Electrolyte Solvation Chemistry for the Solution of High-Donor-Number Solvent for Stable Li-S Batteries.

Passivation of the sulfur electrode by insulating lithium sulfide (Li 2 S) restricts the reversibility and sulfur utilization of lithium-sulfur (Li-S) batteries. Although electrolytes with high donor number (DN) solvents induce tri-sulfur radical intermediate thus 3D nucleation of Li 2 S with fast kinetics can be achieved, their catastrophic reactivities with Li metal hinder practical applications. Here, the use of high DN solvent as an additive instead of as co-solvent to solve their incompatibility between cathode and anode is proposed, by adopting N-methyl-2-pyrrolidone (NMP) as a proof-of-concept. Such a strategy is accomplished by the unique solvation structure of the NMP added electrolyte, where the preference of NMP-Li + coordination squeezes out partial 1,2-dimethoxyethane (DME) molecules while enriching 1,3-dioxolane (DOL) molecules in the first solvation sheath of Li + ions. It affords the robust SEI on Li metal from corrosion either by NMP or the dissolved polysulfides. Spectral analyses (Raman and UV-vis) also verify that the coordinated NMP additive preserves its S 3 •- radicals stabilization ability as it does as a co-solvent, which effectively improves the sulfur conversion kinetics and reversibility. This approach enables competitive capacity retention and a stable cycling performance of 340 cycles, which is one of the longest lifespans known for the high DN solvent involved Li-S batteries.