Electrochimica Acta 51 (2006) 5567–5580

Critical review

Ionic liquids as electrolytes

Maciej Galiński 1 , Andrzej Lewandowski ∗,1 , Izabela St˛epniak 1
Faculty of Chemical Technology, Poznań University of Technology, PL-60 965 Poznań, Poland
Received 7 November 2005; received in revised form 9 March 2006; accepted 12 March 2006
Available online 19 April 2006

Abstract
Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature
ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature
molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high
temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic
liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following
the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However,
ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been
prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view
of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing,
conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application
in aluminium electroplating, lithium batteries and in electrochemical capacitors.
© 2006 Elsevier Ltd. All rights reserved.

Keywords: Ionic liquids; Room temperature molten salts; Electrolytes

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5568
2. General properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5568
3. Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5572
3.1. Influence of viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5573
3.2. Temperature dependence of the conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5573
3.3. Transport and transference numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5574
4. Electrochemical stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5574
5. Ionic liquids containing lithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5575
6. Ionic liquids as electrolytes for electrochemical capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5577
7. Low-temperature aluminium electrodeposition and recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5578
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5578
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5579

Abbreviations: AN, acetonitrile; Bu, butyl; CNT, carbon nanotubes; Di , diffusion coefficient of ion i; DMC, dimethyl carbonate; DME, 1,2-dimethoxy ethane;
DMSO, dimethyl sulphoxide; EC, ethylene carbonate; Et, ethyl; Et2 O, diethylether; Fc/Fc+ , ferrocene/ferrocenium; GC, glassy carbon; Hex, hexyl; Λ, equivalent
molar conductivity; Me, methyl; Me2 SO2 , dimethylsulfone; η, viscosity; Oct, octyl; PC, Propylene carbonate; Pp, piperidinium; Pi, pyridinium; iPr, isopropyl; Pr,
propyl; Py, pyrrolidinium; Qi , charge transported by ion i; ui , mobility of ion i; RTIL, room temperature ionic liquid; RTIL-S, supercooled room temperature ionic
liquid; σ, conductivity; THF, tetrahydrofurane; TM , TX , transference numbers of electrolyte MX constituents; ti , transport number of ion i; Tg , temperature of glass
transition
∗ Corresponding author. Tel.: +48 61 6652309; fax: +48 61 6652571.

E-mail address: Andrzej.Lewandowski@put.poznan.pl (A. Lewandowski).

1 ISE Member.

0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.03.016
5568 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580

1. Introduction is to review the physical and chemical properties of RTILs from

the point of view of their possible application as electrolytes in
Classical solutions of electrolytes are obtained by dissolu- electrochemical processes and devices.
tion of salts in molecular solvents. Such systems consist of
solvated ions, their charged or neutral combinations and sol- 2. General properties
vent molecules. On the other hand, a salt may be melted down,
or in other words ‘liquified’, by providing to the system a heat Room temperature ionic liquids are usually quaternary
to counterbalance the salt lattice energy. Such a system, called ammonium salts (Fig. 1), such as tetralkylammonium [R4 N]+
molten salts or ionic liquid (IL), consists of ions and their com- or based on cyclic amines, both aromatic (pyridinium, imi-
binations and is free of any molecular solvent. Relatively high dazolium) and saturated (piperidinium, pyrrolidinium). Low-
melting points of many salts determine the temperature range temperature molten salts based on sulfonium [R3 S]+ as well
of classical ionic liquids. These temperatures can be lowered as phosphonium [R4 P]+ cations are also known. Cations may
by the addition of other salts forming a eutectic. Even in such be modified by incorporating functionalities to carbon atoms
a case considerable heat is necessary to maintain the system in of the ring: for example incorporating nitrile to 1-alkyl-3-
the liquid state. On the other hand, salts having a low melting methylimidazolium [23]. As well, anions may be based on
point are liquid at room temperature, or even below, and form cyano groups, such as [Ag(CN)2 ]− , [C(CN)3 ]− or [N(CN)2 ]−
a new class of liquids usually called room temperature ionic [24]. Observed temperatures of solidification (freezing) and
liquids (RTIL). Information about RTILs can be found in the lit- melting of some representative salts, based on tetraalkylam-
erature with such key words as: room-temperature molten salt, monium ([R4 N]+ or [R R3 N]+ ), imidazolium [RR Im]+ , pyrro-
low-temperature molten salt, ambient-temperature molten salt, lidinium [RR Py]+ , piperidinium [RR Pp]+ and pyridinium
liquid organic salt or simply ionic liquid. Their physicochemical [RPi]+ cations as well as a number of both inorganic (halide,
properties are the same as high temperature ionic liquids, but the [BF4 ]− , [PF6 ]− , [AsF6 ]− or amide [N(CN)2 ]− and organic
practical aspects of their maintenance or handling are different [C4 F9 SO3 ]− , trifluoroacetic [CF3 CO2 ]− , triflate [CF3 SO3 ]− ,
enough to merit a distinction. The term ’ionic liquid’ is often
extended to salts having a melting point below 100 ◦ C. In such
a case a significant amount of heat must be provided to keep the
salt in the liquid state, and IL cannot be handled as a classical
electrolyte solution.
The first discovered RTIL seems to be ethylammonium
nitrate, [EtNH3 ][NO3 ] [1], described at the beginning of XX
century (1914). In the middle of the last century (1948) the first
RTIL based on chloroaluminate anion was patented [2,3]. Fif-
teen years later (1963), a similar system, based on chlorocuprate
anion, CuCl2 − , and tetraalkylammonium cation, obtained by
mixing cuprous chloride (CuCl) and tretraalkylammonium chlo-
ride, was described [4]. In 1967 the application of tetra-n-
hexylammonium benzoate as a solvent was published [5]. The
class of ionic liquids, based on tetraalkylammonium cation and
chloroaluminate anion, has been extensively studied since late
1970s of the XX century, following the works of Osteryoung
[6–8]. Systematic research on the application of chloroalumi-
nate ionic liquids as solvents was performed in 1980s [9–14].
The most extensively studied RTIL of this type seems to be
dialkylimidazolium chloroaluminates. Such RTILs are good sol-
vents for conducting various reactions as AlCl3 is an acid in
the Lewis meaning and can act as a catalyst. However, ionic
liquids based on aluminium halides are moisture sensitive, as
AlX3 reacts with water with the liberation of HX (X = Cl− or
Br− ). In the 1990s new ionic liquids were described, based on 1-
ethyl-3-methylimidazolium cation and tetrafluoroborate anion,
resistant to moisture traces [15] and showing clearly that the
room temperature ionic liquids are not limited to uncomfortable
chloroaluminate salts. During the last decade an increasing num-
ber of new ionic liquids have been prepared and used as solvents.
There are review articles devoted to RTILs available in the lit-
erature [16–22], including application of non-chloroaluminate
RTILs in electrochemistry [19]. The general aim of this paper Fig. 1. Ionic liquids.
 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580 5569

Table 1
Melting and freezing temperatures of ionic liquids
Ionic liquids Melting point [◦ C] Observed temperature of solidification [◦ C] Ref.

