Surface Gelation on Disulfide Electrocatalysts in Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are deemed as future energy storage devices due to ultrahigh theoretical energy density. Cathodic polysulfide electrocatalysts have been widely investigated to promote sluggish sulfur redox kinetics. Probing the surface structure of electrocatalysts is vital to understanding the mechanism of polysulfide electrocatalysis. In this work, we for the first time identify surface gelation on disulfide electrocatalysts. Concretely, the Lewis acid sites on disulfides trigger the ring-opening polymerization of the dioxolane solvent to generate a surface gel layer, covering disulfides and reducing the electrocatalytic activity. Accordingly, a Lewis base triethylamine (TEA) is introduced as a competitive inhibitor. Consequently, Li–S batteries with disulfide electrocatalysts and TEA afford high specific capacity and improved rate responses. This work affords new insights on the actual surface structure of electrocatalysts in Li–S batteries.