Journal of Physics and Chemistry of Solids 65 (2004) 281–286

www.elsevier.com/locate/jpcs

Carbon –ionic liquid double-layer capacitors

A. Lewandowski*, M. Galiński
Faculty of Chemical Technology, Poznań University of Technology, PL-60 965 Poznań, Poland
Accepted 2 September 2003

Abstract
A series of electrochemical capacitors, based on activated carbon powders (ACP, specific surface area 870 and 2600 m2/g) and ionic
liquids as electrolytes, were prepared and tested. The ionic liquids consisted of 1-ethyl-3-methyl imidazolium (EMImþ), 1-butyl-3-methyl
imidazolium (BMImþ) and 1-methyl-1-propyl pyrrolidinium (BMPyþ) cations, as well as of tetrafluoroborate, hexafluorophosphate and
bis((trifluoromethyl)sulfonyl) imide anions. A typical capacitor consisted of two electrodes each with a mass of ca. 15 – 30 mg, and showed a
capacity of ca. 0.35– 1.5 F; this leads to a specific capacity of the carbon electrode material within the range of 45 (ACP 870 m2/g) – 180 F/g
(ACP 2600 m2/g). The specific capacity expressed versus total surface of carbon material was within the range of 5.2 – 6.9 mF/cm2. The
electrochemical stability window of ionic liquids determined at the glassy carbon electrode is within the range of ca. 3.0 –4.2 V. The energy
stored in a capacitor based on activated carbons and ionic liquids may be high, due to a broad practical electrochemical stability window of
ca. 3 V. Ionic liquids are characterised by negligible vapour pressure; such a capacitor emits no volatile organic compounds and may be
regarded as environmentally friendly.
q 2003 Elsevier Ltd. All rights reserved.

