A New Hybrid Solid/Solvating Sulfur Conversion for Energy-Dense Lithium-Sulfur Batteries

Abstract

To boost the practical energy density of lithium-sulfur batteries, replacing conventional solvating electrolytes with sparingly solvating ones has shown promise by enabling solid-state sulfur conversion and reducing electrolyte consumption. However, this approach often compromises sulfur redox kinetics. This study reports a new sulfur conversion pathway distinct from both traditional solvated and sparingly solvated mechanisms. Specifically, sulfur is converted into a mixture of solid and solvated lithium polysulfides (LPSs). Such a hybrid solid/solvating conversion pathway is achieved using a newly formulated moderately solvating electrolyte, accomplishing both lean-electrolyte operation and fast conversion kinetics for lithium-sulfur batteries. Methoxyacetonitrile (MAN) is selected as the solvent to formulate the moderately solvating electrolyte due to its high relative permittivity (21) that contributes to a high Li⁺ conductivity (11.7 mS cm⁻¹ for 1M lithium bis(trifluoromethane sulfonyl)imide in MAN) and low donor number (14.6 kcal mol⁻¹) that reduces the solubility to LPSs to 1/6 of that in mainstream solvating electrolytes. The as-formulated MAN electrolyte enables sulfur cathodes to operate at a low electrolyte-to-sulfur ratio of 2 μL mg⁻¹ and a low cathode porosity of 52%, displaying excellent prospects for boosting both gravimetric and volumetric energy density.

Keywords

high energy density / lean electrolyte / lithium-sulfur battery / methoxyacetonitrile electrolyte / moderately solvating electrolyte / solid/solvating conversion

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