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.

To develop a basic understanding of a new class of ionic liquids (ILs), "solvate" ILs, the transport properties of binary mixtures of lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) and oligoethers (tetraglyme (G4), triglyme (G3), diglyme (G2), and monoglyme (G1)) or tetrahydrofuran (THF) were studied. The self-diffusion coefficient ratio of the solvents and Li(+) ions (Dsol/DLi) was a good metric for evaluating the stability of the complex cations consisting of Li(+) and the solvent(s). When the molar ratio of Li(+) ions and solvent oxygen atoms ([O]/[Li(+)]) was adjusted to 4 or 5, Dsol/DLi always exceeded unity for THF and G1-based mixtures even at the high concentrations, indicating the presence of uncoordinating or highly exchangeable solvents. In contrast, long-lived complex cations were evidenced by a Dsol/DLi ∼ 1 for the longer G3 and G4. The binary mixtures studied were categorized into two different classes of liquids: concentrated solutions and solvate ILs, based on Dsol/DLi. Mixtures with G2 exhibited intermediate behavior and are likely the borderline dividing the two categories. The effect of chelation on the formation of solvate ILs also strongly correlated with electrolyte properties; the solvate ILs showed improved thermal and electrochemical stability. The ionicity (Λimp/ΛNMR) of [Li(glyme or THF)x][TFSA] exhibited a maximum at an [O]/[Li(+)] ratio of 4 or 5.

A series of equimolar mixtures of Li salts (LiX) and glymes (triglyme (G3) and tetraglyme (G4)), [Li(glyme)]X with different anions (X: [N(SO2C2F5)2] = [BETI]; [N(SO2CF3)2] = [TFSA]; [CF3SO3] = [OTf]; BF4; NO3), were used as electrolytes to study the anionic effects of [Li(glyme)]X on the performance of lithium–sulfur (Li–S) batteries. The dissolution of lithium polysulfides (Li2S m ), which are discharge products of elemental sulfur, was significantly suppressed in the solvate ionic liquid (IL) electrolytes, as seen in [Li(G4)][BETI] and [Li(glyme)][TFSA], wherein all of the glymes participated in the formation of the complex cation [Li(glyme)]+. It was found that NO3 anions were irreversibly reduced at the composite cathode during discharge and BF4 anions formed unexpected byproducts through a chemical reaction with the polysulfide anions. Successful charge/discharge of Li–S cell could not be performed in [Li(glyme)]X in the presence of these anions because of the undesired side reactions. The solvate IL [Li(G4)][BETI] was found to be electrochemically stable in the Li–S cell and allowed a stable operation with a capacity of 600–700 mAh·g–1 and a Coulombic efficiency of 98.5% over 100 cycles, similar to that achieved by [Li(glyme)][TFSA]. In contrast, the Li–S cell with a concentrated electrolyte solution, [Li(G3)][OTf], showed a much lower capacity and Coulombic efficiency.