Imidazolium
[MeMeIm]+ [N(CF3 SO2 )2 ]− RTIL 22 [25,26]
[MeMeIm]+ [CF3 SO3 ]− 39 [25]
[MeMeIm]+ [CF3 CO2 ]− 52 [25]
[EtMeIm]+ [Br]− RTIL-S 79 30 [27]
[EtMeIm]+ [Cl]− RTIL-S 89 33 [27]
[EtMeIm]+ [I]− RTIL-S 79 39 [27]
[EtMeIm]+ [AsF6 ]− RTIL-S 53 −33 [27]
[EtMeIm]+ [BF4 ]− RTIL 11, 14.6, 15 −63 [27,28,29]
[EtMeIm]+ [PF6 ]− RTIL-S 62, 58 5 [27,30]
[EtMeIm]+ [N(CF3 SO2 )2 ]− RTIL −15, −3, −16, −21 −50 [25–28,31]
[EtMeIm]+ [CF3 SO3 ]− RTIL −9 [25]
[EtMeIm]+ [CF3 CO2 ]− RTIL −14 [25]
[EtMeIm]+ [C(CF3 SO2 )3 ]− RTIL-S 39 −34 [27]
[EtMeIm]+ [N(C2 F5 SO2 )2 ]− RTIL −1 −12 [27]
[EtMeIm]+ [CF3 SO2 NCOCF3 ]− RTIL −1,5 [32]
[EtMeIm]+ [N(CN)2 ]− RTIL −21 [33]
[EtEtIm]+ [N(CF3 SO2 )2 ]− RTIL 14 [25,26]
[EtEtIm]+ [CF3 SO3 ]− RTIL 23 [25]
[EtBuIm]+ [CF3 SO3 ]− RTIL 2 [25]
[1,2-Me2 -3-EtIm]+ [Br]− 141 92 [27]
[1,2-Me2 -3-EtIm]+ [Cl]− 188 103 [27]
[1,2-Me2 -3-EtIm]+ [PF6 ]− 196 193 [27]
[1,2-Me2 -3-EtIm]+ [N(CF3 SO2 )2 ]− RTIL 27, 20 −18 [26,27]
[1-Et-2,3-Me2 Im]+ [CF3 SO3 ]− 109 [25]
[1-Et-2,3-Me2 Im]+ [N(CF3 SO2 )2 ]− RTIL 20 [25]
[1-Et-2,3-Me2 Im]+ [CF3 CO2 ]− 59 [25]
[1-Et-3,5-Me2 Im]+ [N(CF3 SO2 )2 ]− RTIL −3 [25]
[1-Et-3,5-Me2 Im]+ [CF3 SO3 ]− RTIL 6 [25]
[1,2-Et2 -3-MeIm]+ [N(CF3 SO2 )2 ]− RTIL 28 [25]
[1,2-Et2 -3-MeIm]+ [CF3 SO3 ]− 113 [25]
[1,2-Et2 -3-MeIm]+ [CF3 CO2 ]− 59 [25]
[1,3-Et2 -4-MeIm]+ [N(CF3 SO2 )2 ]− RTIL −22 [26]
[1,3-Et2 -5-MeIm]+ [N(CF3 SO2 )2 ]− RTIL −22 [25]
[1,3-Et2 -5-MeIm]+ [CF3 SO3 ]− 35 [25]
[BuMeIm]+ [Cl]− 65 [26]
[BuMeIm]+ [PF6 ]− RTIL −8 [26]
[BuMeIm]+ [N(CF3 SO2 )2 ]− RTIL −4 [26]
[BuMeIm]+ [CF3 SO3 ]− RTIL 16 [25,26]
[BuMeIm]+ [C4 F9 SO3 ]− RTIL 20 [26]
[PrMeIm]+ [BF4 ]− RTIL −17 [34]
[PrMeIm]+ [Cl]− RTIL 60 −140 [27]
[PrMeIm]+ [PF6 ]− RTIL-S 40, 21 −81 [27,31]
[iPrMeIm]+ [I]− 114 44 [27]
[iPrMeIm]+ [PF6 ]− 102 35 [27]
[iPrMeIm]+ [N(CF3 SO2 )2 ]− RTIL 19 −29 [27]
[1,2-Me2 -3-PrIm]+ [Cl]− 138 43 [27]
[1,2-Me2 -3-PrIm]+ [PF6 ]− RTIL-S 78 18 [27]
[1,2-Me2 -3-PrIm]+ [N(CF3 SO2 )2 ]− RTIL −81 −130 [27]
[1,2-Me2 -3-PrIm]+ [N(C2 F5 SO2 )2 ]− RTIL-S 34 −26 [27]
Pyrrolidinium
[MeMePy]+ [BF4 ]− 340(decomp.) [35]
[MeMePy]+ [PF6 ]− 390(decomp.) [36]
[MeMePy]+ [CF3 SO2 NCOCF3 ]− RTIL 24 [32]
[MeMePy]+ [N(CN)2 ]− 115 [33]
[EtMePy]+ [BF4 ]− 280 [33]
[EtMePy]+ [N(CN)2 ]− RTIL −10 [33]
[PrMePy]+ [N(CF3 SO2 )2 ]− RTIL 12 [37]
[PrMePy]+ [BF4 ]− 64 [35]
[PrMePy]+ [N(CN)2 ]− RTIL −35 [33]
[BuMePy]+ [BF4 ]− 138 [35]
[HexMePy]+ [N(CN)2 ]− RTIL −11 [33]
5570 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580

Table 1 (Continued )
Ionic liquids Melting point [◦ C] Observed temperature of solidification [◦ C] Ref.

Tetraalkylammonium
[Me4 N]+ [N(CF3 SO2 )2 ]− 130 [38]
[Me4 N]+ [CF3 SO2 NCOCF3 ]− 64 [32]
[Me3 BuN]+ [CF3 SO2 NCOCF3 ]− RTIL 21 [32]]
[EtMe3 N]+ [CF3 SO2 NCOCF3 ]− RTIL 15 [32]
[PrMe3 N]+ [N(CF3 SO2 )2 ]− RTIL 22 [39]
[Et4 N]+ [BF4 ]− 72 45 [27]
[Et4 N]+ [PF6 ]− RTIL-S 70 −58 [27]
[Et4 N]+ [N(CF3 SO2 )2 ]− 104, 105 98 [27,38,32]
[Et4 N]+ [CF3 SO2 NCOCF3 ]− RTIL 20 [32]
[Et4 N]+ [N(C2 F5 SO2 )2 ]− 83 75 [27]
[Et4 N]+ [C(CF3 SO2 )3 ]− RTIL-S 46 29 [27]
[Bu4 N]+ [N(CF3 SO2 )2 ]− 90 68 [27]
[Bu4 N]+ [C(CF3 SO2 )3 ]− 59 34
Piperidinium
[MePrPp]+ [N(CF3 SO2 )2 ]− RTIL 8,7 [39]
Pyridinium
[BuPi]+ [BF4 ]− RTIL −1, 15, 3 [28,29]
[BuPi]+ [N(CF3 SO2 )2 ]− RTIL 26 [28]

amides [N(CF3 SO2 )2 ]− and [CF3 CONCF3 SO2 ]− , methide
[C(CF3 SO2 )3 ]− anions are shown in Table 1. As can be seen,
ionic liquids show a strong tendency for supercooling—the tem-
peratures of freezing and melting are reported as different values,
although thermodynamically they should be identical. A liquid
below its melting point should crystallize, but the formation of
nucleus around which a crystal structure can be formed, is nec-
essary. When a liquid is cooled its viscosity normally increases
and the increased viscosity prevents formation of the first crys-
tals (nucleus). In the absence of such nucleus, the liquid phase
can be maintained down to the temperature at which it solidifies
into an amorphous (non-crystalline) solid phase. This tempera-
ture of solidification is quite often reported (incorrectly) as the
freezing point or as a ‘solidification point’. In principle this is
a transition from a liquid-like system to a solid-like (or glass-
like) system of significantly increased viscosity, and should be
rather characterized in terms of the glass transition tempera-
ture, Tg . The liquid to crystal transition is a thermodynamic
one (the crystal is energetically more favourable than the liq-
uid below the melting point) while the glass transition is of a
kinetic nature. Therefore, glasses and supercooled liquids are
both metastable phases and can undergo a spontaneous transi-
tion to a crystalline solid. In general, the temperature at which the
solidification is observed may depend on a way of ionic liquid
cooling, especially the cooling rate. The choice of terminology
for this phenomenon has been variable and controversial. The
literature values for the temperature of ILs freezing are indicated
here as the ‘temperature of solidification’ (Table 1). A process
equivalent to supercooling does not exist—solids melt at their
thermodynamic melting points. The difference between reported
melting and solidification points may be as high as 200 ◦ C, as
is observed in the case of [PrMeIm][Cl]. The melting point of
this salt is above room temperature (60 ◦ C), while the solidi-
fication point is −140 ◦ C, which suggests that the salt can be
liquid at room temperature. Inspection of the data collected in
Table 1 indicates that such behaviour is quite usual. As a result,
the same compound can be described in the literature as solid or
liquid at room temperature. There are more melting points for
such a group of compounds available in the literature, compared
to temperatures of ILs solidification. Moreover, some authors
never give melting nor freezing points, only stating that a salt is
liquid or not. For instance, [BuMeIm][Br] is presented as a solid
salt [40,41] or as a room temperature ionic liquid [42,43], but
to our knowledge, there are no proper solidification and melting
point data available in the literature.
It had been assumed that ionic liquids are completely non-
volatile since the work of Earle et al. showing that some ILs
may be evaporated and than recondensed [44]. There was also a
communication reporting vapour pressure of [BuMeIm][NTf2 ],
together with the heat of its evaporation [45]. The assumed non-
volatility of ILs had been the base of their common reputation
of ‘green’ solvents.
Generally, RTILs consist of large, unsymmetrical ions. Rel-
atively small and symmetrical halide anions do not form RTILs,
except [PrMeIm][Cl]. The larger BF4 − anion forms RTILs
with imidazolium and pyridinium cations. The considerably
larger amide anion [N(CF3 SO2 )2 ]− forms ionic liquids with
many cations, except symmetrical [R4 N]+ ones. On the other
hand more unsymmetrical amide anion [CF3 CONCF3 SO2 ] may
form RTIL (with melting point of ca. 20 ◦ C) even with a
symmetrical tetraalkylammonium cation [Et4 N]+ . Density of
ionic liquids, shown in Table 2 is typically 1.2–1.5 g/ml, how-
ever, there are ionic liquids (for example those based on the
dicyanoamide anion, [N(CN)2 ]− showing a density lower than
1 g/ml. Viscosity of ionic liquids (Table 2) is much higher than
that characteristic for water (η(H2 O) = 0.89 cP at 25 ◦ C). Typ-
ically it is at the level of 30–50 cP, but in some cases much
higher, even as high as 500–600 cP. The high viscosity, char-
acteristic for ionic liquids, causes some difficulties with their
handling.
 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580 5571

