The Catalytic Chemistry for High‐Performance Lithium‐Sulfur Batteries: A Review and Prospects

Abstract Lithium‐sulfur (Li─S) batteries offer exceptionally high theoretical energy density, making them strong candidates for next‐generation energy storage. However, their practical implementation is hindered by severe polysulfide shuttling and sluggish solid‐liquid‐solid phase transitions, which considerably diminish cycling stability and capacity retention, especially at elevated sulfur loading (≥5 mg cm ⁻² ). Recent advancements highlight the crucial importance of catalytic chemistry in overcoming these obstacles by reducing reaction energy barriers, facilitating long‐range electron transport, and overall performance. Despite progress, a deeper mechanistic understanding of catalytic chemical mediation remains lacking. This review explores catalytic chemistry processes in Li─S batteries, particularly those that promote liquid‐solid conversion and long‐range electron transport. It discusses key approaches, such as the adjustment of adsorption/desorption dynamics, the regulation of solid‐phase nucleation and breakdown energy barriers, and the facilitation of alternate polysulfide conversion routes. Additionally, recent insights from in situ characterization and computational modeling that uncover the molecular‐level mechanisms behind catalytic enhancement are highlighted. Future efforts should integrate catalytic materials with advanced electrode architectures and develop multifunctional catalysts to enable high‐loading, high‐performance Li─S batteries suitable for practical deployment.