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The electrolyte plays a vital role for the performance of rechargeable lithium batteries with a Li metal anode as well as Li-ion batteries. A better understanding of the elementary processes involved in the formation of the electrolyte/electrode interface and charge transfer kinetics in relation to solvent, salt, additive, and electrode material is crucial to the further optimization of Li and Li-ion batteries. This issue will focus on both the fundamental and applied aspects of the electrolyte for Li and Li-ion batteries. Topics include theoretical and experimental studies of structure/property relationships of electrolytes; development of new salts, solvents and additives; development of electrolytes for 5 V Li and Li-ion batteries; studies and approaches leading to the understanding of electrode/electrolyte interfacial phenomena and the charge transfer processes; electrolytes with enhanced non-flammability; electrolytes for wide temperature range operations; and cell performance improvement with respect to that of electrolyte materials.