Table 2
Physical properties of ionic liquids: molar weight (M), density, conductivity (σ), viscosity (η); calculated ILs concentration (c) together with molar conductivity
(Λ = σ/c) and Walden product (Λη)
Ionic liquids Measured (25 ◦ C) References Calculated

M (g/mol) Density σ (mS/cm) η (cP = 0.1 Ns/m2 ) c(IL) (mol/dm3 ) Λ (cm2 / Λη (10−7
(g/cm−3 ) mol) Ns/mol)

Imidazolium
[MeMeIm]+ [N(CF3 SO2 )2 ]− 391.0 1.559 (22) 8.40 (20) 44 (20) [25] 4.0 2.11 93
[EtMeIm]+ [BF4 ]− 197.8 1.24 14 25.7 (25) [44] 6.3 2.23 57
197.8 1.279 14 32 [28] 6.5 2.01 64
197.8 1.28 14 37 [34] 6.5 2.16 80
197.8 13 (26) 43 (26) [47,60] 6.5 2.00 86
[EtMeIm]+ [C(CF3 SO2 )3 ]− 522.0 1.3 (22) [47]
[EtMeIm]+ [CH3 CO2 ]− 170.0 2.8 (20) 162 (20) [25]
[EtMeIm]+ [CF3 SO3 ]− 260.0 1.39 (22) 8.6 (20) 45 (20) [25] 5.3 1.61 72
260.0 11 (22) [45]
[EtMeIm]+ [CF3 CO2 ]− 224.0 1.39 9.6 (20) 35 [56] 6.2 1.55 54
224.0 1.285 (22) 9.6 (20) 35 (20) [25] 5.7 1.67 59
[EtMeIm]+ [N(CF3 SO2 )2 ]− 391.0 1.52 (22) 8.8 (20) 34 [25,26] 3.9 2.26 77
391.0 1.518 5.7 [28] 3.9
391.0 8.6 (22) [47]
391.0 9.2 [26]
391.0 8.4 (26) 28 (26) [63] 3.9 2.15 60
391.0 [49]
[EtMeIm]+ [N(C2 F5 SO2 )2 ]− 491.0 3.4 (26) 61 (26) [60] 3.2 1.06 65
[EtMeIm]+ [N(CN)2 ]− 175.0 1.06 21 [33] 6.1
[EtEtIm]+ [CF3 SO3 ]− 274.0 1.33 (22) 7.5 (20) 53 (20) [25] 4.9 1.55 82
[EtEtIm]+ [N(CF3 SO2 )2 ]− 405.0 1.45 (21) 8.5 (20) 35 [25,26] 3.6 2.37 83
[EtEtIm]+ [CF3 CO2 ]− 238.0 1.25 (22) 7.4 (20) 43 (20) [25] 5.3 1.41 61
[1-Et-2,3-Me2 Im]+ [N(CF3 SO2 )2 ]− 405.0 1.495 (21) 3.2 (20) 88 (20) [25] 3.7 0.87 76
[1-Et-3,5-Me2 Im]+ [N(CF3 SO2 )2 ]− 405.0 1.47 (22) 6.6 (20) 37 (20) [25] 3.6 1.82 67
[1-Et-3,5-Me2 Im]+ [CF3 SO3 ]− 274.0 1.33 (20) 6.4 (20) 51 (20) [25] 4.9 1.32 67
[1,3-Et2 -5-MeIm]+ [N(CF3 SO2 )2 ]− 419.0 1.43 (23) 6.2 (20) 36 (20) [25] 3.4 1.82 65
[BuMeIm]+ [BF4 ]− 225.8 1.21 3.5 (25) 180 [34] 5.4 0.65 118
225.8 1.17 (20) 1.73 (20) 233 (20) [26] 5.2 0.33 78
[BuMeIm]+ [PF6 ]− 284.0 1.8 (22) [49]
284.0 1.36 (20) 1.4 (20) 312 (20) [26] 4.8 0.29 91
284.0 1.33 [56] 4.7
[BuMeIm]+ [N(CF3 SO2 )2 ]− 419.0 1.429 (19) 3.9 (20) 52 (20) [25] 3.4 1.14 59
[BuMeIm]+ [CF3 SO3 ]− 288.0 1.290 (20) 3.7 (20) 90 (20) [25] 4.5 0.83 74
[BuMeIm]+ [CF3 CO2 ]− 252.0 1.209 (21) 3.2 (20) 73 (20) [25] 4.8 0.67 49
[BuMeIm]+ [N(CF3 SO2 )2 ]− 419.0 1.429 (19) 3.9 (20) 52 (20) [25] 3.4 1.14 59
[iBuMeIm]+ [N(CF3 SO2 )2 ]− 419.0 1.428 (20) 2.6 (20) 83 (20) [25] 3.4 0.76 63
[BuEtIm]+ [N(CF3 SO2 )2 ]− 433.0 1.4 (19) 4.1 (20) 48 (20) [25] 3.2 1.27 61
[BuEtIm]+ [CF3 CO2 ]− 266.0 1.18 (23) 2.5 (20) 89 (20) [25] 4.4 0.56 50
[BuMeIm]+ [C4 F9 SO2 ]− 422.0 1.473 (18) 0.45 (20) 373 (20) [25] 3.5 0.13 48
[BuMeIm]+ [C3 F7 CO2 ]− 352.0 1.333 (22) 1.0 (20) 182 (20) [25] 3.8 0.26 48
[BuMeMeIm]+ [BF4 ]− 267.8 0.23 [50]
[BuMeMeIm]+ [PF6 ]− 326.0 0.77 [50]
[PrMeIm]+ [BF4 ]− 211.8 1.24 5.9 103 [34] 5.9 1.01 104
[PrMeMeIm]+ [N(CF3 SO2 )2 ]− 447.0 3.0 (26) 60 (26) [60] 3.5 0.86 51
Pyrrolidinium
[nPrMePy]+ [N(CF3 SO2 )2 ]− 408.0 1.45 (20) 1.4 63 [51,52] 3.6 0.39 25
[PrMePy]+ [N(CN)2 ]− 194.0 0.92 45 [33] 4.7
[nBuMePy]+ [N(CF3 SO2 )2 ]− 422.0 1.41 (20) 2.2 85 [52] 3.3 0.66 56
[BuMePy]+ [N(CN)2 ]− 208.0 0.95 50 [33] 4.6
[HexMePy]+ [N(CN)2 ]− 236.0 0.92 45 [33] 3.9

Tetraalkylammonium
[Me2 Et(CH3 OC2 H4 )N]+ [BF4 ]− 204.8 1.7 [53]
[Me3 BuN]+ [N(CF3 SO2 )2 ]− 386.0 1.41 (20) 1.4 116 [52] 3.7 0.38 44
[nPrMe3 N]+ [N(CF3 SO2 )2 ]− 382.0 3.3 [48]
[Bu3 HexN]+ [N(CF3 SO2 )2 ]− 550.0 1.15 (20) 0.16 595 [54] 2.1 0.08 46
5572 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580

Table 2 (Continued )
Ionic liquids Measured (25 ◦ C) References Calculated

M (g/mol) Density σ (mS/cm) η (cP = 0.1 Ns/m2 ) c(IL) (mol/dm3 ) Λ (cm2 / Λη (10−7
(g/cm−3 ) mol) Ns/mol)

