Theoretical Investigation of the Structure and Physicochemical Properties of Alkaline and Alkaline Earth Metal Perchlorate Solutions in Sulfolane.

Abstract

To assess the possibility of using solutions of perchlorates of alkali and alkaline earth metals in sulfolane as electrolytes for electrochemical energy storage devices with metal negative electrodes, the physicochemical properties of 0.5 M solutions of Me(ClO4)n (Me = Li, Na, K, Mg, and Ca) in sulfolane were simulated by the method of molecular dynamics. The density, viscosity, conductivity, self-diffusion coefficients, and transport numbers are calculated. Satisfactory agreement between the calculated and experimentally measured properties of 0.5 M solutions of LiClO4 and NaClO4 in sulfolane suggests that the calculated values of the physicochemical properties of solutions of K, Mg, and Ca perchlorates are also close to real values. The study of the structure of solvate complexes of salts of alkali and alkaline earth metals with sulfolane by quantum chemical and molecular dynamics modeling showed that the first solvate shell of metal cations consists of sulfolane molecules. Regardless of the nature of the cation, sulfolane is coordinated to the metal cation by only one oxygen atom. Based on the analysis of the calculated values of the physicochemical properties of solutions of metal perchlorates in sulfolane, it can be concluded that they can be used as electrolyte systems of electrochemical energy storage devices with negative electrodes made of alkali and alkaline earth metals.