Characteristics of Lithium Ions and Superoxide Anions in EMI-TFSI and Dimethyl Sulfoxide
S Jung and FF Canova and K Akagi, JOURNAL OF PHYSICAL CHEMISTRY A, 120, 364-371 (2016).
To clarify the microscopic effects of solvents on the formation of the Li+-O-2(-) process of a Li-O-2 battery, we studied the kinetics and thermodynamics of these ions in dimethyl sulfoxide (DMSO) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide (EMI- TFSI) using classical molecular dynamics simulation. The force field for ions solvents interactions was parametrized by force matching first- principles calculations. Despite the solvation energies of the ions are similar in both solvents, their mobility is much higher in DMSO. The free-energy profiles also confirm that the formation and decomposition rates of Li+-O-2(-) pairs are greater in DMSO than in EMI-TFSI. Our atomistic simulations point out that the strong structuring of EMI-TFSI around the ions is responsible for these differences, and it explains why the LiO2 clusters formed in DMSO during the battery discharge are larger than those in EMI-TFSI. Understanding the origin of such properties is crucial to aid the optimization of electrolytes for Li-O-2 batteries.
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