Structure, dynamics and ionic conductivities of ternary ionic liquid/lithium salt/DMSO mixtures

Abstract

In this paper we report classical Molecular Dynamics and ab initio Density Functional Theory simulations of the structure and single particle dynamics of ternary mixtures of a protic (ethylammonium nitrate, EAN) and an aprotic (1-Ethyl-3-methylimidazolium tetrafluoroborate, EMIMBF4) ionic liquid, lithium salts with common anion and a molecular cosolvent, dimethyl sulfoxide (DMSO). The coordination numbers and electrical conductivities of the different mixtures have been calculated throughout the whole concentration range, and the differences between mixtures with the protic and aprotic ionic liquids were analyzed. In both cases, the evolution of the electrical conductivity is seen to correlate well with the formation of mixed tetrahedral solvation complexes of lithium cations with ionic liquid anions and cosolvent molecules. The differences in the solvation and charge transport mechanisms in hydrogen bonded mixtures and those based in the aprotic ionic liquid are analyzed. Our conclusions indicate that the major feature behind the electrical conductivity of the ternary mixtures is the composition of the solvation shell of the metal cations in the mixtures and the rate at which anions in it are replaced by DMSO molecules