Physicochemical and electrochemical properties of lithium trifluoromethanesulfonate solutions in sulfolane-1.3-dioxolane mixtures

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Abstract

The physicochemical properties (specific ion conductivity, viscosity, and density) of 1.0M solutions of LiSO3CF3 in sulfolane – 1.3-dioxolane mixtures in the temperature range of 30–50°C are studied. The specific ion conductivity isotherms is shown to pass through their maximum at a 1.3-dioxolane content of about 60 mol % (1.75×10–3 Ω–1 cm–1, 30°C). It is found that the viscosity and corrected (for viscosity) conductivity of the studied solutions decrease as the 1.3-dioxolane content increases and the temperature grows. It is concluded that the activation energies of the conductivity and viscous flow, as well as their ratio, decrease as the 1.3-dioxolane content increases. Self-diffusion coefficients of all components of the studied electrolyte solutions are estimated by NMR spectroscopy, and lithium cation transport numbers are calculated. The transport number of lithium cation is found to vary nonlinearly depending on the solution composition, viz. the maximum value (0.56) is reached when the ratio of sulfolane:1.3-dioxolane ≈ 2:3, which correlates with the position of the maximum on the conductivity isotherm. The melting points of 1.0M LiSO3CF3 solutions in mixtures of sulfolane with 1.3-dioxolane are shown to decrease as the content of the latter increases. It is noted that when the content of 1.3-dioxolane is more than 50 mol %, electrolyte solutions are in the liquid phase state at temperatures below –70°С.

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About the authors

L. V. Sheina

Ufa Institute of Chemistry of the Ufa Federal Research Center, Russian Academy of Sciences

Author for correspondence.
Email: sheina.l.v@gmail.com
Russian Federation, Ufa

E. V. Karaseva

Ufa Institute of Chemistry of the Ufa Federal Research Center, Russian Academy of Sciences

Email: karaseva@anrb.ru
Russian Federation, Ufa

A. N. Lobov

Ufa Institute of Chemistry of the Ufa Federal Research Center, Russian Academy of Sciences

Email: sheina.l.v@gmail.com
Russian Federation, Ufa

V. S. Kolosnitsyn

Ufa Institute of Chemistry of the Ufa Federal Research Center, Russian Academy of Sciences

Email: sheina.l.v@gmail.com
Russian Federation, Ufa

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3. Fig. 1. Isotherms of specific electrical conductivity (a), dynamic viscosity (b), density (c) and corrected electrical conductivity (d) of 1.0 M LiSO₃CF₃ solutions in SL:DOL mixtures. Temperature (±0.1°C) is indicated in the legends. Measurement errors of physicochemical quantities did not exceed 0.5–1.0%.

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4. Fig. 2. Deviations in viscosity and excess molar volume of SL:DOL mixtures (according to [19]) (a) and deviations in viscosity, specific and corrected electrical conductivity of 1.0 M LiSO₃CF₃ solutions in SL:DOL mixtures (b).

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5. Fig. 3. Change in the chemical shift (δ) of ⁷Li and deviation of the chemical shift (Δδ) (a), dependences of the specific electrical conductivity and transport number of the lithium cation (b) in 1.0 M LiSO₃CF₃ solutions in SL:DOL mixtures on the composition.

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6. Fig. 4. Relative diffusion coefficients of lithium cation in 1.0 M LiSO₃CF₃ solutions in SL:DOL mixtures.

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7. Fig. 5. DSC heating and cooling curves of 1.0 M LiSO₃CF₃ solutions in sulfolane–1.3-dioxolane (DOL) mixtures (mol %).

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8. Fig. 6. Discharge and charge dependences of the first cycle (left), change in discharge capacity and Coulomb cycling efficiency (right) of the LSC with 1.0 M LiCF₃SO₃ solutions in sulfolane (SL) and in a mixture of sulfolane (42 mol.%):1.3-dioxolane (58 mol.%) (SL:DOL).

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