2.1. Ionic Liquids
Ionic liquids are basically a family of molten salts comprising organic cations and organic/inorganic anions [
3]. While common ionic salts at room temperature exist as a solid where cations and anions are alternately packed, ionic liquids have a lower melting point below 100 °C because cations and anions are not packed due to their large difference in ionic size and the resulting low lattice energy [
4]. In particular, ionic liquids that exist as a liquid at room temperature are called room temperature ionic liquids (RTILs), and the number of currently known RTILs reaches about 10
6 [
5,
6].
Figure 2 illustrates the structures of representative molten salt, ionic liquid, and aqueous solution.
Figure 2.
Schematic diagram of (a) molten KCl; (b) ionic liquid; and (c) aqueous KCl structures.
Figure 2.
Schematic diagram of (a) molten KCl; (b) ionic liquid; and (c) aqueous KCl structures.
A large percentage of ionic liquids have organic cations such as imidazolium or pyridinium, alkyl-substituted heterocyclic ring molecules, capable of ionic bonding with various kinds of anions. By a proper combination of cation and anion, we could control the melting point, density, viscosity, hydrophilicity/hydrophobicity of ionic liquids.
Table 1 summarizes the unique properties of ionic liquids.
Table 1.
Unique properties of ionic liquids.
Table 1.
Unique properties of ionic liquids.
Properties | Values |
---|
Melting point | Preferably below 100 °C |
Liquidus range | Often > 200 °C |
Thermal stability | Usually high |
Viscosity | Normally < 100 cP, workable |
Dielectric constant | Implied < 30 |
Polarity | Moderate |
Ionic conductivity | Usually < 10 mS/cm |
Molar conductivity | <10 Scm2/mol |
Electrochemical window | Often > 4 V |
Vapor pressure | Usually negligible |
Contrary to the usual electrolyte where ionic salts are dissolved in a solvent, ionic liquids can act as electrolyte without the addition of solvent. Further, ionic liquids have very low vapor pressure suffering a negligible loss at room temperature and can even be vacuum dried [
7,
8]. Electrochemical stability and ionic conductivity are also very important properties of electrolyte to be considered as well as low vapor pressure. A large number of ionic liquids have wider electrochemical windows than 4 V, and some can have as wide as 6 V. Moreover, ionic liquids have a generally satisfactory ionic conductivity about 10 mS/cm, which can be comparable to that of sea water. However, they have a much larger viscosity than common organic solvents or water, which incurs a reduced ionic conductivity [
9]. Thus, a combination of low viscosity and high ionic conductivity would be favorable to the usage of ionic liquids as electrolyte. The aforementioned features in addition to non-flammability make ionic liquids attractive to various applications such as organic synthesis [
10,
11], fine chemical production [
12,
13], and electrolytes for capacitors [
14], dye-sensitized solar cells [
15] and batteries [
16].
Favorable properties of ionic liquids are different depending on their applications, and the control of their properties is possible by a proper combination of cation and anion. For example, ionic liquids should be aprotic with low volatility, non-flammability, high ionic conductivity, and a wide potential window to be used as electrolytes for energy storage devices such as lithium batteries. On the other hand, ionic liquids need to be protic to be used as electrolytes for fuel cells while zwitterionic ionic liquids are preferable as membranes for metal extraction as illustrated in
Figure 3.
Physicochemical properties of ionic liquids are basically determined by their components, that is, combinations of cations and anions. By combining cations and anions of different structure and size, the melting point, density, viscosity, and chemical reactivity can be controlled. The species in
Figure 4 are usually considered in tuning the relevant properties of ionic liquids for cations, anions and substituents. For example,
Figure 5 shows the temperature dependence of viscosity (η) for the six N(SO
2CF
3)
2-anion-based RTILs. The obtained viscosities increase in the order EMIm (1-ethyl-3-methylimidazolium) < P13 (
N-methyl-
N-propylpyrrolidinium) < EDMIm (1-ethyl-2,3-dimethylimidazolium) < TMPA (trimethylpropylammonium) < ETMP (1-ethyl-2,3,5-trimethylpyrazolium) < PP13 (
N-methyl-
N-propylpiperidinium) at all measured temperatures.
Figure 3.
Design of ionic liquids for special purposes (Reprinted with permission from ref. [
17] Copyright 2009 Rights Managed by Nature Publishing Group).
