Electrochimica Acta 140 (2014) 132138

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Effect of binder on the performance of carbon/carbon symmetric

capacitors in salt aqueous electrolyte

Qamar Abbas, Dorota Pajak, Elzbieta

Frackowiak,
Francois Bguin ,1
Institute of Chemistry and Technical Electrochemistry, Poznan University of Technology, Piotrowo 3, 60-965 Poznan, Poland

a r t i c l e

i n f o

Article history:
Received 23 January 2014
Received in revised form 15 April 2014
Accepted 17 April 2014
Available online 24 April 2014
Keywords:
Supercapacitor
activated carbon
salt aqueous electrolyte, PVDF binder, PTFE
binder
potentiostatic oating

a b s t r a c t
The performance of AC/AC (AC = activated carbon) symmetric capacitors based on two commonly used
binderspoly(vinylidene diuoride) (PVDF) and poly(tetrauoroethylene) (PTFE)introduced in the electrodes at same amount (10 wt%) has been compared in 1 molL1 NaNO3 aqueous electrolyte. For
capacitors charged up to 1.6 V, the PTFE and PVDF-based carbon electrodes exhibit capacitance values of
116 Fg1 and 104 Fg1 , respectively. This difference in capacitance is related to the presence of the binder
which, in the case of the PVDF-based electrodes, causes a more pronounced reduction of pore volume as
compared to the pristine powder. The positive electrode of the AC-PTFE/AC-PTFE cell operates under the
thermodynamic potential limit of di-oxygen evolution (in 1 molL1 NaNO3 , Eox = 0.834 V vs. SHE) up to
1.4 V voltage, while this limit is reached at a voltage of 1.2 V with the AC-PVDF/AC-PVDF cell. This shows
that the porosity of the electrode strongly impacts the potential range of the positive electrode. Accelerated ageing performed by potentiostatic oating at 1.6 V for 120 h shows higher capacitance decrease and
internal resistance increase in the case of the AC-PVDF/AC-PVDF cell due to a stronger oxidation of the
positive electrode caused by the higher potential reached by this electrode. Hence, these results suggest
that the performance of supercapacitors might differ depending on the selected binder, and discussions
relating the capacitance performance to the textural parameters of the pristine carbon may be biased by
a change of porosity. Therefore, it is highly recommended to take into account the gas adsorption data of
the electrodes instead of the original powder.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Electrical double-layer capacitors (EDLCs), also known as supercapacitors, are energy storage devices based on activated carbon
(AC) electrodes, which deliver high power in short periods of time
with excellent cycle life [1,2]. They are used for both mobile and
stationary applications - e.g., hybrid electric vehicles (HEVs), emergency systems in aircrafts, elevators, cranes and so on. In order
to realize such devices, the use of low cost, environment friendly
and industrially viable materials is preferred, while optimizing the
energy density.
The energy density (E) of electrochemical capacitors is
expressed by equation (1):
E = 12 CU 2

Corresponding author. Tel.: +48 61 665 3632.

E-mail address: francois.beguin@put.poznan.pl (F. Bguin).
1
ISE Member.
http://dx.doi.org/10.1016/j.electacta.2014.04.096
0013-4686/ 2014 Elsevier Ltd. All rights reserved.

(1)

where C is the capacitance and U the operating voltage; the maximum voltage depends on the electrochemical stability window of
the electrolyte. Although H2 SO4 and KOH aqueous electrolytes display a high electrical conductivity, and consequently allow a low
equivalent series resistance (ESR) and high capacitance values, they
have a restricted industrial viability due to the limited voltage of
AC/AC systems in these media, usually less than 1 V [3,4].
excellent
cycle
life
under
galvanostatic
Recently,
charge/discharge up to 1.6 V has been demonstrated for AC/AC
symmetric capacitors in salt aqueous electrolyte (Na2 SO4 - 0.5
molL1 ) [5,6]. Later, it has been even found that voltage around
2 V can be reached in aqueous Li2 SO4 [79]. Such high values are
possible due to the high over-potential for di-hydrogen evolution
at the negative electrode [7]. Taking into account the environmental friendly character and low corrosive properties of salt aqueous
electrolytes, promising prospects can be expected from AC/AC
systems built in these media.
Besides, it is now well-accepted that capacitance can be
enhanced by a good tting between the pore size of AC and the size
of electrolyte ions. In aqueous media, pores in the range of 0.71 nm
demonstrate better efciency for forming effectively the electrical

