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Intermediate polysulfides (Sn, where n = 2–8) play a critical role in both mechanistic understanding and performance improvement of lithium–sulfur batteries. The rational management of polysulfides is of profound significance for high‐efficiency sulfur electrochemistry. Here, the key roles of polysulfides are discussed, with regard to their status, behavior, and their correspondingimpact on the lithium–sulfur system. Two schools of thoughts for polysulfide management are proposed, their advantages and disadvantages are compared, and future developments are discussed.
Polysulfides (PS) play a vital role in lithium–sulfur batteries. The role of polysulfides is revisited with regard to their status, behavior, and critical impact on battery chemistry. Rational management of polysulfides including PS‐retain and PS‐bypass strategies are thoroughly discussed, and their future outlook is examined.