Ionic liquids (ILs) are liquids consisting entirely of ions and can be further defined as molten salts having melting points lower than 100 °C. One of the most important research areas for IL utilization is undoubtedly their energy application, especially for energy storage and conversion materials and devices, because there is a continuously increasing demand for clean and sustainable energy. In this article, various application of ILs are reviewed by focusing on their use as electrolyte materials for Li/Na ion batteries, Li-sulfur batteries, Li-oxygen batteries, and nonhumidified fuel cells and as carbon precursors for electrode catalysts of fuel cells and electrode materials for batteries and supercapacitors. Due to their characteristic properties such as nonvolatility, high thermal stability, and high ionic conductivity, ILs appear to meet the rigorous demands/criteria of these various applications. However, for further development, specific applications for which these characteristic properties become unique (i.e., not easily achieved by other materials) must be explored. Thus, through strong demands for research and consideration of ILs unique properties, we will be able to identify indispensable applications for ILs.

The oxidative stability of glyme molecules is enhanced by the complex formation with alkali metal cations. Clear liquid can be obtained by simply mixing glyme (triglyme or tetraglyme) with lithium bis(trifluoromethylsulfonyl)amide (Li[TFSA]) in a molar ratio of 1:1. The equimolar complex [Li(triglyme or tetraglyme)(1)][TFSA] maintains a stable liquid state over a wide temperature range and can be regarded as a room-temperature ionic liquid consisting of a [Li(glyme)(1)](+) complex cation and a [TFSA](-) anion, exhibiting high self-dissociativity (ionicity) at room temperature. The electrochemical oxidation of [Li(glyme)(1)][TFSA] takes place at the electrode potential of ~5 V vs Li/Li(+), while the oxidation of solutions containing excess glyme molecules ([Li(glyme)(x)][TFSA], x > 1) occurs at around 4 V vs Li/Li(+). This enhancement of oxidative stability is due to the donation of lone pairs of ether oxygen atoms to the Li(+) cation, resulting in the highest occupied molecular orbital (HOMO) energy level lowering of a glyme molecule, which is confirmed by ab initio molecular orbital calculations. The solvation state of a Li(+) cation and ion conduction mechanism in the [Li(glyme)(x)][TFSA] solutions is elucidated by means of nuclear magnetic resonance (NMR) and electrochemical methods. The experimental results strongly suggest that Li(+) cation conduction in the equimolar complex takes place by the migration of [Li(glyme)(1)](+) cations, whereas the ligand exchange mechanism is overlapped when interfacial electrochemical reactions of [Li(glyme)(1)](+) cations occur. The ligand exchange conduction mode is typically seen in a lithium battery with a configuration of [Li anode|[Li(glyme)(1)][TFSA]|LiCoO(2) cathode] when the discharge reaction of a LiCoO(2) cathode, that is, desolvation of [Li(glyme)(1)](+) and insertion of the resultant Li(+) into the cathode, occurs at the electrode-electrolyte interface. The battery can be operated for more than 200 charge-discharge cycles in the cell voltage range of 3.0-4.2 V, regardless of the use of ether-based electrolyte, because the ligand exchange rate is much faster than the electrode reaction rate.

To demonstrate a new family of ionic liquids (ILs), i.e., "solvate" ionic liquids, the properties (thermal, transport, and electrochemical properties, Lewis basicity, and ionicity) of equimolar molten mixtures of glymes (triglyme (G3) and tetraglyme (G4)) and nine different lithium salts (LiX) were investigated. By exploring the anion-dependent properties and comparing them with the reported data on common aprotic ILs, two different classes of liquid regimes, i.e., ordinary concentrated solutions and "solvate" ILs, were found in the glyme-Li salt equimolar mixtures ([Li(glyme)]X) depending on the anionic structures. The class a given [Li(glyme)]X belonged to was governed by competitive interactions between the glymes and Li cations and between the counteranions (X) and Li cations. [Li(glyme)]X with weakly Lewis basic anions can form long-lived [Li(glyme)](+) complex cations. Thus, they behaved as typical ionic liquids. The lithium "solvate" ILs based on [Li(glyme)]X have many desirable properties for lithium-conducting electrolytes, including high ionicity, a high lithium transference number, high Li cation concentration, and high oxidative stability, in addition to the common properties of ionic liquids. The concept of "solvate" ionic liquids can be utilized in an unlimited number of combinations of other metal salts and ligands, and will thus open a new field of research on ionic liquids.

Innovation in the design of electrolyte materials is crucial for realizing next-generation electrochemical energy storage devices such as Li–S batteries. The theoretical capacity of the S cathode is 10 times higher than that of conventional cathode materials used in current Li–ion batteries. However, Li–S batteries suffer from the dissolution of lithium polysulfides, which are formed by the redox reaction at the S cathode. Herein, we present simple solvate ionic liquids, glyme–Li salt molten complexes, as excellent electrolyte candidates because they greatly suppress the dissolution of lithium polysulfides. The molten complexes do not readily dissolve other ionic solutes, which leads to the stable operation of the Li–S battery over more than 400 cycles with discharge capacities higher than 700 mAh g-sulfur−1 and with coulombic efficiencies higher than 98% throughout the cycles. Such high performance has not been realized to the best of our knowledge. Furthermore, the addition of a nonflammable fluorinated solvent, which does not break the solvate structure of the glyme–Li salt molten complexes, greatly enhances the power density of the Li–S battery. The strategic design of electrolyte properties provides opportunities for the development of new electrochemical devices with many different electrode materials.