Twinborn TiO ₂ –TiN heterostructures enable smooth trapping–diffusion–conversion of polysulfides and produce ultralong life lithium–sulfur batteries.

Lithium–sulfur (Li–S) battery has emerged as one of the most promising next‐generation energy‐storage systems. However, the shuttle effect greatly reduces the battery cycle life and sulfur utilization, which is great deterrent to its practical use. This paper reviews the tremendous efforts that are made to find a remedy for this problem, mostly through physical or chemical confinement of the lithium polysulfides (LiPSs). Intrinsically, this “confinement” has a relatively limited effect on improving the battery performance because in most cases, the LiPSs are “passively” blocked and cannot be reused. Thus, this strategy becomes less effective with a high sulfur loading and ultralong cycling. A more “positive” method that not only traps but also increases the subsequent conversion of LiPSs back to lithium sulfides is urgently needed to fundamentally solve the shuttle effect. Here, recent advances on catalytic effects in increasing the rate of conversion of soluble long‐chain LiPSs to insoluble short‐chain Li₂S₂/Li₂S, and vice versa, are reviewed, and the roles of noble metals, metal oxides, metal sulfides, metal nitrides, and some metal‐free materials in this process are highlighted. Challenges and potential solutions for the design of catalytic cathodes and interlayers in Li–S battery are discussed in detail.