1. Introduction This paper presents the results of studies on the

Over the last decade electrochemical capacitors have
received much attention due to their possible application as
high-power energy-storage devices. Double-layer electro-
chemical capacitors, based on carbon materials having a very
high-surface area, have been developed with very promising
results [1 – 3]. Both aqueous and various non-aqueous
liquid electrolytes as well as solid polymer electrolytes
have been applied [4 – 12]. Application therein of
electrolyte solutions in non-aqueous solvents offers a greater
electrochemical stability window, and hence, higher energy
density.
Ionic liquids, a new kind of solvent [13 – 15], may be
regarded as potential electrolytes for application in double-
layer electrochemical capacitors. Ionic liquids, which are
molten salts, consist entirely of ionic species. Until now,
ionic liquids have been applied in capacitors, as solutions in
molecular liquids (cyclic carbonates) [16,15], making the
system similar to conventional solutions of organic salts in
non-aqueous solvents.
* Corresponding author. Fax: þ 48-6187825.
E-mail address: andrzej.lewandowski@put.poznan.pl
Lewandowski).
0022-3697/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2003.09.009
application of ionic liquids as electrolytes for electroche-
mical capacitors without using any solvent as a diluent. The
main purpose of the work was to examine the performance
of a capacitor based on activated carbon as an electrode
material and a fused salt as an electrolyte (ionic liquids are
room-temperature fused salts). Capacitor electrodes were
prepared by the casting technique, from activated carbon
powder and a copolymer of poly(vinylidene fluoride) with
hexafluoropropylene (PVdF-co-HFP) playing the role of a
binder. The PVdF-co-HFP system has been used before as a
matrix of a gel polymer electrolyte [18], as a membrane in
lithium batteries, and as an electrode binder material
[19 –21] or as a membrane [22].
2. Experimental
2.1. Materials
Activated carbon powders (ACP): Fluka (cat. No. 231533,
loss on drying 10 wt%, 870 m2/g) and Kansai (Maxsorb,
(A. 2600 m2/g), were dried for 8 h at 120 8C prior to their
application as electrode active materials. Poly(vinylidene
282 A. Lewandowski, M. Galiński / Journal of Physics and Chemistry of Solids 65 (2004) 281–286
Table 1
Ionic liquids used in this work
Ionic liquid Cation
EMImBF4
BMImBF4
BMImPF6
EMImN(Tf)2
BMPyN(Tf)2
fluoride-co-hexafluoropropylene) (PVdF-co-HFP, Aldrich,
Cat. No. 42,716-0) was used as received.
2.2. 1-Ethyl-3-methyl imidazolium bromide (EMImBr)
EMIBr was prepared from 147 g of ethylbromide (Fluka,
freshly distilled) which was slowly added to a solution of
37 g of 1-methyl imidazole (Fluka) in 100 ml of 1,1,1-
trichloroethane (P.O.Ch.). The solution was stirred for 3 h at
room temperature and then refluxed for 4 h at 70 8C. The
two-phase system was separated in a separatory funnel, and
the lower phase, containing the salt washed twice with
100 ml portions of 1,1,1-trichoroethane and then dried at
70 8C at reduced pressure. Yield: 53.5 g (62%).
2.3. Silver tetrafluoroborate (AgBF4)
AgBF4 was prepared by reacting tetrafluoroboric acid
(HBF4, Fluka, 48% solution in water) with silver oxide
(P.O.Ch. Gliwice, Poland).
2.4. 1-Ethyl-3-methyl imidazolium tetrafluoroborate
(EMImBF4) in aqueous solution
The clear aqueous solution of AgBF4, obtained in the
manner described above, was titrated with a solution of
EMImBr (30 g in 100 ml of water) versus a silver indicating
electrode (silver wire) with saturated calomel reference
electrode, until the equivalent point (22.0 g EMImBr).
Then, the solution was stirred for 2 h. The yellow AgBr
precipitate was filtered off from the EMImBF4 solution, and
water removed from the clear filtrate by vacuum evapor-
ation at 80 8C and the remaining pale-yellow liquid salt
dried at same condition for 6 h. Yield: 15.0 g (70%)
2.5. 1-Ethyl-3-methyl imidazolium tetrafluoroborate
(EMImBF4) in acetonitrile solution
Anion
Into a solution of 14.2 g EMImBr in 250 ml of
BF2
4 acetonitrile, 7.78 g of NH4BF4 (Aldrich) was added and
the solution stirred for 3 h. The white NH4Br precipitate was
BF2
4
filtered off and acetonitrile evaporated from the clear filtrate
(EMImBF4 solution in acetonitrile) under vacuum at 60 8C;
PF2
the remaining liquid salt was dried at 80 8C under vacuum.
6
Yield: 13.7 g (93%).
2.6. 1-Ethyl-3-methyl imidazolium
bis((trifluoromethyl)sulfonyl) imide (EMImN(CF3SO2)2,
or EMImNTf2)
An aqueous solution of 17.6 g of LiN(CF3SO2) (Fluka) in
60 ml of water was mixed with a solution of 11.0 g of
EMImBr in 30 ml of water and the system stirred for 2 h at
70 8C. The ionic liquid (EMImN(Tf)2) was extracted from
the aqueous phase with two 30 ml portions of dichloro-
methane and the solvent distilled off under vacuum at 60 8C
and dried for 2 h. Yield: 24.0 g (89%).
2.7. 1-Butyl-3-methylimidazolium chloride (BMImCl)
A 92.5 g of chlorobutane (Fluka) was mixed with 82.0 g
of 1-methylimidazole and stirred for 70 h at 60 8C. The
resulting yellow, viscous liquid mixture was cooled to room
temperature, washed three times with 100 ml portions of
ethyl acetate and the BMImCl crystals were dried under
vacuum at 60 8C for 4 h. Yield: 138.4 g (79%)
2.8. 1-Butyl-3-methyl imidazolium hexafluorophosphate
(BMImPF6)
An aqueous solution of 50 ml of HPF6 (Fluka) was
dropwise added into a solution of 52 g of BMImCl in 300 ml
of water and stirred for 36 h. The two-phase system was
