Direct Intermediate Regulation Enabled by Sulfur Containers in Working Lithium–Sulfur Batteries

Abstract Polysulfide intermediates (PSs), the liquid‐phase species of active materials in lithium–sulfur (Li‐S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high‐energy‐density Li‐S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide‐polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid‐species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li‐S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li‐S batteries and multi‐phase electrochemical systems.