Q. Abbas et al. / Electrochimica Acta 140 (2014) 132138

double-layer [10,11]. However, taking into account that the porosity of AC might be partly blocked by additives used in preparing
electrodes, e.g., binder [12], it is important to consider their role
in the discussion of relationship between the porous texture and
capacitance of AC electrodes in salt aqueous electrolytes.
So far, mainly two types of binderspoly(tetrauoroethylene)
(PTFE) [7,13,14] and poly(vinylidene diuoride) (PVDF) [5,6,8] have been employed indifferently in order to maintain the integrity
of electrodes during operation of AC/AC capacitors in salt aqueous electrolytes. This work aims at comparing the performance
of AC-based symmetric capacitors in 1 molL1 sodium nitrate
with electrodes based on either PVDF or PTFE binders. It has been
observed that the PTFE-based capacitor performs better than the
PVDF-based one and has ability to withstand oating at high voltage. We will demonstrate that different porosity of the electrodes,
due to the presence of binder, is at the origin of different electrochemical performance.

2. Experimental
2.1. Electrode preparation
The activated carbon (AC) used for the study was Norit DLC
Supra 30 (SBET = 2066 m2 g1 ). The carbon SUPER C65 from
Timcal was used as percolator and the binders were either
poly(tetrauoroethylene) (PTFE - 60 wt. % dispersion in water,
Sigma-Aldrich) or poly(vinylidene uoride) (PVDF - Kynar HSV900
from Arkema, France). The PTFE-based electrodes (AC-PTFE) were
made by mixing AC (80 wt. %), C65 (10 wt. %) and PTFE (10 wt. %)
in 10 ml of ethanol. The dough obtained after mixing was rolled
to a thickness of nearly 0.3 mm and was left overnight for ethanol
to evaporate. Pellets were cut out from the rolled dough, pressed
under 5 toncm2 and nally dried under vacuum at 120 C for 12 h.
The PVDF-based electrodes (AC-PVDF) were prepared by adding
10 ml of acetone to all components (AC 80 wt. %, C65 10 wt. % and
PVDF 10 wt. %) in a mortar and by continuous mixing until its evaporation. The powder was pressed under 5 toncm2 in order to make
pellets. The later were dried under vacuum at 120 C for 3 h. The
pellets had a diameter of 1 cm, a thickness of about 0.3 mm and
a weight varying between 10 to 15 mg, whatever the preparation
method.
2.2. Physicochemical characterization
The porous texture of the materials was determined by nitrogen adsorptiondesorption at 77 K using an Accelerated Surface
Area and Porosimetry analyzer (ASAP 2020Micromeritics, USA).
Before the measurements, the samples were outgassed at 140 C
for 24 h. The specic surface area was calculated by applying
the BrunauerEmmettTeller (BET) equation to the N2 adsorption
data, while the average pore sizeL0 was calculated by applying
the Dubinin-Radushkevich (DR) and Stoeckli equations [15]. The
Quenched Solid Density Functional Theory (QSDFT) was used to
assess the pore size distribution, the micropore (< 2 nm) and mesopore (2-50 nm) volumes [16,17]. In order to allow a comparison in
the case of electrodes, the amount of nitrogen adsorbed and the
textural data were referred to the AC mass.
2.3. Electrochemical testing
Electrochemical capacitors were built in a Teon Swagelok
vessel, by sandwiching a glass microber separator (GF/A,
WhatmanTM , 0.26 mm) between two pellet electrodes and using
stainless steel (316L) current collectors and 1 molL1 NaNO3 (pure

133

p.a., Sigma-Aldrich, conductivity = 74 mScm1 , pH 6.7) as electrolyte. Taking into account equation (2):
m+ C+ E+ = m C E

