Advanced Electrolyte Additives for Enhanced Homogeneous Sulfur Fixation in Lithium–Sulfur Batteries

Abstract Lithium–sulfur (Li–S) batteries are regarded as leading contenders for next‐generation energy storage owing to their exceptional theoretical energy density. However, severe sulfur electrode depletion causes rapid capacity fading and compromised cycling stability. Electrolyte engineering effectively enables homogeneous sulfur fixation, improving battery performance. The study investigates the mechanisms behind these homogeneous reactions, focusing on sulfur fixation processes. Sulfur fixation is explored through multiple perspectives, including the inhibition of polysulfide shuttling, mitigation of electrode passivation, and the combined application of both strategies. Regarding polysulfide shuttling inhibition, three distinct mechanisms for sulfur fixation are identified: 1) chemisorption‐based sulfur fixation, involving the formation of chemical bonds with polysulfides; 2) redox‐mediated sulfur fixation, which accelerates the kinetics of sulfur species; and 3) hybrid sulfur fixation, which combines elements of both approaches. Furthermore, the review analyzes current methods for homogeneous sulfur fixation, focusing on electrolyte designs that enable homogeneous sulfur fixation under limited conditions. It provides insights to optimize electrolytes, advancing Li–S battery performance and commercialization.