Electrolyte Engineering for High‐Energy Conversion‐Type Cathodes in Lithium Metal Batteries: Progress and Challenges

Driven by the growing demand for next‐generation high‐energy‐density energy storage systems, conversion‐type cathodes have emerged as promising candidates for lithium metal batteries (LMBs) owing to their multi‐electron redox chemistry and ultrahigh theoretical capacities. However, their practical application is hindered by sluggish kinetics, severe structural degradation and active material dissolution, which are closely associated with complex phase evolution and unstable electrode–electrolyte interfaces. Electrolyte engineering has emerged as a critical strategy to address these challenges, primarily by tailoring the Li + solvation structure to regulate interfacial reactions and reaction pathways. This review provides a comprehensive overview of recent advances in electrolyte design for conversion‐type cathodes, including conventional electrolytes, high‐concentration electrolytes (HCEs), localized HCEs (LHCEs), weakly solvating electrolytes (WSEs), additive‐engineered systems, and ionic liquid electrolytes (ILEs). Particular emphasis is placed on the correlation among Li + solvation structures, interfacial chemistry, and overall electrochemical performance. Finally, the remaining challenges and future perspectives for rational electrolyte design toward practical, high‐energy‐density conversion‐type cathodes‐based LMBs are outlined.