https://www.chem.ccu.edu.tw/~joyce/referance/gump/IL/Chem.%20Rev.%201999,%2099,%202071.pdf

Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis

The challenges for further development of Li rechargeable batteries for electric vehicles are reviewed. Most important is safety, which requires development of a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) or a constituent (or additive) that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery. A high Li-ion conductivity (σ Li > 10 ―4 S/cm) in the electrolyte and across the electrode/ electrolyte interface is needed for a power battery. Important also is an increase in the density of the stored energy, which is the product of the voltage and capacity of reversible Li insertion/extraction into/from the electrodes. It will be difficult to design a better anode than carbon, but carbon requires formation of an SEI layer, which involves an irreversible capacity loss. The design of a cathode composed of environmentally benign, low-cost materials that has its electrochemical potential μ C well-matched to the HOMO of the electrolyte and allows access to two Li atoms per transition-metal cation would increase the energy density, but it is a daunting challenge. Two redox couples can be accessed where the cation redox couples are "pinned" at the top of the O 2p bands, but to take advantage of this possibility, it must be realized in a framework structure that can accept more than one Li atom per transition-metal cation. Moreover, such a situation represents an intrinsic voltage limit of the cathode, and matching this limit to the HOMO of the electrolyte requires the ability to tune the intrinsic voltage limit. Finally, the chemical compatibility in the battery must allow a long service life.

Challenges for Rechargeable Li Batteries

Ionic liquids are salts that are liquid at low temperature (<100 degrees C) which represent a new class of solvents with nonmolecular, ionic character. Even though the first representative has been known since 1914, ionic liquids have only been investigated as solvents for transition metal catalysis in the past ten years. Publications to date show that replacing an organic solvent by an ionic liquid can lead to remarkable improvements in well-known processes. Ionic liquids form biphasic systems with many organic product mixtures. This gives rise to the possibility of a multiphase reaction procedure with easy isolation and recovery of homogeneous catalysts. In addition, ionic liquids have practically no vapor pressure which facilitates product separation by distillation. There are also indications that switching from a normal organic solvent to an ionic liquid can lead to novel and unusual chemical reactivity. This opens up a wide field for future investigations into this new class of solvents in catalytic applications.

Ionic Liquids-New "Solutions" for Transition Metal Catalysis.

Electrolytes and interphases in Li-ion batteries and beyond.

Within the framework of green chemistry, solvents occupy a strategic place. To be qualified as a green medium, these solvents have to meet different criteria such as availability, non-toxicity, biodegradability, recyclability, flammability, and low price among others. Up to now, the number of available green solvents are rather limited. Here we wish to discuss a new family of ionic fluids, so-called Deep Eutectic Solvents (DES), that are now rapidly emerging in the current literature. A DES is a fluid generally composed of two or three cheap and safe components that are capable of self-association, often through hydrogen bond interactions, to form a eutectic mixture with a melting point lower than that of each individual component. DESs are generally liquid at temperatures lower than 100 °C. These DESs exhibit similar physico-chemical properties to the traditionally used ionic liquids, while being much cheaper and environmentally friendlier. Owing to these remarkable advantages, DESs are now of growing interest in many fields of research. In this review, we report the major contributions of DESs in catalysis, organic synthesis, dissolution and extraction processes, electrochemistry and material chemistry. All works discussed in this review aim at demonstrating that DESs not only allow the design of eco-efficient processes but also open a straightforward access to new chemicals and materials.