separated, and the lower phase (the ionic liquid) washed
with 100 ml water portions until the neutral pH value. The
yellow liquid salt was dried under vacuum at 80 8C. Yield:
66.0 g (78%).
2.9. 1-Butyl-3-methyl imidazolium tetrafluoroborate
(BMImBF4)
A solution of 32 g NaBF4 in 40 ml of water was added
dropwise to a solution of 52 g of BMICl in 40 ml of water
and stirred for 12 h; the reacting vessel was cooled with ice.
The two-phase system was separated and the lower phase
(liquid BMImBF4) was washed twice with 100 ml portions
of dichloromethane and twice with 30 ml portions of water.
The ionic liquid was first dried with an addition of
anhydrous MgSO4 and after filtration under vacuum at
60 8C for 4 h. Yield: 43 g (65%).
 A. Lewandowski, M. Galiński / Journal of Physics and Chemistry of Solids 65 (2004) 281–286
2.10. 1-Methyl-1-propyl pyrrolidinium iodide (BMPyI)
Butyl iodide (30.25 ml) was added to a solution of 27 ml
of 1-methyl-pyrrolidine (Fluka) in 70 ml of acetonitrile, and
the resulting solution stirred for 24 h at 60 8C. The
acetonitrile was distilled off under vacuum and the crystals
of BMPyI washed four times with n-hexane and dried for
24 h under vacuum. Yield: 60 g (89%).
2.11. 1-Butyl-1-methyl pyrrolidinium
bis((trifluoromethyl)sulfonyl)imide (BMPyN(CF3SO2)2,
or BMPyNTf2)
A solution of 30 g (0.111 mol) of BMPyI in 40 ml of
water was mixed with a solution of 32 g (0.111 mol) of
LiN(CF3SO2) in 40 ml of water and the resulting mixture
stirred for 24 h at room temperature. The resulting two-
phase system was separated in a separating funnel, the lower
phase consisting of BMPyNTf2 was washed twice with
70 ml portions of water, and finally the ionic liquid was
dried under vacuum at 60 8C for 8 h. Yield: 42.5 g (90%).
All ionic liquids were finally dried at reduced pressure over
molecular sieves. Ionic liquids used in this work are shown
in Table 1.
2.12. Capacitors
Polymer (PVdF-co-HFP) was left overnight in 1-methyl-
2-pyrrolidone (NMP, Merck, . 99%) and carbon material
(ACP mixed with acetylene black, AB) was added into the
viscous solution of PVdF-co-HFP in NMP and stirred for
1 h. The slurry was cast on to an aluminium plate and after
NMP evaporation (under a stream of dry nitrogen) a PVdF-
co-HFP þ ACP þ AB membrane, with a thickness of ca.
0.4 mm, was removed from the plate. Capacitor electrodes
of 12.5 mm diameter were cut out of the membrane. The
capacitor, having a coin-type shape, was built from two
electrodes separated by a filtering paper, all soaked with
ionic liquid and locked in a test cell. All operations were
done in a glove-box in a dry nitrogen atmosphere.
2.13. Measurements
Capacitors impedance spectra were measured over the
frequency range from 0.01 Hz to 100 kHz (applying the
Atlas-Sollich system, Poland). The cyclic voltammetry
measurements of capacitors were performed in a two-
electrode cell using an electrochemical system mAutolab
(EcoChemie, the Netherlands). The galvanostatic charging
and discharging experiments were performed using the ZT-
980-4 system (Unitra, Poland). The self-discharge charac-
teristic was measured with the mAutolab after charging the
capacitor potentiostatically. The electrochemical stability
windows of ionic liquids were obtained from cyclic
voltammetry using the mAutolab in a three electrode cell.
Electrolytes were placed between a gold counter electrode
283
with a diameter of 18 mm and a surface of 2.2 cm2 (with
a central hole for a reference electrode) as well as a working
glassy carbon electrode with a surface of 0.286 cm2. A
silver/silver(I) couple in dimethylsulphoxide (Ag/Agþ
0.01 mol dm23 in DMSO) was used as the reference
electrode.
3. Results and discussion
Fig. 1 shows an example of a typical cyclic voltammo-
gram of a capacitor containing EMIBF4 as an electrolyte,
taken at a voltage range of ^ 1 V at a polarisation rate of
5 mV/s. As may be seen, the voltammogram has an almost
ideal rectangular shape, typical of the pure capacitive
behaviour of the device. Capacitors soaked with the
remaining ionic liquids led to a similar shape of the cyclic
voltammogram. A typical capacitor, based on activated
carbon of the specific surface area of ca. 2600 m2/g (an
example is shown in Fig. 1) consisted of two electrodes of a
mass each of ca. 15 – 30 mg, had a capacity of ca. 0.7 – 1.5 F,
which leads to a specific capacity of the carbon material
within the range of 160 –180 F/g (Table 2). Capacitors
based on activated carbons of a lower specific surface area
(870 m2/g) showed a capacity at the level of ca. 45– 55 F/g.
The specific capacity expressed versus total surface of
carbon material was within the range of 5.2 –6.9 mF/cm2.
The same values of specific capacity were obtained from
galvanostatic charging – discharging.
It is difficult to compare the specific double-layer
capacitance obtained here with those determined for non-
porous electrodes (solid glassy-carbon and liquid mercury)
due to the fact that the proper literature data on ionic liquids
are limited to a few works [23,24]. Except the report on
ionic liquids based on the chloroaluminate ion [24], a paper
Fig. 1. Cyclic voltammetry of a capacitor consisting of two electrodes, a
mass of 16.8 mg, 17.0 mg, and a composition: PVdF-co-HFP (42.8 wt%),
ACP Kanasiw 2600 m2/g, (51.6 wt%), AB (5.6 wt%). Electrolyte:
EMImBF4. Sweep rate 5 mV/s.
284 A. Lewandowski, M. Galiński / Journal of Physics and Chemistry of Solids 65 (2004) 281–286

