Molecular Simulations of Phase Equilibria and Transport Properties in a Model CO2-Expanded Lithium Perchlorate Electrolyte.

Abstract

Carbon-dioxide (CO2)-expanded liquids, in which a significant mole fraction of CO2 is dissolved into an organic solvent, have been of significant interest, especially as catalytic support media. Because the CO2 mole fraction and density can be controlled over a significant range by changing the CO2 partial pressure, the transport properties of these solvents are highly tunable. Recently, these liquids have garnered interest as potential electrolyte solutions for catalytic electrochemistry; however, little is currently known about the influence of the electrolyte on CO2 expansion. In the present work, we use molecular-dynamics simulations to study diffusion and viscosity in a model lithium perchlorate electrolyte in CO2-expanded acetonitrile and demonstrate that these properties are highly dependent on the concentration of the electrolyte. Our present results indicate that the electrolyte slows down diffusion of both CO2 and MeCN, and that the slowed diffusion in the former is driven by changes in the activation entropy, whereas slowed diffusion in the latter is driven by changes in the activation energy.