(2)

where m+ and m- are the masses, C+ and C- the specic capacitance

and E+ and E- the potential windows for positive and negative electrodes, respectively, we selected higher mass (by 15%)
for the positive electrode, in order to reduce its maximum potential and consequently its irreversible oxidation. In some cases, an
Hg/Hg2 SO4 in 1 mol.L1 H2 SO4 (+0.674 V vs. Standard Hydrogen
Electrode - SHE) reference electrode with 1 molL1 NaNO3 salt
bridge was incorporated in the capacitor cell in order to measure
the potential of both electrodes. At pH 6.7, the thermodynamic
di-hydrogen and di-oxygen evolution potentials calculated from
the Nernst equation are EH2 -0.396 V vs. SHE and EO2 0.834 V
vs. SHE, respectively.
The electrochemical performance of the cells was investigated by cyclic voltammetry (2 mVs1 ) and galvanostatic (200
mAg1 ) charge-discharge in a voltage range from 0 to 1.6 V using
a VMP3 multichannel potentiostat/galvanostat (Biologic, France).
The gravimetric capacitance (Fg1 ) has been calculated from the
galvanostatic discharge characteristics using equation (3):
C = (2)I/[(dU/dt)mam ]

(3)

where I is the current (A), dU/dt the slope of the discharge curve
(Vs1 ), mam is the average mass (g) of AC in one electrode.
Impedance spectra were recorded in the range of 1 mHz to
100 kHz at different voltages from 0 V to 1.6 V. Potentiostatic oating at 1.6 V has been applied to estimate the ageing of capacitors;
in these experiments, the cell is charged at constant current up to
1.6 V and is maintained at this value for periods of 2 h. A total of
60 such oating periods were applied; each of them was followed
by ve galvanostatic charge/discharge cycles at 1 Ag1 in order to
estimate the discharge capacitance and the equivalent series resistance (ESR) from the voltage drop between 5th charge and discharge
when reversing the sign of current.
3. Results and Discussion
3.1. Two-electrode cell performance
Fig. 1 shows the cyclic voltammograms of AC/AC cells in 1
molL1 NaNO3 when the electrodes are manufactured with the
two binders. Whatever the voltage range, up to 0.8 V or 1.6 V, a
higher capacitive current is observed with the PTFE binder. At low
voltage range (Fig. 1a), both systems display a rectangular shape of
CV which is typical for electrical double-layer charging; the slightly
more rectangular curve in case of AC-PTFE electrodes reveals a
better charge propagation. For the higher voltage range of 1.6 V
(Fig. 1b), the current leap at high voltage is essentially attributed
to hydrogen storage at the negative electrode. It has an associated
hump below 0.4 V during the negative scan - more visible in the case
of the AC-PTFE electrodes - suggesting that hydrogen stored in the
negative electrode [18] is desorbed when the voltage decreases, it
means when the potential of the negative electrode becomes higher
than the thermodynamic limit for water reduction [7].
The capacitance and efciency (discharge to charge time ratio)
of the AC/AC capacitors in 1 molL1 NaNO3 are plotted vs voltage
for both kinds of binders in Fig. 2. The capacitance slightly increases
with voltage being higher with AC-PTFE electrodes in all the voltage range. At 1.6 V, the capacitance values are 116 Fg1 and 104
Fg1 for the AC-PTFE and AC-PVDF electrodes, respectively. Whatever the binder, the efciency decreases with increasing voltage,
but values are higher for the AC-PTFE capacitor than for the ACPVDF one. Low efciency values may indicate the occurrence of

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Q. Abbas et al. / Electrochimica Acta 140 (2014) 132138

150

AC-PTFE

(a)

Capacitance / F g-1

Capacitance / F g-1

100
50
0
-50

-100
0.0

0.2

0.4

AC-PTFE

(b)

AC-PVDF

0.6

AC-PVDF

200

100

-100

0.8

0.0

U/V

0.4

0.8

1.2

1.6

U/V

Fig. 1. Cyclic voltammograms (2 mVs1 ) up to 0.8 V (a) and 1.6 V (b) of AC/AC capacitors in 1 molL1 NaNO3 with PTFE and PVDF binders.

