Size Effect for Inhibiting Polysulfides Shuttle in Lithium‐Sulfur Batteries

Abstract It is undeniable that the dissolution of polysulfides is beneficial in speeding up the conversion rate of sulfur in electrochemical reactions. But it also brings the bothersome “shuttle effect”. Therefore, if polysulfides can be retained on the cathode side, the efficient utilization of the polysulfides can be guaranteed to achieve the excellent performance of lithium‐sulfur batteries. Based on this idea, considerable methods have been developed to inhibit the shuttling of polysulfides. It is necessary to emphasize that no matter which method is used, the solvation mechanism, and existence forms of polysulfides are essential to analyze. Especially, it is important to clarify the sizes of different forms of polysulfides when using the size effect to inhibit the shuttling of polysulfides. In this review, a comprehensive summary and in‐depth discussion of the solvation mechanism, the existing forms of polysulfides, and the influencing factors affecting polysulfides species are presented. Meanwhile, the size of diverse polysulfide species is sorted out for the first time. Depending on the size of polysulfides, tactics of using size effect in cathode, separator, and interlayer parts are elaborated. Finally, a design idea of materials pore size is proposed to satisfy the use of size effect to inhibit polysulfides shuttle.