Lithium-ion batteries (LIBs) are the predominant power source for portable electronic devices, and in recent years, their use has extended to higher-energy and larger devices. However, to satisfy the stringent requirements of safety and energy density, further material advancements are required. Due to the inherent flammability and incompatibility of organic solvent-based liquid electrolytes with materials utilized in high energy devices, it is necessary to transition to alternative conductive mediums. The focus is shifting from molecular materials to a class of materials based on ions, including ionic liquids (ILs) and their derivatives such as zwitterionic ILs, polymerized ILs, and solvated ILs, which possess high levels of safety, stability, compatibility, and the ability to rationally design ILs for specific applications. Ion design is crucial to achieve superior control of electrode/electrolyte interphases (EEIs) both on anode and cathode surfaces to realize safer and higher-energy lithium-metal batteries (LMBs). This review summarizes the different uses of ILs in electrolytes (both liquid and solids) for LMBs, reporting the most promising results obtained during the last years and highlighting their role in the formation of suitable EEIs. Furthermore, a discussion on the use of deep-eutectic solvents is also provided, which is a class of material with similar properties to ILs and an important alternative from the viewpoint of sustainability. Lastly, future prospects for the optimization of IL-based electrolytes are summarized, ranging from the functional design of ionic structures to the realization of nanophases with specific features.
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