Solvent−ion and ion−ion interactions have significant effects on the physicochemical properties of electrolyte solutions for lithium batteries. The solvation structure of Li + and formation of ion pairs in electrolyte solutions composed of triglyme (G3) and a hydrofluoroether (HFE) containing 1 mol dm −3 Li[TFSA] (TFSA: bis(trifluoromethanesulfonyl)amide) were analyzed using pulsed-field gradient spin−echo (PGSE) NMR and Raman spectroscopy. It was found that Li + is preferentially solvated by G3 and forms a [Li(G3)] + complex cation in the electrolytes. The HFE scarcely participates in the solvation because of low donor ability and relatively low permittivity. The dissociativity of Li[TFSA] decreased as the molar ratio of G3/Li [TFSA] in the solution decreased. The activity of G3 in the electrolyte diminishes negligibly as the molar ratio approaches unity because G3 is involved in 1:1 complexation with Li + ions. The negligible activity of G3 in the electrolyte solutions has significant effects on the electrochemical reactions in lithium batteries. As the activity of G3 diminished, the oxidative stability of the electrolyte was enhanced. The corrosion rate of the Al current collector of the positive electrode was suppressed as the activity of G3 diminished. The high oxidative stability and low corrosion rate of Al in the G3/Li[TFSA] = 1 electrolyte enabled the stable operation of 4-Vclass lithium batteries. The activity of G3 also has a significant impact on the Li + ion intercalation reaction of the graphite electrode. The desolvation of Li + occurs at the interface of graphite and the electrolyte when the activity of G3 in the electrolyte is significantly low, while the cointercalation of Li + and G3 takes place in an electrolyte containing excess G3. The activity of G3 influenced the electrochemical reaction process of elemental sulfur in a Li−S battery. The solubility of lithium polysulfides, which are reaction intermediates of the sulfur electrode, decreased as the activity of G3 in the electrolyte decreased. In the G3/ Li[TFSA] = 1 electrolyte, the solubility of Li 2 S m is very low, and highly efficient charge/discharge of the Li−S battery is possible without severe side reactions.

Highly concentrated, molten mixtures of lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) and ether solvents (tetrahydrofuran (THF), monoglyme (G1), diglyme (G2), and triglyme (G3)) were investigated as electrolytes for Li batteries. To compare the electrochemical reactions in the electrolytes with different solvents, the ratio of ether–oxygen atoms and Li+ ([O]/[Li]) in the electrolytes was fixed at four. The capacity of a Li–LiCoO2 cell with [Li(THF)4][TFSA] dramatically decreased upon charge/discharge cycling, whereas [Li(G3)1][TFSA] allowed the cell to have a stable charge–discharge cycles and a Coulombic efficiency of greater than 99% over 100 cycles. Corrosion of the Al current collector of the cathode was also affected by the composition of the electrolytes. Persistent Al corrosion took place in [Li(THF)4][TFSA] and [Li(G1)2][TFSA], which contain shorter ethers, but the corrosion was effectively suppressed in [Li(G3)1][TFSA]. Furthermore, lithium polysulfides, which are formed as discharge intermediates at the sulfur cathode of the Li–S cell, were much less soluble in electrolytes with longer ethers. Therefore, a higher Coulombic efficiency and more stable cycle ability were achieved in Li–S cells with [Li(G3)1][TFSA]. All the electrochemical properties in the batteries were dominated by the presence or absence of uncoordinating solvents in the concentrated electrolytes. This paper demonstrates that the structural stability of [Li(glyme or THF) x ]+ cations in electrolytes plays an important role in the performance of Li batteries.

Off-channel temporary pools on riverbanks have characteristic seasonal wet-dry cycles resulting from direct inflow of river water or hyporheic flow seepage. This study addressed two questions regarding the role of temporary pools in supporting diversity of riparian vegetation in a regulated river in Japan: (1) do temporary pools maintain high native riparian plant species diversity? And, (2) how do physical environmental factors affect the pattern of plant species distribution? The study was conducted on a 1-km section of the Hayade River alluvial fan in Niigata Prefecture, central Japan. Two to five transect belts consisting of 20 contiguous plots (1 m · 1 m) were laid out in two offchannel temporary pools and six other sites classified by physiognomy. Vascular plant presence, relative elevation, and substratum type were recorded in all plots. Species richness, Simpson's reciprocal index (1/D), and Shannon-Wiener function (H¢) were calculated by life form to estimate plant species diversity. Two conclusions could be drawn from the results. First, the temporary pools maintained high native riparian plant species diversity in this regulated river floodplain. Second, several environmental factors (seasonal wet-dry cycle, low elevation, complex micro-topography, and fine substrata) created spatial and seasonal heterogeneity of moisture conditions in the temporary pools, supporting plant species diversity. For sustainable maintenance of riparian plant species diversity, progressive river-management should restore original riverine dynamics to generate a shifting mosaic of diverse geomorphology.

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