higher capacitance by 15 Fg1 at low frequency (1 mHz), whereas

at higher frequency (around 1 Hz), the capacitance is higher for the
AC-PVDF based system. It suggests that, at open circuit voltage,
deeper pores are more accessible in AC-PVDF electrodes than in
AC-PTFE ones, due to better initial wetting. This lesser accessible
porosity for AC-PTFE electrodes in 1 molL1 NaNO3 correlates with
their more hydrophobic nature demonstrated by the contact angle
measurements realized (in absence of polarization) at room temperature, with values decreasing from 156o to 129o and 64o to 24o

(a)

0V
0.8V
1.2V
1.6V

300
5
4

200

-Z" / ohm

-Z" / ohm

irreversible redox side reactions during charging. However, with

AC-PTFE electrodes, the efciency is higher than 98% in all voltage
range, revealing an excellent reversibility of these electrodes.
The Nyquist plots realized at different voltages in two-electrode
cells in 1 molL1 NaNO3 are presented in Fig. 3 for both binders. At
0 V, the two systems exhibit comparable internal resistance values
(ESR = 0.461  and 0.427  for AC-PTFE and AC-PVDF, respectively)
originating mainly from the bulk electrolyte; at all voltages, the ESR
values remain unchanged. Besides, the charge transfer resistance
(semi-circle region), which is believed to be related to the resistances of the electrode/electrolyte and electrode/current collector
interfaces, is smaller with the AC-PTFE electrodes than with the
AC-PVDF ones indicating a good contact between AC and current
collectors and between activated carbon particles when using PTFE.
Next to the semi-circle is the Warburg region, with a phase angle of
45o , up to the knee frequency; this so-called mass transport region is
essentially governed by the diffusion of the charged species within
the porosity. Hence, the AC-PTFE based capacitor displays a more
prominent Warburg diffusion region than the AC-PVDF one, which
could be related to a higher porosity available for the transport of
ions in the case of the former. The knee frequency for the AC-PTFE
capacitor shifts to higher values when the voltage increases. This
shift results in almost linear decrease of the EDR values (Table 1),
revealing a more accessible porosity of the AC-PTFE electrode(s)
at higher voltage. By contrast, the negligible shift with increasing
voltage in case of AC-PVDF seems to reveal good initial wetting of
the electrodes. The near vertical line in the Nyquist plot at low frequency (10 mHz to 1 mHz) characterizes the capacitive behavior of
the system [19].
The frequency dependence of capacitance at open circuit voltage
presented in Fig. 4 conrms that the PTFE-based capacitor displays

3
2
1

100

Knee frequency

0
0

100

2
3
Z' / ohm

200

300

Z' / ohm

(b)

0V
0.8V
1.2V
1.6V

300
5

100

140

80
60

94

AC-PVDF
AC-PTFE

40

92

20

90

0
0.8

1.0

1.2

1.4

1.6

U/V
Fig. 2. Discharge (200 mAg1 ) capacitance and efciency of AC/AC capacitors in 1
molL1 NaNO3 vs. maximum voltage.

200
-Z" / ohm

96

-Z" / ohm

100

Capacitance / F g-1

Efficiency (%)

120

98

100

3
2
Knee frequency

1
0
0

0
0

100

2
3
Z' / ohm

200

300

Z' / ohm
Fig. 3. Nyquist plots of two-electrode cells in 1 molL1 NaNO3 at 0 V, 0.8 V, 1.2 V
and 1.6 V: a) AC-PTFE electrodes, b) AC-PVDF electrodes.

Q. Abbas et al. / Electrochimica Acta 140 (2014) 132138

Table 1
EDR values () estimated from the Nyquist plots (as described in [3]) at different
cell potentials for AC/AC capacitors with PTFE and PVDF binders.
0V

0.8 V

1.2 V

1.6 V

AC-PTFE
AC-PVDF

3.72
3.0

3.49
2.98

3.28
2.96

2.96
2.73

120

Capacitance / F g-1

Cell potential

135

in 10 minutes for AC-PTFE and AC-PVDF electrodes, respectively.

