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The sluggish kinetics of sulfur redox reactions and the potential of polysulfide shuttling pose significant challenges to the practical application of metal–sulfur batteries (MSBs). Heterostructured materials that integrate the advantages of various components serve as ideal electrocatalysts to address these issues. This review first summarizes and analyzes the engineering strategies and the proposed working principles for heterostructures. Recent advancements in the utilizations of heterostructures in sulfur hosts, separator coating layers, and interlayers are then concluded. The material designs, preparation approaches, and the crucial roles played by heterostructures are subsequently discussed, elucidating the relationship between their structural characteristics and MSB performance. Finally, the remaining challenges are identified, and the future research directions are outlined in this promising area. This work provides invaluable insights into the development of highly efficient heterostructured electrocatalysts and the regulation of sulfur conversion processes in MSBs.

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