Models of Ion Solvation Thermodynamics in Ethylene Carbonate and Propylene Carbonate.

Abstract

Ethylene carbonate (EC) and propylene carbonate (PC) are organic solvents used extensively in energy storage applications such as lithium-ion batteries and supercapacitors. Using statistical mechanical theory and computer simulations, this paper compares and contrasts the thermodynamics of ion solvation in EC and PC with the behavior observed in water. The EC and PC solvents are modeled with the AMBER (GAFF) force field. Ion-solvent interactions are treated with two point-charge models: one using an existing Lennard-Jones ion parameter set optimized for solvation in water, and the other based on high-level quantum calculations on ion-solvent dimers and fitting to a Buckingham-type potential form. The second model produces a coordination number for the Li(+) ion in closer agreement with experiment. Neither model yields consistently accurate solvation thermodynamic quantities (free energies, enthalpies, and entropies), however. The simulations and thermodynamic analysis illustrate key physical aspects of the solvation; the studies also point to necessary modifications of these simple models. In particular, the calculations show that polarization and associated dispersion forces are important and that well-optimized polarizable or quantum models are likely required to accurately reproduce condensed-phase properties of ions in these technologically important solvents.