Modulating Bond Interactions and Interface Microenvironments between Polysulfide and Catalysts toward Advanced Metal–Sulfur Batteries

Abstract Advanced metal–sulfur batteries (MSBs) are regarded as promising next‐generation energy storage devices. Recently, engineering polysulfide redox catalysts (PSRCs) to stabilize and catalytically convert polysulfide intermediates is proposed as an effective strategy to address the grand challenge of “shuttle effects” in the cathode. Therefore, modulating the bond interactions and interface microenvironments and disclosing the structure–performance correlations between polysulfide and catalysts are essential to guide the future cathode design in MSBs. Herein, from a multidisciplinary view, the most recent process in the reaction principles, in situ characterizations, bond interaction modulation, and interface microenvironment optimization of polysulfide redox catalysts, is comprehensively summarized. Especially, unique insights are provided into the strategies for tailoring the bond interactions of PSRCs, such as heteroatom doping, vacancy engineering, heterostructure, coordination structure arrangements, and crystal phase modulation. Furthermore, the importance of interface microenvironments and substrate effects in different PSRCs are exposed, and a detailed comparison is given to unveil the critical parameters for their future developments. Finally, the critical design principles on electrode microenvironments for advanced MSBs are also proposed to stimulate the practically widespread utilization of PSRCs‐equipped cathodes in MSBs. Overall, this review provides cutting‐edge guidance for future developments in high‐energy‐density and long‐life MSBs.