The shift of Knee frequency to lower values, when voltage decreases
for AC-PTFE electrodes, is also a proof of a lesser accessible porosity.
Overall, the AC-PTFE based capacitor performs better under polarization conditions where ionic species are forced into the carbon
porosity.

AC-PVDF
AC-PTFE

100
80
60
40
20
0
1E-3 0.01

0.1

10

100 1000 10000100000

Frequency / Hz
3.2. Porous texture of pristine carbon and electrodes
In order to understand the differences in capacitance values and
Nyquist plots displayed with electrodes made from the two binders,
and taking into account that it has been already shown that the
binder may block a part of carbon porosity [12], the porous texture
of the electrodes and of the pristine carbon powder has been investigated by nitrogen adsorption at 77 K. Fig. 5a shows a remarkable
decrease of the amount of gas adsorbed from the pristine AC carbon
to the AC-PTFE and AC-PVDF electrodes. As shown in Table 2, the
BET specic surface area drops from 2066 m2 g1 to 1835 m2 g1
and 1544 m2 g1 , respectively. Hence, the PVDF binder blocks more
the porosity than the PTFE one. The plot of pore size distribution
(PSD, Fig. 5b) demonstrates that all pores are affected by the presence of the binder. In Table 2, it is seen that the Vmicro /Vmeso ratio
is comparable for the electrodes and the pristine carbon, meaning
that micropores and mesopores are almost affected equally by the
presence of the binder. However, the slightly higher value of average micropore size L0 in the case of the AC-PVDF electrodes reveals
that small micropores are more affected by this binder, as proved
by a lower contribution below 0.8 nm in the PSD (Fig. 5b). Hence,
the different change of porous texture provoked by the binder is
the reason for the differences in electrochemical performance of
both types of electrodes.

Fig. 4. Capacitance vs. frequency at open circuit voltage for AC/AC cells with PTFE
and PVDF-based electrodes operating in 1 molL1 NaNO3 .

(200 mAg1 ) charge/discharge are shown in Fig. 6. In the PTFEbased symmetric capacitor, the maximum potential of the positive
electrode exceeds the thermodynamic limit for di-oxygen evolution (Eox = 0.834 V vs. SHE) at a voltage of 1.4 V (Fig. 6a), while this
limit is reached at 1.2 V for the cell with PVDF-based electrodes
(Fig. 6b), that is the positive electrode in the PVDF-based system
undergoes irreversible carbon oxidation at voltage values lower
by 200 mV than in the PTFE-based system. By contrast, in both
AC cells, the operating potential of the negative electrode is well
above the potential for practical di-hydrogen evolution (EH2 0.8 V vs SHE) at all voltage values. This potential was determined
by cyclic voltammetry in three electrode cell while polarizing AC
to more negative potentials. Below the thermodynamic potential
of water reduction, hydrogen is rst chemisorbed in the porosity of carbon, and polarizing to more negative potentials results in
di-hydrogen production producing oscillations in the cyclic voltammograms [7,18]. Below the thermodynamic potential for water
reduction, OH ions are generated in the porosity of AC according
to equation (4), provoking a local increase of pH and consequently a
decrease of practical di-hydrogen evolution potential (as explained
by application of the Nernst relation E = -0.06 pH) [20].
AC + xH2 O + xe < ACHx > + xOH

The effect of the kind of binder on the potential range of both

electrodes at increasing voltage values has been investigated in a
two-electrode cell equipped with a reference electrode. The values of potential extrema vs voltage determined from galvanostatic

Fig. 7 shows the capacitance values of positive and negative electrodes obtained from galvanostatic (200 mA.g1 ) discharge when
AC-PTFE/AC-PTFE and AC-PVDF/AC-PVDF cells with reference electrode are charged up to 1.6 V. Whatever the binder, the capacitance

(a)
700
600

Nitrogen Adsorption Isotherm

AC
AC-PTFE

Pore Size Distribution - PSD

(b)

1.0
AC

0.8

AC-PTFE

AC-PVDF

500

(4)

0.6

AC-PVDF

400

0.4

300

0.2
0.0

200

Differential pore volume

/ cm3 g-1 nm-1

Adsorbed amount (STP) / cm3 g-1

3.3. Potential range of the electrodes

Pristine

100

PTFE

PVDF

0.0

0.2
0.4
0.6
0.8
1.0
Relative pressure, (P/P0)

2
3
4
Pore width / nm

Fig. 5. Nitrogen adsorption/desorption isotherms obtained at 77 K (a) and QSDFT pore size distribution (b) of AC, AC-PTFE and AC-PVDF electrodes. For the electrodes, the
amount of nitrogen adsorbed is referred to the mass of AC.

