Computational Studies of Solubilities of LiO₂and Li₂O₂in Aprotic Solvents

Knowledge of the solubilities of Li 2 O 2 and LiO 2 in aprotic solvents is important for insight into the discharge and charge processes of Li-O 2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO 2 and Li 2 O 2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular dynamics (AIMD) methods. The solvation energies from these calculations along with calculated lattice energies of Li 2 O 2 and LiO 2 were used to determine the solubility of bulk LiO 2 and Li 2 O 2 . The computed solubility of LiO 2 (1.8 × 10 −2 M) is about 15 orders higher than that of Li 2 O 2 (2.0 × 10 −17 M) due to a much less negative lattice energy of bulk LiO 2 compared to that of Li 2 O 2 . The difference in solubilities between LiO 2 and Li 2 O 2 likely will affect the nucleation and growth mechanisms and resulting morphologies of the products formed during battery discharge, influencing the performance of the battery cell. The calculated LiO 2 and Li 2 O 2 solubilities provide important information for fundamental studies of discharge and charge chemistries in Li-O 2 batteries.