Physicochemical Properties of Lithium Bis(trifluoromethanesulfonyl)imide Solutions in Sulfolane

Abstract

Abstract A study is performed of the physicochemical properties (ionic conductivity, viscosity, and density in the 30–50°C range of temperatures) and the electrochemical and thermal stability of lithium bis(trifluoromethanesulfonyl)imide solutions in sulfolane in the 0.001–1.89 M range of concentrations. It is shown that lithium bis(trifluoromethanesulfonyl)imide solutions in sulfolane exhibit high electrochemical stability (5.75 V vs. Li/Li+) and moderate ionic conductivity (2.75 × 10−3 Ω−1 cm−1 at 30°C for a 1 M solution), which are comparable to the respective parameters of sulfolane solutions of lithium hexafluorophosphate. The structure and transport properties of sulfolane solutions of lithium bis(trifluoromethanesulfonyl)imide are determined by their concentrations. In dilute solutions, lithium bis(trifluoromethanesulfonyl)imide is weakly associated. The degree of electrolytic dissociation of LiN(SO2CF3)2 initially falls and then rises upon an increase in its concentration. The electrolytic dissociation of lithium bis(trifluoromethanesulfonyl)imide rises along with its concentration, due to the formation of ion triplets and more complex ion associates. The constant of association and limit equivalent conductivity of LiN(SO2CF3)2 in sulfolane rise along with temperature, due to a drop in the degree of self-association and the degradation of the solvent’s structure. A specific feature of sulfolane solutions of lithium bis(trifluoromethanesulfonyl)imide is their tendency to form stable supercooled solutions.