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A Comparative Study on the Thermophysical Properties for Two Bis[(trifluoromethyl)sulfonyl]imide-Based Ionic Liquids Containing the Trimethyl-Sulfonium or the Trimethyl-Ammonium Cation in Molecular Solvents B

Couadou, Erwan, Jacquemin, Johan, Galiano, Hervé, Hardacre, Christopher, Anouti, Mérièm
The Journal of physical chemistry 2013 v.117 no.5 pp. 1389-1402
acetonitrile, ambient temperature, cations, data collection, electrolytes, equations, ionic liquids, melting, models, propylene, solubility, thermal properties, viscosity
Herein, we present a comparative study of the thermophysical properties of two homologous ionic liquids, namely, trimethyl-sulfonium bis[(trifluoromethyl)sulfonyl]imide, [S₁₁₁][TFSI], and trimethyl-ammonium bis[(trifluoromethyl)sulfonyl]imide, [HN₁₁₁][TFSI], and their mixtures with propylene carbonate, acetonitrile, or gamma butyrolactone as a function of temperature and composition. The influence of solvent addition on the viscosity, conductivity, and thermal properties of IL solutions was studied as a function of the solvent mole fraction from the maximum solubility of IL, xₛ, in each solvent to the pure solvent. In this case, xₛ is the composition corresponding to the maximum salt solubility in each liquid solvent at a given temperature from 258.15 to 353.15 K. The effect of temperature on the transport properties of each binary mixture was then investigated by fitting the experimental data using Arrhenius’ law and the Vogel–Tamman–Fulcher (VTF) equation. The experimental data shows that the residual conductivity at low temperature, e.g., 263.15 K, of each binary mixture is exceptionally high. For example, conductivity values up to 35 and 42 mS·cm–¹ were observed in the case of the [S₁₁₁][TFSI] + ACN and [HN₁₁₁][TFSI] + ACN binary mixtures, respectively. Subsequently, a theoretical approach based on the conductivity and on the viscosity of electrolytes was formulated by treating the migration of ions as a dynamical process governed by ion–ion and solvent–ion interactions. Within this model, viscosity data sets were first analyzed using the Jones–Dole equation. Using this theoretical approach, excellent agreement was obtained between the experimental and calculated conductivities for the binary mixtures investigated at 298.15 K as a function of the composition up to the maximum solubility of the IL. Finally, the thermal characterization of the IL solutions, using DSC measurements, showed a number of features corresponding to different solid–solid phase transitions, TS–S, with extremely low melting entropies, indicating a strong organizational structure by easy rotation of methyl group. These ILs can be classified as plastic crystal materials and are promising as ambient-temperature solid electrolytes.