Abstract

The development of new electrolytes for lithium–sulfur (Li–S) batteries is important. Electrolytes based on 1:1 glyme:Li+ complexes can be locally destroyed to form free glyme during charge/discharge cycles. Free glyme can cause Li2Sx dissolution, which is a major factor in Li–S battery degradation. To decrease the local generation of free glyme, the glyme:Li+ electrolytes with higher proportions of Li salts are developed to control the Li2Sx dissolution into the electrolyte. The chemical solubility of Li2S8 and the charge/discharge properties of Li–S cells are investigated by varying the glyme:Li salt molar ratio. Nonequimolar (high Li salt concentration) glyme:Li salt mixture electrolytes directly suppress the Li2S8 dissolution and improve the charge/discharge properties (cycling and coulombic efficiency) of Li–S cells. The electrolyte composition can control the chemical stability of reactive intermediates at the Li2Sx electrode and provide high‐performance Li–S cells for next‐generation batteries.

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