Figure 3.
Design of ionic liquids for special purposes (Reprinted with permission from ref. [
17] Copyright 2009 Rights Managed by Nature Publishing Group).
Figure 4.
Species that are usually considered as cations, anions and substituents for designing task specific ionic liquids.
Figure 4.
Species that are usually considered as cations, anions and substituents for designing task specific ionic liquids.
Figure 5.
Effect of cations on the viscosity of ionic liquids (Reprinted with permission from ref. [
18] Copyright 2010 Elsevier B.V).
Figure 5.
Effect of cations on the viscosity of ionic liquids (Reprinted with permission from ref. [
18] Copyright 2010 Elsevier B.V).
Although an ionic liquid could be synthesized by various routes, [Dmim]BF
4, an imidazolium-based ionic liquid, can be prepared in a relatively simple method as illustrated in
Figure 6. The synthesis steps are sequentially conducted as follows: quaternization of amine, solvent removal, anion exchange with a metal salt, solvent/salt removal and refining. Using this method, a wide spectrum of physicochemical property of ionic liquids can be obtained by different functionalization (through the variation of alkyl-X) and anion species (through the variation of metal salt).
Figure 6.
Synthesis procedure of an ionic liquid ([Dmim]BF4).
Figure 6.
Synthesis procedure of an ionic liquid ([Dmim]BF4).
Electrochemical characteristics such as electrochemical window and ionic conductivity can be controlled as well.
Figure 7 shows the dependency of electrochemical window of ionic liquids on their constituting cations and anions. The stability limits of electrochemical window with respect to oxidation and reduction are respectively determined by anion and cation of an ionic liquid. Meanwhile, the ionic conductivity of ionic liquids can be regulated indirectly by adjusting the viscosity of ionic liquids and taking the inverse relationship between conductivity and viscosity into account. The viscosity and the according ionic conductivity are usually varied by changing the type and size of functional groups of cations or by selecting different kinds of anions. For instance, in the choice of anions, relatively small anions such as BF
4 and PF
6 known to have high conductivity were often considered as anions of ionic liquids, whereas TFSI anion is nowadays most frequently adopted thanks to its improved stability.
Figure 7.
Effect of ion group on electrochemical window of ionic liquids.
Figure 7.
Effect of ion group on electrochemical window of ionic liquids.
To overcome the intrinsic limitation of properties belonging to ionic liquids, conventional solvents could be incorporated. Chaban
et al. reported that the addition of acetonitrile to BF
4 anion-based ionic liquid can improve the ionic conductivity in
Figure 8 [
19]. Meanwhile, the understanding of physicochemical properties of metal salt-containing ionic liquids is also important for the application of these materials to hydrometallurgy or electrometallurgy.
Figure 9 is an example to investigate the phase diagram and complexation behavior of Al salt-containing ionic liquids.
Figure 8.
Enhancement of ionic conductivity of ionic liquids by mixing with organic solvents (Reprinted with permission from ref. [
19] Copyright 2012 American Chemical Society).
Figure 8.
Enhancement of ionic conductivity of ionic liquids by mixing with organic solvents (Reprinted with permission from ref. [
19] Copyright 2012 American Chemical Society).
Figure 9.
Phase diagram and complexation behavior of [C
2C
1im]Cl-AlCl
3 (Reprinted with permission from ref. [
20,
21] Copyright 1984 American Chemical Society).
Figure 9.
Phase diagram and complexation behavior of [C
2C
1im]Cl-AlCl
3 (Reprinted with permission from ref. [
20,
21] Copyright 1984 American Chemical Society).
2.3. Electrolysis of Metals
Ionic liquids have been adopted more extensively on the field of metal electrolysis than the other fields belonging to metal manufacturing industry. Because there are too many references in this field to cover their details in this review, we try to restrict the contents of this section to our own results.
Table 2 is the literature survey result where the combination of some selected metals and ionic liquids is specified with reference information. Readers may refer to other review papers including F. Endre’s [
39,
40,
41] for a more extensive overview in this field.
Table 2.
Literature survey result for the combination of some selected metals and ionic liquids in the field of metal electrolysis (A–G).
