Correlating Li + -Solvation Structure and its Electrochemical Reaction Kinetics with Sulfur in Subnano Confinement.

Combining theoretical and experimental approaches, we investigate the solvation properties of Li ⁺ ions in a series of ether solvents (dimethoxyethane, diglyme, triglyme, tetraglyme, and 15-crown-5) and their subsequent effects on the solid-state lithium-sulfur reactions in subnano confinement. The ab initio and classical molecular dynamics (MD) simulations predict Li ⁺ ion solvation structures within ether solvents in excellent agreement with experimental evidence from electrospray ionization-mass spectroscopy. An excellent correlation is also established between the Li ⁺ -solvation binding energies from the ab initio MD simulations and the lithiation overpotentials obtained from galvanostatic intermittent titration techniques (GITT). These findings convincingly indicate that a stronger solvation binding energy imposes a higher lithiation overpotential of sulfur in subnano confinement. The mechanistic understanding achieved at the electronic and atomistic level of how Li ⁺ -solvation dictates its electrochemical reactions with sulfur in subnano confinement provides invaluable guidance in designing future electrolytes and electrodes for Li-sulfur chemistry.