There is a critical need to evaluate lithium-sulfur (Li-S) batteries with practically relevant high sulfur loadings and minimal electrolyte. Under such conditions, the concentration of soluble polysulfide intermediates in the electrolyte drastically increases, which can alter the fundamental nature of the solution-mediated discharge and thereby the total sulfur utilization. In this work, we present an investigation into various high donor number (DN) electrolytes that allow for increased polysulfide dissolution, and demonstrate how this property may in fact be necessary for increasing sulfur utilization at low electrolyte and high loading conditions. The solvents dimethylacetamide, dimethyl sulfoxide, and 1-methylimidazole are holistically evaluated against dimethoxyethane as electrolyte co-solvents in Li-S cells, and they are used to investigate chemical and electrochemical properties of polysulfide species at both dilute and practically relevant conditions. The nature of speciation exhibited by lithium polysulfides is found to vary significantly between these concentrations, particularly in regards to the S₃ ^•- species. Furthermore, the extent of the instability in conventional electrolyte solvents and high DN solvents with both lithium metal and polysulfides is thoroughly investigated. These studies establish a basis for future efforts into rationally designing an optimal electrolyte for a lean electrolyte, high energy density Li-S battery.

Keywords: UV-vis spectroscopy; donor number; high concentration; lithium-sulfur batteries; polysulfide speciation.