[nHexEt3 N]+ [N(CF3 SO2 )2 ]− 466.0 1.27 (20) 0.67 167 [52,54] 2.7 0.25 41
[nOctEt3 N]+ [N(CF3 SO2 )2 ]− 494.0 1.25 (20) 0.33 202 [54] 2.5 0.13 26
[nOctBu3 N]+ [N(CF3 SO2 )2 ]− 578.0 1.12 (20) 0.13 574 [54] 1.9 0.07 39
[Me3 (CH3 OCH2 )N]+ [N(CF3 SO2 )2 ]− 384.0 4.7 [48]
[Me2 EtPrN]+ [N(CF3 SO2 )2 ]− 396.0 1.41 (20) 1.2 83 [52] 3.6 0.34 28
[Me2 EtBuN]+ [N(CF3 SO2 )2 ]− 410.0 1.37 (20) 1.2 110 [52] 3.3 0.36 40
[Me2 PrBuN]+ [N(CF3 SO2 )2 ]− 424.0 1.34 (20) 0.82 170 [52] 3.2 0.26 44

Pyridinium
[BuPi]+ [BF4 ]− 223.0 1.220 1.9 [30] 5.5
223.0 3.0 (30) [31]
[BuPi]+ [N(CF3 SO2 )2 ]− 416.0 1.449 2.2 [30] 3.5

Piperidinium
[MePrPp]+ [N(CF3 SO2 )2 ]− 422.0 1.51 117 [41]

Sulfonium
[Et3 S]+ [N(CF3 SO2 )2 ]− 399.0 7.1 [55]
[nBu3 S]+ [N(CF3 SO2 )2 ]− 483.0 1.4 [55]

3. Conductivity acetonitrile, for application in double-layer capacitors, is char-

The specific conductivity of a number of representative ionic
liquids is shown in Table 2. As can be seen, the room tempera-
ture conductivities, σ, are within a broad range of 0.1–18 mS/cm.
Generally, conductivity of the order of 10 mS/cm is typical of
ionic liquids based on [EtMeIm]+ . On the other hand, ionic
liquids based on tetraalkylammonium, pyrrolidinium, piperi-
dinium and pyridinium cations are characterised by considerably
lower conductivities, in the range between 0.1 and 5 mS/cm.
Even the highest room temperature ionic liquid conductivity is
much lower in comparison to conventional aqueous electrolyte
solutions applied in electrochemistry (Table 3). For example,
the specific conductivity of aqueous KOH (29.4 wt.%) solu-
tion, applied in alkaline batteries, is 540 mS/cm. The electrolyte
applied in lead-acid batteries, 30 wt.% aqueous H2 SO4 , shows
a conductivity at the level of ca. 730 mS/cm. However, non-
aqueous solutions show one order of magnitude lower con-
ductivity. One of the most conductive Et4 NBF4 solutions, in
acterised by σ = 60 mS/cm. Lithium ion containing solutions, for
use in lithium-ion batteries, show a conductivity at the level of
10 mS/cm, similar to that characteristic for some ionic liquids.
The conductivity of a solution of LiPF6 (1 mol/dm3 ) in a mixture
of ethylene carbonate with l,2-dimethoxyethane (EC + DME)
is 16.6 mS/cm. A dilution of neat ionic liquids with solvents
(molecular liquids) also brings about an increase in conductiv-
ity. For example, the specific conductivity of neat [EtMeIm]
[BF4 ] is 14 mS/cm, while its 2 mol/dm solution in acetonitrile
shows a conductivity of 47 mS/cm. This is not unexpected, as
an ionic liquid + molecular liquid mixture is a solution of a salt
in a solvent, and therefore, ions are separated by solvent neu-
tral molecules. However, at high salt concentrations all solvent
molecules are involved in the ions primary salvation shell and
the resulting system, called ‘solvent in salt solution’ may show
properties rather characteristic for ionic liquids than that typical
of classical solutions. In such a case the conductivity increases
with the increasing amount of the salt, goes through a maximum

Table 3
Examples of conductivity of classical electrolytes in various electrochemical applications
Electrolyte Solvent σ [mS/cm] Application Reference

H2 SO4 (30 wt.%) H2 O 730 Lead-acid battery [57]

KOH (29.4 wt.%) H2 O 540 Alkaline battery [57]
NH4 Cl (25 wt.%) H2 O 400 Leclanche battery [57]
[Et4 N]+ [BF4 ]− (1 mol/dm3 ) AN 60 Double-layer capacitor
LiN(CF3 SO2 )2 (1 mol/dm3 ) EC + DME (1:1) 13.3 Lithium-ion battery [58]
LiN(CF3 SO2 )2 (1 mol/dm3 ) EC + DC (1:1) 6.5 Lithium-ion battery [57]
LiCF3 SO3 (1 mol/dm3 ) EC + DME (1:1) 8.3 Lithium-ion battery [58]
LiPF6 (1 mol/dm3 ) EC + DME (1:1) 16.6 Lithium-ion battery [58]
[Et4 N]+ [BF4 ]− (0.65 mol/dm3 ) PC 10.6 Double-layer capacitor [59]
[EtMeIm]+ [BF4 ]− (2 mol/dm3 ) AN 47 Double-layer capacitor [60]
[EtMeIm]+ [BF4 ]− (2 mol/dm3 ) PC 16 Double-layer capacitor [60]
 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580
and decreases with a further increase of the salt concentration.
However, most of molecular liquids have relatively low viscos-
ity, and therefore, the dilution of the viscous neat ionic liquid
with a molecular diluent decreases the viscosity of the mixture.
3.1. Influence of viscosity
The influence of the viscosity η on the ionic liquid conduc-
tivity (expressed as the molar conductivity Λ) may be illustrated
by a Λη value, having a sense of the Walden product (collected
in Table 2). Inspection of the Λη values, collected in Table 2,
shows that they are typically contained within a relatively narrow
range of 50 ± 20 × 10−7 Ns/mol, while the specific conductiv-
ities are within a broad range of 0.1–14 mS/cm. This indicates
that the viscosity plays important role in the ionic liquid con-
ductivity.
In a description of classical electrolyte solutions, the mobile
charge carrier is related to its diffusion coefficient D through the
Nernst–Einstein equation:
z2 e0 FD z2 NA e20 D
Λ= = (1)
kB T kB T
where, z represents the valence of the charge carrier, e0 the ele-
mentary charge, NA the Avogadro number, kB the Boltzmann
constant and F the Faraday constant. On the other hand, the dif-
fusion coefficient of a model spherical species of an effective
radius r depends on the medium viscosity, η, according to the
Stokes–Einstein equation:
kB T
D= (2)
6πrη
Combining Eqs. (1) and (2) and taking into account that
σ = Λc = Λn/V (n is the number of moles of the charge carrier)
and N = nNA is the number of charge carriers present in the vol-
ume V, lead to the following equation:
z2 e20 N
σ= (3)
6Vπr η
Hence, the conductivity σ of a classical electrolyte solution
is proportional to the number of charge carriers N and inversely
proportional to the medium viscosity η. However, the model of
ionic liquids assuming that the system consists entirely of ions
causes a conceptual problem regarding the distinction of indi-
vidual ionic species formed in the melt. If some ions of opposite
sign are sufficiently close to form relatively stable aggregates,
they may be regarded as neutral species which cannot be charge
carriers. At least one may expect that different ion–ion interac-
tion in various ionic liquid mixtures leads to the formation of
different ionic species (or ionic aggregates), and this is difficult
to define the number of charge carriers N.
3.2. Temperature dependence of the conductivity
In classical salt solutions solvent molecules separate ions, and
the thermodynamic properties of such solutions are described by
ion–solvent, ion–ion and solvent–solvent interactions, while in
5573
ionic liquids ions are not separated by solvent molecules, and
hence, they are always in contact. Their thermodynamic proper-
ties are described by ion–ion interactions, London interactions
and in some ILs by possible hydrogen bonding. If ionic liquids
consist entirely of ions, what is the number of charge carriers?
The ‘free space model’ called also the ‘hole model’ seems to be
the most efficient way of describing the ILs conductivity. The
model is based on the observation of a large fusion volume, of
ca. 20–30 vol%, exhibited by salts on their melting. The model
assumes that within the molten salt there are empty spaces, con-
stantly fluctuating in size, due to thermal motions. To quantify a
model, a probability of finding the hole in IL is calculated, which
leads to the following expressions for the diffusion coefficient
and conductivity:


−B
D = A exp (4)
(T − T0 )