(A)
| Metal | Li | Mg | Au | Pt | Pd |
---|
Ionic Liquids | |
---|
BMI[TFSI] | | | [42] | | |
BMP[TFSI] | | | | [43] | [44] |
Bu3HexP+[TFSI]− | [45] | | | | |
Bu3HexN+[TFSI]− | [45] | | | | |
C3mpyr[TFSI] | [46] | | | | |
DEME[TFSI] | | [47,48] | | | |
EMI[TFSI] | [49] | | | | |
EMIm[TFSI] | [50] | | | | |
N1113[TFSI] | [49] | | | | |
N1114[TFSI] | [51] | | | | |
(B)
| Metal | Li | Mg | Au | Ta | Si | Nd |
---|
Ionic Liquids | |
---|
PP13[TFSI] | | [52] | | | | |
Pyr14[TFSI] | | | | | [53] | |
TMHA[TFSI] | | | | | [54,55] | |
C3mpyr[FSI] | [56] | | | | | |
BMP[TFSA] | | | [57] | | | |
EMIm[TFSA] | | | [58] | | | |
PMIm[TFSA] | | | | | [59] | |
PP13[TFSA] | [60,61] | | | | | |
P2225[TFSA] | | | | | | [62] |
Py14[TFSA] | [60,63] | | | [64] | | |
(C)
| Metal | Li | Mg | Au | Pt | Ti | Ta | Si | In |
---|
Ionic Liquids | |
---|
TMHA[TFSA] | [60] | | | | | | | |
EMI[FSA] | [61] | | | | | | | |
EMI[TSAC] | [49] | | | | | | | |
N2222[TSAC] | [49] | | | | | | | |
ABN1n[Tf2N] | [65] | | | | | | | |
BEPip[Tf2N] | | | | | | | | [66] |
BMIm[Tf2N] | | | | | [67] | | | |
BMP[Tf2N] | | [68] | | | [69] | [67,70,71,72,73] | [67,69,74,75] | [76] |
C3(OH)2mim[Tf2N] | | | | [77] | | | | |
C4Mim[Tf2N] | | | [78] | [78] | | | | |
(D)
| Metal | Mg | Au | Pt | Pd | Ti | Si |
---|
Ionic Liquids | |
---|
C10MIm[Tf2N] | | [79] | | | | |
EMIm[Tf2N] | | | | | [80] | |
P66614[Tf2N] | | [81] | [81,82] | | | |
P(C6)3C14[Tf2N] | | [83] | [83,84,85] | | | |
Py14[Tf2N] | | | | | | [86,87,88] |
TBMA[Tf2N] | | [89] | | | | |
BMP[TfO] | [68] | | | | | |
BMIm[Cl] | | [90] | [90] | [91,92,93,94,95,96,97,98] | [99,100] | |
C3COOH[Cl] | | | [77] | | | |
C3OHMIm[Cl] | | | [77] | | | |
(E)
| Metal | Li | Au | Pt | Ti |
---|
Ionic Liquids | |
---|
C3CNmim[Cl] | | | [77] | |
C3(OH)2mim[Cl] | | | [77] | |
C3(OCOCH2SH)2mim | | | [77] | |
BMECl[AlCl3] | [101] | | | |
BMIC[AlCl3] | | | | [102] |
BTMAC[AlCl3] | | | [103] | |
EMICl[AlCl3] | [51,104] | | | |
EMImCl[AlCl3] | [105] | | | |
EtMelmCl[AlCl3] | | | | [106,107] |
BMI[BF4] | | [108] | | |
(G)
| Metal | Au | Pt | Pd | In |
---|
Ionic Liquids | |
---|
BMIm[PF6] | [122] | [113,123] | | |
C3(OH)2mim[PF6] | | [77] | | |
C8Py[PF6] | | | [124] | |
ZnCl2[EMIC] | | [125,126,127] | | |
ZnCl2[EMIm-Cl] | | [67] | | |
EMI[Cl-BF4] | [42] | | [42] | [128] |
mercapto IL[1-methyl-3(2'-mercaptoacetoxyethyl) imidazoliumhexafluorophosphate] | [129] | [129] | [129] | |
TOMAC(Aliquat 336 chloride-IL) | | | [98,130] | |
TOMAN(Aliquat 336 nitrate-IL) | | | [130] | |
Active/light metals such as magnesium, rare earth metals such as neodymium and silicon are usually recovered by pyrometallurgical processes where metal phases are obtained by direct melting or by reduction with reductants often after the additional formation steps of specific metal salts. Generally these recovery processes have problems such as high operating temperature (600–2000 °C), high operating cost, low energy efficiency (50%–80%), high energy consumption (~100 kWh/kg metal), environmental issues, and waste management. Alternatively, these metals could be recovered by electrolysis, but its practicability is limited by the use of conventional aqueous electrolytes because of low reduction potential and high chemical activity of the metals in aqueous systems. However, the properties of ionic liquids such as wide electrochemical window, low vapor pressure and satisfactory ionic conductivity shed light on the expansion of electrolysis to the recovery of active/light metals, rare earth metals and silicon.
