Electrolyte-Induced Interphase Programming for Aprotic High-Energy Lithium Metal Batteries

The increasing global demand for renewable, high-energy-density energy storage systems has revitalized interest in lithium–metal-based batteries (LMBs) as a viable alternative to conventional graphite-based Li-ion batteries. Electrolyte engineering has emerged as a promising approach to mitigate the persistent issue of Li dendrite formation, which is a critical barrier to the practical implementation of LMBs. This strategy aims to optimize the dynamic solvation structure and regulate ion transport via orchestrating the composition of the electrolyte and the distribution of constituents within the electrode–electrolyte interphase layer. This review focuses on the achievements of aprotic liquid electrolytes over the past five years, particularly in the context of LMBs with high-nickel layered oxide-based and sulfur-based cathodes, emphasizing high-concentration electrolytes and their localized variants, electrolyte additives, and novel electrolyte systems. The design principles, operating mechanisms, and performance trade-offs of leading electrolyte strategies are presented, culminating in insights and future prospects for practical LMBs.