−B
σ = σ0 exp (5)
(T − T0 )
Eqs. (4) and (5) are similar to the Vogel–Tammann–Fulcher
(VTF) equation originally describing the temperature depen-
dence of the viscosity: η = A exp(−B/(T − T0 ) [61]. The refer-
ence temperature T0 is related to a glass transition tempera-
ture (Tg ): T0 = Tg − const, as the charge is transported in the
amorphous phase of the system. The Tg value indicates the
temperature at which a solid-like material changes to a liquid-
like system. On the other hand, the reference temperature T0
may be ascribed to the ideal vitreous transition temperature, at
which segments of the system start to move. The glass tran-
sition temperature is always higher than the vitreous transition
temperature (Tg > T0 ), according to an empirical approximation:
T0 /Tg ≈ 0.75. Temperature of the glass transition, Tg , may be
determined from DSC measurements; T0 is adjusted arbitrarily
by subtracting ca. 50 K from the experimental Tg value, as for Tg
close to 200 K, T0 is expected to be close to 150 K (T0 ≈ 0.75Tg ).
The VTF equation may also be expressed in a number of mod-
ified forms. The most frequent modification is based on the
assumption that the pre-exponential factor is temperature depen-
dent: σ 0 = f(T), usually as σ 0 = AT−1/2 or σ 0 = A/T. Generally, in
the case of ionic liquids, the Tg value is not evaluated experi-
mentally together with the conductivity, but it is estimated from
a curve-fitting procedure, which usually leads to a reasonable fit
of the experimental data. However, different procedures or/and
data taken in a different temperature range may give different
output parameters (T0 , B, σ 0 or A). The liquid-to-glass transition
is still not theoretically well described and in addition, there are
a number of glass transition temperature practical definitions
[62,63]. Another problem is a possibility of ILs existence as a
different type of a glass former: ‘fragile’ or ‘strong’ liquid [64],
with possibility of a fragile-to-strong transition. Both types of
liquids shows qualitatively different temperature dependency of
the viscosity: strong liquids behave according to the Arrhenius
law, while the fragile liquids show a non-Arrhenius changes
of viscosity. Moreover, it was found experimentally that the
fragility is related to the potential of interactions between the
system elementary units (van der Waals, hydrogen-bonding).
5574 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580
This could explain different types of equations describing the
conductivity dependence on temperature, applicable for differ-
ent ionic liquids.
3.3. Transport and transference numbers
In most of the practical electrolyte applications not only a
high conductivity level, but also the contribution of various
charged species into the transfer of the total charge is impor-
tant. Let us assume a simple 1:1 electrolyte MX consisting of
monovalent ions M+ and X− . This property is usually described
in terms of the transport number, ti that can be defined for the
1:1 salt, consisting of monovalent ion, as follows:
Q+ u+
t+ = = and
(Q+ + Q− ) (u+ + u− )
Q− u−
t− = = (6)
(Q+ + Q− ) (u+ + u− )
where Qi is the charge transported by the charged species i and
ui is the corresponding ionic mobility. In such a case:
t+ + t − = 1 and 0 ≤ ti ≤ 1. (7)
The model neglects the possibility of ion association and is
valid as long as the mobile species are only simple ions M+ and
X− . The definition of the transport number is useful in diluted
electrolyte solutions. In ionic liquids the charge may be trans-
ported by all the mobile species present in the system, such as
simple ions as well as their charged combinations, for example
M+ X− , and MX2 − . In the general case, transference numbers
TM and TX , defined as the charge carried by a constituent M or
X, may be used instead of transport numbers ti for example as:
TM + tM+ − tMX2 − and TX = tX− (8)
Another problem is the reference against which the moving
charged species are observed. The flux may be measured against
the vessel containing the electrolyte or against species present
in the electrolyte solution. The external transport numbers are
expressed versus an element of the electrochemical cell, for
example a membrane or porous separator. The internal transport
numbers are expressed versus a component of the electrolyte.
In conventional electrolyte solutions, ions exist in the form of
solvato-complexes, and hence, the solvent molecules are parts of
moving ions. Consequently, in addition to the flux of ions, there
also exists a flux of the solvent. This flux leads to the formation
of a concentration change in the cathodic and anodic compart-
ments during the electrolysis. This concentration change is the
basis of the most popular Hittorf method of transference num-
bers determination. However, in the case of ionic liquids there is
no solvent and therefore the passage of electric current through
the cell brings about a difference of the molten salt mass in the
cathodic and anodic compartments, instead of the concentration
change, provided that a reversible reaction occurs at both elec-
trodes (for example Li+ reduction at cathode and simultaneous
oxidation of metallic Li anode). The external transport numbers
may be estimated using a three-compartment Hittorf-like cell,
where the compartments are separated by porous discs. After
the passage of the current through the cell, the mass of the ionic
liquid in each compartment may be determined by weighting.
However, the mass measurement is difficult and therefore the
use of the method is limited. Moreover, in the case of typical
cations present in ILs, such as quaternary ammonium, sulpho-
nium or phosphonium cations, the electrode reactions may be
irreversible and the products ill defined, which limits strongly
the application of the method. The moving boundary method
may also be applied for the external transport number determi-
nation in a U-shape cell. The boundary is established between
two phases possessing a common ion and a differing counter-
ion. To eliminate the hydrostatic flow, a porous disc is inserted
into the cell between cathodic and anodic compartment. The flux
brings about changes of the mass of electrolyte in both compart-
ments, and hence, the changes of the meniscus. If all the charge
is carried by the common ion, no movement of the meniscus
is observed. If the counter-ion is involved in the charge trans-
port, a movement of the meniscus would be observed. One of
the main problems is keeping a sharp boundary between both
phases. Transference numbers may be also estimated from the
diffusion coefficient of both cation and anion, according to:
D+ D−
t+ = and t− = (9)
(D+ + D− ) (D+ + D− )
The self-diffusion coefficient, as well as its temperature
dependence, of both anion and cation, may be estimated by using
pulsed-gradient spin-echo nuclear magnetic resonance (PGSE-
NMR) [28,65–69]. The measurements may be done with 1 H
(belonging to the quaternary ammonium cation) or 19 F (belong-
ing to tetrafluoroborate, triflate or imide anions). The method
does not distinguish ions and neutral associates, as NMR detects
the nucleus signal. Therefore, the self-diffusion coefficient esti-
mated with this method are average coefficients of ions and
their associates. The diffusion coefficient may be also deter-
mined with voltammetry, according to the Cotrell equation for
diffusion-controlled limiting current I0 [70].
Diffusion coefficients and transport numbers for some ionic
liquids are collected in Tables 4 and 5 respectively. It can be
seen from the Table 4 that the self-diffusion coefficients of ionic
liquid ions are of the order of 10−10 –10−11 m2 /s. These rela-
tively low values are due to the high ILs viscosity. On the other
hand, transport numbers are determined not by absolute dif-
fusion coefficient values, but by the differences between their
cationic and anionic values (D+ and D− ). It can be seen from
Table 5 that t+ and t− may be comparable, as in the case of
[BuPi][BF4 ] (t+ = 0.48, t− = 0.52) but they also may differ con-
siderably; [EtMeIm][AlBr4 ] may serve as an example (t+ = 0.76,
t− = 0.24).
4. Electrochemical stability
Electrolytes for application in electrochemical devices should
be resistant for electrochemical reduction and oxidation. There
are literature data (Table 6) on ionic liquids electrochemical
stability at different electrode materials, such as Pt, W, glassy
carbon (GC), graphite (G). The measurements were performed
in three electrode cells, applying different reference electrodes.
 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580 5575

Table 4
Diffusion coefficients for ionic liquid
Ionic liquid D+ [1011 m2 s−1 ] D− [1011 m2 s−1 ] T [K] Method Reference

[EtMeIm]+ [BF 4 ]− 5.0 4.2 298 NMR [28]a

[EtMeIm]+ [BF4 ]− 3.0 – 300 NMR [71]
[EtMeIm]+ [CF3 SO2 ]− 5.0 3.0 298 NMR [68]b
[EtMeIm]+ [N(CF3 SO2 )2 ]− 6.3 3.5 298 NMR [28]a
[EtMeIm]+ [N(CF3 SO2 )2 ]− 5.0 4.0 298 NMR [68]b
[BuPi]+ [BF4 ]− 0.91 1.0 298 NMR [28]a
[BuPi]+ [N(CF3 SO2 )2 ]− 2.4 2.0 298 NMR [28]a
[EtMeIm]+ [Al2 Cl7 ]− (1:2) 14.4 – 303 Electrochem. [65]
[EtMeIm]+ [AlCl4 ]− (1:0.8) 1.02 6.1c 303 Electrochem. [70]
[EtMeIm]+ [AlCl4 ]− (1:1) – 5.7c 299 Electrochem. [72]
[EtMeIm]+ [AlCl4 ]− (1:0.96) – 5.3c 299 Electrochem. [72]
[EtMeIm]+ [AlCl4 ]− (1:0.94) – 4.6c 299 Electrochem. [72]
[BuPi]+ [Al2 Cl7 ]− (1:2) 11.5 8.85 303 Electrochem. [73]
a Diffusion coefficients calculated from VTF parameters.
b Diffusion coefficients estimated from graphical data.
c Diffusion coefficients for the chloride ion.