Deep eutectic solvents: syntheses, properties and applications

Room temperature molten salts composed of the 1-ethyl-3-methylimidazolium cation and a chloroaluminate anion have received much attention for use in a variety of commercial applications such as batteries, photovoltaics, metal deposition, and capacitors. The room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF{sub 4}) was demonstrated as a versatile electrolyte by examining three representative electrochemical couples: ferrocene and tetrathiafulvalene oxidations and lithium ion reduction. Square-wave voltammetric data for ferrocene oxidation were fit to a reversible one-electron process using the COOL algorithm to give a half-wave potential of 0.490 V vs. Al/Al(III) and a diffusion coefficient of 5.1 {times} 10{sup {minus}7} cm{sup 2}/s. The two-electron oxidation of tetrathiafulvalene was reversible and proceeded through two consecutive one-electron steps; although data collected at lower square-wave frequencies indicated a slow precipitation of the TTF{sup +} species. Lithium ion was reduced to lithium metal at a Pt electrode following the addition of water to the EMIBF{sub 4} electrolyte, whereas lithium ion reduction at an Al wire produced the {beta}-LiAl alloy. Conductivities and kinematic viscosities of EMIBF{sub 4} were measured from 20 to 100 C and had values of 14 mS/cm and 0.275 cm{sup 2}/s, respectively, at 25 C.

The room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate : Electrochemical couples and physical properties

The crystal structure of 1-ethyl-3-methylimidazolium (EMI+) hexafluorophosphate consists of interionic interactions dominated by cation–anion coulombic forces with minimal hydrogen bonding and serves as a model for EMI+ room temperature molten salts containing weakly complexing anions.

Structure of 1-ethyl-3-methylimidazolium hexafluorophosphate : model for room temperature molten salts

The reductive and oxidative intercalation of ions into graphite from room-temperature and low temperature molten salts is demonstrated For this investigation, the molten salts use 1-ethyl-3-methylimidazolium (EMI[sup +]) or 1,2-dimethyl-3-propylimidazolium (DMPI[sup +]) as the cation and AlCl[sup [minus]][sub 4], BF[sup [minus]][sub 4], PF[sup [minus]][sub 6], CF[sub 3]SO[sup [minus]][sub 3], or C[sub 6]H[sub 5]CO[sup [minus]][sub 2] as the anion In a two-electrode battery configuration, the molten salt electrolyte provides both the cation and anion which are intercalated into the graphite anode and cathode, respectively A cell employing a (DMPI)(AlCl[sub 4]) electrolyte and two graphite rod electrodes achieved an open-circuit voltage of 35 V and a cycling efficiency of 85%

Dual Intercalating Molten Electrolyte Batteries

The -1, -2, and -3 anions of C[sub 60] were generated electrochemically in 4:1 toluene-acetonitrile. The visible/near-IR spectra were monitored in situ. Square wave voltammograms and electronic spectra showed that after bulk electrolysis to produce the anions, the following percentages of the starting C[sub 60] concentration could be reoxidized to neutral C[sub 60] in typical data sets: -1 anion, 75%; -2 anion, 66%; -3 anion, 46%. Continuous wave (CW) electron paramagnetic resonance (EPR) spectra of the -1 and -3 anions exhibited broad signals that were temperature dependent. The averaging of anisotropy of the signals between 15 and 60 K is attributed to dynamic Jahn-Teller distortion. Electron spin-echo and saturation recovery EPR data for the -1 anion at 10 and 16 K showed that the electron spin relaxation rates are dependent upon position in the spectrum, which is attributed to variations in the Jahn-Teller distortion. For both the -1 and -3 anion above about 70 K the CW line shape of the EPR signal is electron spin-lattice relaxation rate determined. The EPR data indicate that the -2 anion is diamagnetic. 53 refs., 14 figs.

Electrochemical Generation and Electron Paramagnetic Resonance Studies of C60-, C602-, and C603-

The electrochemistry of titanium (IV) has been examined in acidic (AlCl 3 -rich) compositions of the ambient-temperature molten salt, AlCl 3 -1-ethyl-3-methylimidazolium chloride (ImCl). Titanium is reduced to Ti(III) and Ti(II) in two one-electron steps, both of which exhibit slow electron-transfer kinetics

Richard T. Carlin

Papers

The room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate : Electrochemical couples and physical properties

Structure of 1-ethyl-3-methylimidazolium hexafluorophosphate : model for room temperature molten salts

Dual Intercalating Molten Electrolyte Batteries

Electrochemical Generation and Electron Paramagnetic Resonance Studies of C60-, C602-, and C603-

Studies of titanium(IV) chloride in a strongly Lewis acidic molten salt: electrochemistry and titanium NMR and electronic spectroscopy