Linear ether-based highly concentrated electrolytes for Li–sulfur batteries

Abstract

Li–S batteries have attracted attention as next-generation rechargeable batteries owing to their high theoretical capacity and cost-effectiveness. Sparingly solvating electrolytes hold promise because they suppress the dissolution and shuttling of polysulfide intermediates to increase the coulombic efficiency and extend the cycle life. This study investigated the solubility of polysulfide (Li₂S₈) in a range of liquid electrolytes, including organic electrolytes, highly concentrated electrolytes, and ionic liquids. The Li₂S₈ solubility was well correlated with the donor number (DN_NMR), estimated via ²³Na-NMR, and was lower than 100 mM_(elemental sulfur) in electrolytes with DN_NMR < 14, regardless of the type of electrolyte. Highly concentrated electrolytes comprising lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and linear chain dialkyl ethers such as methyl propyl ether (MPE), n-butyl methyl ether (BME), and ethyl propyl ether (EPE) were studied as sparingly solvating electrolytes for Li–S batteries. Monomethyl ethers, such as BME, showed more pronounced Li-ion coordination and higher ionic conductivity, whereas the steric hindrance of the longer alkyl chains in EPE lowered the solvation number, enhanced ion association, and lowered the ionic conductivity despite the solvents having similar dielectric constants. The charge–discharge rate capabilities of Li–S cells with dialkyl ether-based electrolytes were more impressive than those of cells with a localized high-concentration electrolyte using sulfolane (SL) and hydrofluoroether (HFE), [Li(SL)₂][TFSA]-2HFE. The higher rate performance was attributed to the superior Li-ion transport properties of the dialkyl ether-based electrolytes. A pouch-type cell using lightweight [Li(BME)₃][TFSA] demonstrated an energy density exceeding 300 W h kg⁻¹ under lean electrolyte conditions.