Preferential Solvation of Lithium Cations and Impacts on Oxygen Reduction in Lithium-Air Batteries.

The solvation of Li+ with 11 nonaqueous solvents commonly used as electrolytes for lithium batteries was studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li+ was determined. The Lewis acidity of the solvated Li+ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O2•- depends on the relative Lewis acidity of the solvated Li+ ion. The impact of the solvated Li+ cation on the O2 redox reaction was also investigated.