Comparison of the data is difficult as reference systems were dif-
ferent and in some cases not strictly electrochemically defined.
For example, such systems as platinum [81], aluminium [83–86]
or silver [51,60] wires immersed in a solution under study were
used as a, quasi reference’. In such a case a redox couple deter-
mining the potential is not defined at all. However, in some cases
the reference system was defined exactly, for example Fc/Fc+
[39], I− /I3 − [25] or Ag/Ag+ (0.01 mol dm−3 in DMSO) [79].
The stability windows are reported to be in a broad range from
2 to 6 V. Halide anions such as F− or Br− , which undergo
anodic oxidation at relatively low potentials, are responsible
for a narrow stability of the order of ca. 2–3 V. The amide
anion, [N(CF3 SO2 )2 ]− , on the contrary, is oxidised at relatively
high anodic potentials, which implies the broad stability of ILs
based on this anion. The most common stability is around 4.5 V.
On the other hand, ionic liquids based on tetraalkylammonium
cations, which show cathodic reduction at relatively negative
potentials, are characterised by enhanced stability (4.0–5.7 V).
Stability windows obtained at Pt and GC electrodes are compa-
rable. On the other hand, the ILs/tungsten interface shows much
enhanced stability of the order of ca. 6.5–7 V. Both the reduc-
tion potential of cation and that of anion oxidation depend on the
counter-ion.
5. Ionic liquids containing lithium
The reduction of alkali metal cations, Na+ and Li+ , at such
electrodes as tungsten, glassy carbon, or aluminium in [EtMeIm]
[AlCl4 ] room temperature ionic liquid has been studied [87].
The general aim of these studies was to examine the possibility
of applying [EtMeIm] [AlCl4 ] as electrolyte in secondary bat-
teries. It has been found that lithium plated on tungsten could
not be stripped quantitatively from neutral [EtMeIm] [AlCl4 ]
melts. However, a reversible plating-stripping on a mercury
drop has been reported [88]. Later it was discovered that the
addition of hydrogen chloride to the [EtMeIm] [AlCl4 ] melt
resulted in a shift of the cathodic limit of the voltage window
to more negative values with nearly reversible plating-stripping
behaviour [85]. In 1996 Piersma and co-workers [89] applied the
trietanolamine complex with hydrogen chloride as a source of
protons: [EtMeIm][AlCl4 ] + LiCl + trietanolamine·HCl. It has
been found that the presence of the trietanolamine complex with
hydrogen chloride shifted the reduction potential of the melt to
more negative values as well as the lithium deposition-stripping
became nearly reversible.
In 1999 a room temperature ionic liquid for the use in lithium
battery was prepared by mixing solid salts: EtMeImCl, AlCl3

Table 5
Transport number for ionic liquid
Ionic liquid tcation tanion T [K] Method References

[EtMeIm]+ [BF4 ]− 0.54 0.46 298 NMR [28]a

[EtMeIm]+ [N(CF3 SO2 )2 ]− 0.64 0.36 298 NMR [28]a
[BuPi]+ [BF4 ]− 0.48 0.52 298 NMR [28]a
[BuPi]+ [N(CF3 SO2 )2 ]− 0.55 0.45 298 NMR [28]a
[EtMeIm]+ [AlCl4 ]− /[Al2 Cl7 ]− (0.8:1) 0.71 0.23 303 MH [74]
[EtMeIm]+ [AlCl4 ]− (1:1) 0.7 0.3 ca. 303 MB [75]
[EtMeIm]+ [AlCl4 ]− /Cl− (1:0.7) 0.71 0.29 298 MH [76]
[EtMeIm]+ [AlBr4 ]− (1:1) 0.76 0.24 333 MH [77]

PGSE: pulse-gradiend spin echo NMR; MH: modified Hittorf; MB: moving boundary.
a Transport numbers determined from self-diffusion data provided in the reference.
5576 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580

Table 6
Electrochemical stability windows of ionic liquids
Ionic liquids Cathodic limit [V] anodic limit [V] Electro-chemical References Working Ref. electrode
window electrode

Imidazolium
[EtMeIm]+ [F]− 0.7 2.4 3.1 [78] Pt Pt
[EtMeIm]+ [BF4 ]− −1.6 1 2.6 [79] Pt Ag|Ag+ in DMSO
−2.1 2.2 4.3 [29] Pt Ag|AgCl -wire
4.5 [46] Pt
1 5 4.0 [34] GC Li|Li+
[EtMeIm]+ [CF3 SO3 ]− −1.8 2.3 4.1 [25] Pt I− |I3 −
[EtMeIm]+ [N(CF3 SO2 )2 ]− −1.8 2.5 4.3 [25] Pt I− |I3 −
4.5 [48] GC
−2 2.1 4.1 [60] Pt Ag wire
−2 2 4.0 [51] Pt Ag wire
−2 −2.5 4.5 [79] Pt Ag|Ag+ in DMSO
[EtMeIm]+ [N(C2 F5 SO2 )2 ]− −2 2.1 4.1 [60] GC Ag wire
[EtMeIm]+ [(CN)2 N]− −1.6 1.4 3.0 [51] Pt Ag wire
[BuMeIm]+ [Br]− −2 0.2 2.2 [79] Pt Ag|Ag+ in DMSO
[BuMeIm]+ [BF4 ]− 1.2 5 4.2 [34] GC Li|Li+
4.1 [80] Pt
−1.6 4.5 6.1 [81] W Pt
−1.6 3 4.6 [81] Pt Pt
−1.8 2.4 4.2 [79] Pt Ag|Ag+ in DMSO
[BuMeIm]+ [PF6 ]− −1.1 2.1 3.2 [51] Pt Ag wire
4.2 [75] CNT
−2.1 >5 [81] W Pt
−2.3 3.4 5.7 [81] Pt Pt
−1.9 2.5 4.4 [79] Pt Ag|Ag+ in DMSO
[BuMeIm]+ [N(CF3 SO2 )2 ]− −2 2.6 4.6 [79] Pt Ag|Ag+ in DMSO
[EtMeMeIm]+ [N(CF3 SO2 )2 ]− −2 2.4 4.4 [25] Pt I− |I3 −
[PrMeIm]+ [N(CF3 SO2 )2 ]− 1 5.3 4.3 [34] GC Li|Li+
[PrMeMeIm]+ [N(CF3 SO2 )2 ]− −1.9 2.3 4.2 [60] GC Ag wire
5.0 5.2 [82] GC Li|Li+
[PrMeMeIm]+ [C(CF3 SO2 )3 ]− 5.4 5.4 [82]a GC Li|Li+
[PrMeMeIm]+ [PF6 ]− 5.0 4.3 [82]a GC Li|Li+
[PrMeMeIm]+ [AsF6 ]− 5.0 4.4 [82]a GC Li|Li+

Pyrrolidinium
[nPrMePy]+ [N(CF3 SO2 )2 ]− −2.5 2.8 5.3 [51] Pt Ag wire
−1.5 2.2 3.7 [79] Pt Ag|Ag+ in DMSO
[nBuMePy]+ [N(CF3 SO2 )2 ]− −3.0 2.5 5.5 [37] GC Ag|Ag+
−3.0 3.0 6.0 [52] grapfite Ag|Ag+
−1.8 2.0 3.8 [79] Pt Ag|Ag+ in DMSO
Tetraalkylammonium
[nMe3BuN]+ [N(CF3 SO2 )2 ]− −2.0 2.0 4.0 [52] carbon
[nPrMe3 N]+ [N(CF3 SO2 )2 ]− 5.7 [48] GC
−3.2 2.5 5.7 [39] GC Fc|Fc+
[nHexEt3 N]+ [N(CF3 SO2 )2 ]− 4.5 [54] GC
[nOctEt3 N]+ [N(CF3 SO2 )2 ]− 5.0 [54] GC
[nOctBu3 N]+ [N(CF3 SO2 )2 ]− 5.0 [54] GC
[Me3 (CH3 OCH2 )N]+ [N(CF3 SO2 )2 ]− 5.2 [37] GC
Pyridinium

