Evaluating the Free Energies of Solvation and Electronic Structures of Lithium‐Ion Battery Electrolytes

Adaptive biasing force molecular dynamics simulations and density functional theory calculations were performed to understand the interaction of Li⁺ with pure carbonates and ethylene carbonate (EC)‐based binary mixtures. The most favorable Li carbonate cluster configurations obtained from molecular dynamics simulations were subjected to detailed structural and thermochemistry calculations on the basis of the M06‐2X/6‐311++G(d,p) level of theory. We report the ranking of these electrolytes on the basis of the free energies of Li‐ion solvation in carbonates and EC‐based mixtures. A strong local tetrahedral order involving four carbonates around the Li⁺ was seen in the first solvation shell. Thermochemistry calculations revealed that the enthalpy of solvation and the Gibbs free energy of solvation of the Li⁺ ion with carbonates are negative and suggested the ion–carbonate complexation process to be exothermic and spontaneous. Natural bond orbital analysis indicated that Li⁺ interacts with the lone pairs of electrons on the carbonyl oxygen atom in the primary solvation sphere. These interactions lead to an increase in the carbonyl (C=O) bond lengths, as evidenced by a redshift in the vibrational frequencies ν(C=O)] and a decrease in the electron density values at the C=O bond critical points in the primary solvation sphere. Quantum theory of atoms in molecules, localized molecular orbital energy decomposition analysis (LMO‐EDA), and noncovalent interaction plots revealed the electrostatic nature of the Li⁺ ion interactions with the carbonyl oxygen atoms in these complexes. On the basis of LMO‐EDA, the strongest attractive interaction in these complexes was found to be the electrostatic interaction followed by polarization, dispersion, and exchange interactions. Overall, our calculations predicted EC and a binary mixture of EC/dimethyl carbonate to be appropriate electrolytes for Li‐ion batteries, which complies with experiments and other theoretical results.