifluoromethanesulfonyl)imide [Li][IM14] and [Li][TFSI] (0 ≤ xLi ≤ 0.3), with addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) (0 ≤ xTTE ≤ 0.45) were studied. While [IM14] increases glass transition, TTE improves conductivity over a wider liquidus range. Li+ is solvated primarily by [TFSI] with some contribution by [IM14]. However, both 7Li- 19F HOESY NMR and spatial distribution functions (SDFs) derived from molecular dynamics (MD) indicate short contacts between the fluorines of TTE and Li+. This is a result of tighter anion-solvated Li+ without aggregation of the Li+ solvates, consistent with Raman measurements, thus confirming the existence of fluorous domains in the bulk which leads to improved fluidity and a Li+ diffusivity of 1.26 × 10−12 m2/s at 0 °C (xLi = 0.20) with a Li+ transference of 0.16. Improved transport properties translated to a higher capacity of the TTE/IL electrolyte in a Li||LiFePO4 half-cell with 95mAh/g at 0.1C, compared to the IL electrolyte without TTE (60 mAh/g). This study demonstrates the tunability of solvation and transport properties in IL electrolytes by asymmetric fluorinated anions and hydrofluoroether co-solvents for low temperature Li-ion batteries.