From molten salts to room temperature ionic liquids: Simulation studies on chloroaluminate systems

Abstract

An interaction potential including chloride anion polarization effects, constructed from first-principles calculations, is used to examine the structure and transport properties of a series of chloroaluminate melts. A particular emphasis was given to the study of the equimolar mixture of aluminium chloride with 1-ethyl-3-methylimidazolium chloride, which forms a room temperature ionic liquid EMI⁺–AlCl⁻₄. The structure yielded by the classical simulations performed within the framework of the polarizable ion model is compared to the results obtained from entirely electronic structure-based simulations: An excellent agreement between the two flavors of molecular dynamics is observed. When changing the organic cation EMI⁺ by an inorganic cation with a smaller ionic radius (Li⁺, Na⁺, K⁺), the chloroaluminate speciation becomes more complex, with the formation of Al₂Cl⁻₇ in small amounts. The calculated transport properties (diffusion coefficients, electrical conductivity and viscosity) of EMI⁺–AlCl⁻₄ are in good agreement with experimental data.