Table 2
Conductivity of ionic liquids (IL) and their electrochemical stability window at the glassy carbon (potentials (V) expressed versus Ag/Agþ 0.01 M in DMSO
reference) as well as specific mass (F/g) and surface (mF/cm2) capacity at the AC/IL interface for two activated carbons (AC) of specific surface 870 and
2600 m2/g; T ¼ 25 8C

Ionic liquid Stability window Conductivity (mS/cm) AC 870 m2/g AC 2600 m2/g

Cathodic Anodic F/g mF/cm2 F/g mF/cm2

EMImBF4 22.1 2.1 13.8 [17] 55 6.3 178 6.8

BMImBF4 22.1 2.1 2.3 [25] 50 5.7 155 5.7
BMImPF6 22.1 2.0 1.9 [25] 45 5.2 160 6.1
EMImN(Tf)2 22.1 2.0 8.4 [17] 51 5.9 180 6.9
BMPyN(Tf)2 21.0 2.0 2.2 [26] 48 5.8 167 6.4

about specific capacitance at the electrode/IL interface for electrode reactions, which can additionally limit the stability
glassy carbon (GC), mercury and a commercial carbon as window. At higher polarisation voltages (Figs. 2 and 3), as
electrode material and four ionic liquids based on 1-ethyl-3- well as at higher polarisation rates, voltammetric curves
methyl imidazolium cation can be found in the literature. may change their shape. Here, with increasing voltage (up to
The integral capacitance of various ionic liquids at the 3.5 V) applied to the electrodes, the shape of the voltam-
dropping mercury electrode (DME) ranged between 10.6 metric curves still remains rectangular.
and 12.4 mF/cm2. For the EMImN(Tf)2 electrolyte the Although the process of charge separation (charging–
capacitance was 11.7 mF/cm2 at DME and 12.0 at GC, but discharging of the double layer) takes place at the two-
only 3.7 mF/cm2 at a high-surface SpectraCarb 2220 yarn dimensional electrode/electrolyte interface, a coupled
(ca. 2000 m2/g). This may indicate that the accessibility of process of ions transfer (diffusion and migration) takes
the electrolyte to the carbon electrode surface limits the place in porous, three-dimensional carbon electrodes.
realisable specific capacitance of the device. Fig. 4 shows the relation between imaginary ðZ 00 Þ and
The cathodic limit of the electrochemical stability window real ðZ 0 Þ impedance components of the system for a
of the ionic liquids based on EMImþ and BMImþ cations, frequencies range (0.01 Hz –99.9 kHz). The impedance
investigated at the glassy carbon electrode, is 22.1 V against plot consists of a semicircle at higher frequency and two
the Ag/Agþ (0.01 M in DMSO) reference. The BMPyþ cation
linear sections at middle and low frequencies. The line
is reduced at the glassy carbon at considerably more positive
within the middle frequency range exhibits a slope close
potential, at ca. 2 1.0 V. The anodic oxidation of the
to 458, and represents the Warburg impedance of the
tetrafluoroborate anion occurs at potentials higher than
system. Such an impedance spectrum shape is typical of
2.1 V and the remaining hexafluorophosphate and imide
systems consisting of distributed capacitance and inter-
anions are oxidised at potentials higher than 2.0 V. Hence, the
facial resistance, or in other words, of devices built of
stability window of the EMImBF4 and BMImBF4 is
4.2 V. Ionic liquids BMImPF6 and EMImN(Tf)2 shows a porous, high-area electrodes [1]. The imaginary part of
similar stability window of ca. 4.1 V. However, the window of
the BMPyN(Tf)2, is considerably lower: ca. 3.0 V. This is
consistent with data (ca. 4.1–4.2 V) reported for a series of
ionic liquids based on EMImþ and DMPImþ (1,2-dimethyl-3-
propylimidazolium) cations [16]. The addition of a diluent
(solvent), increases the conductivity, but also influences the
stability window. It has been found, that among the most