[BP]+ [BF4 ]− −1 2.4 3.4 [29] Pt Ag|AgCl -wire

Piperidinium
[MePrPp]+ [N(CF3 SO2 )2 ]− −3.3 2.3 5.6 [29] GC Fc|Fc+

Sulfonium
[Et3 S]+ [N(CF3 SO2 )2 ]− 4.7 [55] GC
[nBu3 S]+ [N(CF3 SO2 )2 ]− 4.8 [55] GC
 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580
Table 6 (Continued )
Ionic liquids Cathodic limit [V] anodic limit [V]
Chloroaluminated
[EtMeImCl]/AlCl3
[EtMeImCl]/AlCl3 /LiCl
[EtMeImCl]/AlCl3 /NaCl −2.2 2.3
[PrMeMeImCl]/AlCl3 /NaCl
a Measured at 80 ◦ C.
and LiCl in the molar ratio: 1:1.2:0.15, respectively [90]. In
some cases C6 H5 SO2 Cl was added to the system, in order to
improve the stability of the system. The electrochemical sta-
bility window of the electrolyte was found to be 4.85 V at
the tungsten electrode. The anodic limit was detected at 2.5 V
and cathodic at −2.35 V, versus an Al/[EtMeIm] [AlCl4 ] ref-
erence. The electrolyte was tested in a LiAl/LiCoO2 battery
(based on lithium–aluminium alloy anode) showing a cell volt-
age of 3.45 V, coulombic efficiency of 90% and the capacity of
ca. 112 mAh/gram of LiCoO2 cathode at a current density of
1 mA/cm2 .
A number of room temperature ionic liquids containing
quaternary ammonium cations (1-ethyl-3-methylimidazo-
lium, [EtMeIm]+ , trimethylpropylammonium, [TMePrA]+ , N-
methyl-N-propylpyridinum, [MePrPi]+ , and N-methyl-N-pro-
pylpiperidinium, [MePrPp]+ ) and bis(trifluoromethanes-
ulfonyl)imide [N(CF3 SO2 )2 ]− anion were examined as elec-
trolytes for lithium anode batteries [39]. The electrochemical
stability window of the electrolytes were examined in a three
electrode cell applying a glassy carbon working electrode and
the ferrocene/ferrocinium (Fc/Fc+ ) redox-couple reference.
The stability window, shown in a picture, was of ca. 4 V in
the case of [EtMeIm][N(CF3 SO2 )2 ], and much broader for
the remaining electrolytes: ca. 5 V. The electrolytes were
tested in a Li/LiCoO2 system with a lithium-foil anode. The
[PrMePp][N(CF3 SO2 )2 ] electrolyte showed the best properties
in the battery: the charge/discharge coulombic efficiency was
close to 100% at a voltage between 3.2–4.2 V. The cell based on
[EtMeIm][N(CF3 SO2 )] did not show reproducible behaviour.
The best ionic liquid [MePrPp][N(CF3 SO2 )2 ], however, shows
a relatively low conductivity of ca. 1.5 mS/cm.
A eutectic melt, liquid in room temperature, was obtained
by mixing lithium bis(trifluoromethanesulfonyl)imide
(LiN(CF3 SO2 )2 ) with acetamide, with the eutectic tempera-
ture of −67 ◦ C, the eutectic composition of LiN(CF3 SO2 )2 :
Acetamide = 1:4 [91] and the conductivity at a level of ca.
1 mS/cm. The electrochemical stability window, determined in
a three-electrode cell with nickel or copper working electrodes
and lithium counter- and reference-electrodes, was of ca.
4 V. The electrolyte was tested in a cell with lithium anode:
Li/LiMnO2 . A long voltage plateau at 2.82 V was observed dur-
ing discharge of the cell and two plateau at 3.1 and 3.4 V during
charging. Ternary ionic liquids: [EtMeIm]+ + [BF4 ]− + Li+
and [EtMeIm]+ + [N(CF3 SO2 )2 ]− + Li+ have been stud-
ied as electrolytes in lithium-ion battery with Li4 Ti5 O12
anode and LiCoO2 cathode [92]. Cyclic and power
experiments with ionic liquids have been compared to
5577
Electro-chemical References Working Ref. electrode
window electrode
4.4 [83] W Al wire
4.3 [84] W Al wire
4.5 [85] W Al wire
4.6 [86] W Al wire
those obtained with conventional 1 mol/dm3 solution of
[LiN(CF3 SO2 )2 ]− in organic solvent (EC + DMC). Batteries
with [EtMeIm]+ + [N(CF3 SO2 )2 ]− + Li+ ionic liquid delivered
up to 106 mAh/g after 200 cycles. The result was better than
that obtained with [EtMeIm]+ + [BF4 ]− + Li+ ionic liquid or
with the conventional LiN(CF3 SO2 )2 in EC + DMC electrolyte.
Ionic liquids based on quaternary ammonium cations contain-
ing cyano groups have been examined from the point of view
of their potential application in lithium batteries. It has been
found, that the presence of such a cation in a multicomponent
IL a reversible reduction/oxidation of lithium at stainless steel
may be achieved [93,94]. To our knowledge, ionic liquids have
not been applied in lithium-ion batteries with the graphite anode.
6. Ionic liquids as electrolytes for electrochemical
capacitors
Electrochemical capacitors, based on the capacity of the
double layer formed at the electrode/electrolyte interface, have
received considerable attention during the last decade, as
they seem to be promising high power-density energy-storage
devices. Double-layer electrochemical capacitors (DLEC) offer
an order of magnitude higher power density and at least two
orders of magnitude higher number of charge–discharge cycles
(>100,000), but an order of magnitude lower energy-density, all
in comparison to batteries [95,96].
The literature data on the capacity of the electrode/IL inter-
face are limited to a few studies [47,97]. Osteryoung and co-
workers studied the capacity of the electrode/electrolyte inter-
face in ionic liquid based on the chloroaluminate ion [97].
Only one paper [47] about specific capacitance at the elec-
trode/electrolyte interface for glassy carbon (GC), mercury
and a commercial carbon and four ionic liquids based on 1-
ethyl-3-methyl imidazolium cation can be found in the litera-
ture. The integral capacitance of the ionic liquids at the drop-
ping mercury electrode ranged between 10.6 and 12.4 ␮F/cm2 .
For the [EtMeIm][N(CF3 SO2 )2 ] electrolyte the capacitance
was 11.7 ␮F/cm2 at DME and 12.0 at glassy carbon, but
only 3.7 ␮F/cm2 at a high-surface SpectraCarb 2220 yarn (ca.
2000 m2 /g), probably due to poor wettability of the activated
carbon pores by the ionic liquid. This may indicate that the
accessibility of the electrolyte to the carbon electrode surface
limits the realisable specific capacitance of the device.
As ionic liquids show a broad electrochemical stability win-
dow of ca. 4 V, conductivity at a level of ca. 10 mS/cm as well as
an acceptable specific capacity of ca. 10 ␮F/cm2 , makes them
5578 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580
promising candidates for electrolytes. However, there are only a
few papers about capacitors based on carbon materials and ionic
liquids. In 1997–1999 some results on applying IL solutions
in supercapacitors were reported [60,98]. Ionic liquids based
on the [EtMeIm]+ cation ([EtMeIm][BF4 ] and [EtMeIm][PF6 ])
were dissolved in cyclic carbonates. Capacitors showed a spe-
cific capacity, of ca. 130 ␮F expressed versus 1 g of active carbon
and the electrochemical stability within the voltage range of ca.
3.5 V.
A series of electrochemical capacitors, based on acti-
vated carbon powders (ACP, specific surface area 870 and
2600 m2 /g) and ionic liquids as electrolytes, were prepared
and tested [99]. The ionic liquids consisted of 1-ethyl-3-
methyl imidazolium EtMeIm]+ , 1-buthyl-3-methyl imidazolium
[BuMeIm]+ and 1-methyl-1-propyl pyrrolidinium [BuMePy]+
cations as well as of tetrafluoroborate, hexafluorophosphate
and bis((trifluoromethyl)sulfonyl)imide anions. The capacity
expressed versus the total surface of the carbon material was in
the range of 5.2–6.9 ␮F/cm2 and expressed versus the activated
carbon mass in the range of 45 F/g (ACP 870 m2 /g)–180 F/g
(ACP 2600 m2 /g). The electrochemical stability window of ionic
liquids determined at a glassy carbon electrode was in the range
of ca. 3.0–4.2 V.
Electrochemical capacitors, based on carbons as electroac-
tive materials and polymer-IL solid electrolytes were prepared
and tested [100]. Both polymer electrolytes as well as capacitor
electrodes, in the form of thin foils, were prepared by a cast-
ing technique. All-plastic capacitors, having a coin-like shape,
a diameter of 18 mm and a mass of ca. 200–900 mg, were con-
structed by sandwiching a polymer electrolyte between two elec-
trodes. Ionic liquids: 1-ethyl-3-methylimidazolium tetrafluorob-
orate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethane sul-
fonyl)imide and l-butyl-3-methylimidazolium hexafluorophos-
phate served both as sources of ions as well as polymer plasti-
cizers. In some cases sulpholane was added to the system as an
additional plasticizer. The capacity calculated per total surface
of the carbon material was in the range of 4.2–7.7 ␮F/cm2 , and