For example, the electrochemical reduction behavior of silicon at room temperature was examined by using two kinds of ionic liquids (1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide ([Bmpy]Tf
2N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim]Tf
2N)) of which cations were different, and the resulting electrodeposited silicon thin films were obtained with the added salt of SiCl
4 as shown in
Figure 13 [
131]. Further, the recycling of silicon single crystal cutting sludge was suggested based on the above reduction behavior of silicon in the ionic liquids, emphasizing that the proper choice of cation in ionic liquids is very important for the effective silicon recycling [
132].
Figure 13.
Electrochemical behavior of silicon in [Bmpy]Tf
2N and electrodeposited silicon thin film [
131].
Figure 13.
Electrochemical behavior of silicon in [Bmpy]Tf
2N and electrodeposited silicon thin film [
131].
The electrowinning of magnesium, a representative light metal, is not feasible in aqueous electrolytes at room temperature because of its low reduction potential and high reactivity with water. However, the electrodeposition of magnesium could be possible when an electrochemically stable ionic liquid is used as electrolyte. This possibility was examined by adopting an imidazolium-based ionic liquid and Mg(CF
3SO
3)
2 as a magnesium source [
133]. The magnesium electrodeposited at a potential of 1.5 V (
vs. Mg) has a particulate morphology as depicted in
Figure 14. Although the electrodeposits on silver substrate include some impurities of F and O, which might originate from the Mg salt, in addition to Mg, this study showed that a careful choice of ionic liquid and metal salt enables the room temperature electrodeposition of active/light metals.
Figure 14.
Electrochemical behavior of magnesium in [Bmim]BF
4 and its electrodeposited thin film [
133].
Figure 14.
Electrochemical behavior of magnesium in [Bmim]BF
4 and its electrodeposited thin film [
133].
Rare earth metals are extensively used in high-tech industries despite their scarcity on earth. For example, neodymium, of which usage has been expanded in recent years because of a proliferation of high-performance magnets for advanced motors in electric vehicles, needs to be reused or recycled considering its limited availability. The conventional extraction method of neodymium metal is fused salt electrolysis, which has some disadvantages such as high operating cost, high energy consumption, environmental issues of chlorine gas emission and so on. The production of neodymium compounds also needs complicated and costly separation and purification stages. By contrast,
Figure 15 shows that simple and relatively low-cost production and recycling of neodymium metal are possible by electrowinning or electrorefining of waste magnets in ionic liquids. This possibility was examined by using a gold substrate and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim]TFSI) containing Nd(TFSI)
3 as a neodymium source.
Figure 15.
Electrodeposition of neodymium in [Emim]TFSI.
Figure 15.
Electrodeposition of neodymium in [Emim]TFSI.
For the selective separation/recovery of platinum group metals, hydrometallurgy or pyrometallurgy techniques could be used. A leaching process based on hydrometallurgy adopts strong acid leaching agents, which can dissolve and recover various kinds of platinum group metals constituting automotive catalysts, however, in large quantities and which incurs environmental problems [
134]. On the other hand, pyrometallurgical techniques need substantial energy input and large-scale facilities because crushing and grinding pre-treatment and high temperature smelting of platinum group metal-containing materials such as spent catalysts are required in these techniques. To overcome the disadvantages of the established techniques based on hydrometallurgy or pyrometallurgy, a newly proposed separation/recovery of platinum group metals by using ionic liquids is investigated as seen in
Figure 16 where platinum, palladium and rhodium have different reduction behavior depending on applied potential.
Figure 16.
Compositional change of platinum group metals in [Bmim]Cl depending on applied potentials.
Figure 16.
Compositional change of platinum group metals in [Bmim]Cl depending on applied potentials.