popular organic solvents, 2 M solutions in acetonitrile showed
the highest conductivity level (EMImN(Tf)2: 47 mS/cm and
EMImPF6: 60 mS/cm) and a broader stability window
(ca. 4 V) [16]. Carbonate solvents decrease the cathodic
limit by ca. 0.2–0.4 V, depending on the carbonate structure.
Ionic liquids are well known of broad electrochemical
stability windows, however, the practical voltage which can
be applied to capacitor carbon electrodes seems to be
considerably lower. This is because the stability window is
usually determined at glassy carbon electrodes while the
Fig. 2. Cyclic voltammetry of a capacitor consisting of two electrodes, a
capacitor electrodes are formed from different kinds of mass of 19.4 mg, 19.7 mg, and a composition: PVdF-co-HFP (42.8 wt%),
activated carbons, possessing functional groups at their ACP Kanasiw 2600 m2/g, (51.6 wt%), AB (5.6 wt%). Electrolyte:
surface. Moreover, the polymer may also undergo redox EMImN(Tf)2. Sweep rate 5 mV/s.
 A. Lewandowski, M. Galiński / Journal of Physics and Chemistry of Solids 65 (2004) 281–286
Fig. 3. Cyclic voltammetry of a capacitor consisting of two electrodes, a
mass of 29.0 mg, 26.9 mg, and a composition: PVdF-co-HFP (34.9 wt%),
ACP 870 m2/g, (58.7 wt%), AB (6.4 wt%). Electrolyte: BMPyN(Tf)2.
Sweep rate 5 mV/s.
the impedance, Z 00 ; determines the capacity of the device,
according to: C ¼ ð2pfZ 00 Þ21 : The capacity increases with
decreasing frequency of the polarisation, and at the lower
frequency section the capacity stabilises at values
comparable to that obtained from cyclic voltammetry or
galvanostatic charging – discharging (Fig. 5).
The charged capacitor is thermodynamically in a state of
higher energy in respect to the discharged device, which is
equivalent to a driving force for a spontaneous self-
discharge process when the device is left on open circuit.
When capacitors were loaded initially to the potential
difference between electrodes of 1.5 V, the potential
difference dropped by about 100 mV, to ca. 1.4 V after
1000 s. There is no mechanism for self-discharge of an
Fig. 4. Impedance spectrum of a capacitor consisting of two electrodes, a
mass of 16.8 mg, 17.0 mg, and a composition: PVdF-co-HFP (42.8 wt%),
ACP Kanasiw 2600 m2/g, (51.6 wt%), AB (5.6 wt%). Electrolyte:
EMImBF4.
285
Fig. 5. Dependence of the capacity on the polarisation frequency of a
capacitor consisting of two electrodes, a mass of 16.8 mg, 17.0 mg, and a
composition: PVdF-co-HFP (42.8 wt%), ACP Kanasiw 2600 m2/g,
(51.6 wt%), AB (5.6 wt%). Electrolyte: EMImBF4.
ideally polarizable electrode, and therefore, the potential
drop with time is due to Faradaic electron transfer processes
which can occur at the electrode/electrolyte interface. The
Faradaic processes may be caused by redox reactions
involving (i) functionalities present at the carbon electrode
surface or (ii) electrolyte impurities.
4. Conclusions
The capacity of the double layer formed at the
interface between activated carbon and ionic liquid,
obtained at the level of ca. 180 F/g, is comparable to that
characteristic for solutions of organic salts. For example
(C2H5)4NBF4, in organic solvents, such as acetonitrile or
propylene carbonate. The energy stored in a capacitor
containing ionic liquids can be high, due to a broad
practical electrochemical stability window of ca. 3 V. In
addition, ionic liquids are characterised by negligible
vapour pressure, which leads to systems containing no
volatile component, and the resulting device may be
regarded as environmentally friendly.
Acknowledgements
This work was supported by grant KBN31-
1693/T10/2001.
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