the specific capacity (expressed versus the mass of the carbon)
up to 200 F/g.
To date, the literature on the subject is limited to a few papers,
described above, on ionic liquid based capacitors. However,
ionic liquids seem to be promising candidates for electrolytes in
high-energy capacitors, as they (i) produce high specific capacity
at the AC/IL interface of the order >100 ␮F/g of carbon and (ii)
they show a broad electrochemical stability window (as deter-
mined at the glassy carbon) of the order of 4 V.
7. Low-temperature aluminium electrodeposition and
recovery
Most aluminium metal is produced by electrolysis of Al2 O3
eutectic with Na3 AlF6 at temperature of ca. 1000 ◦ C. Aluminium
coatings exposed to air become covered with the aluminium
oxide layer which shows very good adherence to the protected
steel surface and is resistant to corrosion. There are a few
methods of plating with aluminium such as: spray coating, roll
binding, hot dipping or electrolytic plating. Due to the negative
standard potential of the Al/Al(III) couple the electrodeposition
of aluminium from aqueous solutions is not possible. Hence,
solutions of electrolytes in organic aprotic solvents or molten
salts may be applied for aluminium electrodeposition. Moreover,
the system must operate in an inert atmosphere, free of mois-
ture. There are three types of organic solvents successfully used
for aluminium electroplating: aromatic hydrocarbons (benzene,
toluene, xylene), dimethylsulfone (Me2 SO2 ) and ethers (Et2 O
or THF).
Room temperature ionic liquids have been researched from
the point of view of their application for aluminium production
and electroplating on steel [101–105]. Low-temperature electro-
plating melts can be represented as MX + AlX3 binary systems,
where X is a halide anion (Cl− or Br− ) and M is an inorganic
cation (Li+ , Na+ or K+ ) or organic cation (quaternary ammo-
nium cation). Generally, MX + AlX3 melts with organic cation
are liquid in room temperature, while inorganic are liquid above
100 ◦ C. Mixing of aluminium halide AlX3 with a salt RX results
in the following equilibria:
mAlCl3 + nMX
mMAlX4 + (n − m)MX (for n > m)
(10)
mAlCl3 + nMX
(2n − m)MAlX4 + (m − n)MAl2 X7
(for n < m) (11)
In other words, at the excess of MX, aluminium exists mainly
in the AlX4 − form and at the AlCl3 excess as both AlX4 − and
Al2 X7 − , but the latter may be predominant. The equilibrium
between AlX4 − and Al2 X7 − can be expressed as follows:
Al2 X7 − + X−
2AlX4 − (12)
The Al2 X7 − anion is a Lewis acid and hence the X− anion is a
conjugate Lewis base. Consequently, melts in which halide ions
are in excess (n > m) are basic, and melts formed from equivalent
amounts of both components (n = m) are neutral. An addition of
an excess of MX salt leads to acidic melts in the Lewis sense.
Aluminium deposition is possible from both AlX4 − and
Al2 X7 − anions:
AlX4 − + 3e− → Al + 4X− (13)
4Al2 X7 − + 3e− → Al + 7AlX4 − (14)
If the salt MX contains inorganic cation M+ , aluminium
electrodeposition is possible both from basic and acidic melts.
However, in the case of organic room temperature ionic liquids
the anion AlX4 − is reduced at potentials more negative than
those typical for organic cations M+ and as a result, aluminium
electroplating from RTILs is possible only from acidic melts.
8. Conclusions
1. The physicochemical properties of room temperature (or
low temperature) ionic liquids are the same as those char-
acteristic for high temperature ionic liquids, but the prac-
tical aspects of their maintenance or handling are different
enough to merit a distinction.
 M. Galiński et al. / Electrochimica Acta 51 (2006) 5567–5580
2. RTILs show a strong tendency for supercooling. The dif-
ference between melting point and temperature of solidi-
fication may be as high as 200 ◦ C. As a result, the same
compound can be described in the literature as solid or liq-
uid at room temperature. Moreover, some authors never give
melting nor freezing (solidification) points, only stating that
a salt is liquid or not.
3. Density of ionic liquids, shown is usually higher than 1 g/ml,
typically 1.2–1.5 g/ml. However, there are ionic liquids
showing a density lower than 1 g/ml. Viscosity of ionic liq-
uids, typically at the level of 30–50 cP, is much higher than
that characteristic for water and aqueous solutions (a level
of ca. 1 cP), but in some cases as high as 500–600 cP. The
high viscosity of ionic liquids, causes difficulties with their
handling.
4. The room temperature conductivity of RTILs, contained
within a broad range of 0.1–14 mS/cm, is much lower
than that characteristic for conventional aqueous electrolyte
solutions applied in electrochemistry (500–700 mS/cm) as
well as some nonaqueous solutions (60 mS/cm), but may
be in some cases comparable to lithium electrolytes (ca.
10 mS/cm). A dilution of neat ionic liquids with solvents
(molecular liquids) brings about an increase in conduc-
tivity. The influence of the viscosity on the ionic liquid
conductivity may be illustrated by a Λη value, having a
sense of the Walden product. The Λη values are within
a relatively narrow range of 50 ± 20 × 10−7 Ns/mol, in
contrast to the specific conductivities. This indicates that
the viscosity plays important role in the ionic liquids con-
ductivity. Usually, temperature dependence of conductivity
is described by the Arrhenius equation. However, in many
cases the ln σ = f(l/T) function is not linear, and instead of
the Arrhenius relation the Vogel–Tammann–Fulcher equa-
tion is applied (σ = σ 0 exp{−B/(T − T0 )} where σ 0 = AT−1/2
or σ 0 = A/T).
5. The self-diffusion coefficients of ionic liquid ions are of the
order of 10−10 –10−11 m2 /s. These relatively low values are
due to the high ILs viscosity.
6. Transport numbers of ions in RTILs are determined not by
absolute diffusion coefficient values, but by the differences
between their cationic and anionic values (D+ and D− ). In
some cases t+ and t− are comparable, but in some cases they
may differ considerably.
7. Ionic liquids electrochemical stability was measured at
different electrode materials, such as Pt, W, glassy car-
bon (GC), graphite (G), applying different reference elec-
trodes. Comparison of the data is difficult as the ref-
erence electrodes were in some cases not strictly elec-
trochemically defined (quasi-reference electrodes, such
as silver or platinum wire immersed in the solution
under study). The stability windows are reported to
be in a broad range from 2 to 6 V, typically 4.5 V.
RTILs based on tetraalkylammonium cations, which show
cathodic reduction at relatively negative potentials, are
characterised by enhanced stability (4–5.7 V). Potentials
of cation reduction and anion oxidation are mutually
dependent.
5579
8. The literature data on the capacity of the electrode/IL inter-
face are limited to a few studies. The capacity of the
ionic liquids/mercury interface ranged between 10.6 and
12.4 ␮F/cm2 and 11.7–12.0 ␮F/cm2 at ionic liquid/glassy
carbon interface.
9. There were some attempts to use room temperature ionic
liquids as electrolytes in lithium batteries, by dissolving a
lithium salts in an ionic liquid. The resulting electrolyte
was an ionic liquid consisting of three or four ions. Also
a eutectic obtained by mixing a lithium salt with a molec-
ular compound (acetamide) was applied as an electrolyte.
The following anodes were tested: Li4 Ti5 O12 , lithium and
aluminium, but not graphite. Cyclic and power experiments
with ionic liquids showed poor properties as compared to
those obtained with conventional lithium salt solutions in
organic solvent, working with graphite anode.
10. Room temperature ionic liquids have been researched from
the point of view of their application for aluminium pro-
duction and electroplating on steel, without any promising
results.
11. As ionic liquids show a broad electrochemical stability win-
dow of ca. 4 V, conductivity at a level of ca. 10 mS/cm as
well as the double-layer specific capacity of ca. 10 ␮F/cm2 ,
they are very good electrolytes for double-layer capacitors.
The specific capacity of electrodes based on high surface
carbon and ionic liquids may be as high as 180 ␮F/g.
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