136

Q. Abbas et al. / Electrochimica Acta 140 (2014) 132138

(a)

1.2 Thermodynamic oxygen

1.2 Thermodynamic oxygen

evolution potential

0.0
Thermodynamic hydrogen
evolution potential

-0.8

EH

Practical di-hydrogen evolution potential

Eox

0.8

E vs. SHE / V

E vs. SHE / V

E0
E+
E-

0.4

-0.4

evolution potential

Eox

0.8

(b)

0.4
E0
E+
E-

0.0
-0.4
-0.8

Thermodynamic hydrogen
evolution potential
Practical di-hydrogen evolution potential

EH

-1.2

-1.2

0.8

1.0

1.2

1.4

0.8

1.6

1.0

1.2

1.4

1.6

U/V

U/V

Fig. 6. Potential extrema vs SHE reached by each electrode during galvanostatic (200 mAg1 ) charge/discharge of AC-PTFE/AC-PTFE (a) and AC-PVDF/AC-PVDF (b) cells with
reference electrode in 1 molL1 NaNO3 up to different voltage values. Hg/Hg2 SO4 reference electrode with 1 molL1 NaNO3 salt bridge.

values of the positive and negative electrodes are comparable at all

voltages. By contrast, the AC-PTFE positive electrode exhibits much
higher capacitance than the AC-PVDF one, due to a higher electrosorption of the bulky NO3 anions favored by the higher pore
volume of the former compared to the later. According to equation
(2), the AC-PTFE positive electrode then operates in a lower potential range, and for this reason reaches a lower maximum potential
than the AC-PVDF positive one when the voltage is increased
up to 1.6 V. One might expect the generation of oxygenated
functionalities on the surface of the AC-PVDF electrode which
should affect its long-term performance.

Capacitance / F g-1

140
120
100
80
60

AC-PVDF (+)
AC-PVDF (-)
AC-PTFE (+)
AC-PTFE (-)

40
20
0
0.8

1.0

1.2

1.4

3.4. Accelerated ageing by potentiostatic oating

1.6

U/V
Fig. 7. Discharge capacitance of electrodes measured by galvanostatic (200 mAg1 )
cycling of AC-PTFE/AC-PTFE and AC-PVDF/AC-PVDF cells with reference electrode
in 1 molL1 NaNO3 up to different voltage values. Hg/Hg2 SO4 reference electrode
with 1 molL1 NaNO3 salt bridge.

Accelerated ageing by oating at 1.6 V has been performed on

AC/AC capacitors with electrodes made from the two binders, in
order to detect the impact of different porosity and different operating potential range of the positive electrode on the cycle life. Fig. 8
displays, for the two binders, the evolution of cell capacitance and

Table 2
Textural data of AC, AC-PVDF and AC-PTFE electrodes. For the electrodes, the specic surface area and the pore volumes are referred to the mass of AC.
Material

SBET [m2 g1 ]

Vtotal a [cm3 g1 ]

Vmicro b [cm3 g1 ]

Vmeso c [cm3 g1 ]

Vmicro /Vmeso

L0 d [nm]

AC
AC-PVDF
AC-PTFE

2066
1544
1835

1.100
0.855
1.003

0.908
0.675
0.807

0.172
0.130
0.156

5.28
5.19
5.17

1.54
1.61
1.51

a, b, c
d

Calculated from the cumulative pore volume using the QSDFT method [16,17].
The average micropore size L0 is calculated by applying the Dubinin-Radushkevich (DR) and Stoeckli equations [15] to the adsorption data.

100

Resistance / ohm

Capacitance / F g-1

120

80
60
AC-PVDF

(a)

AC-PTFE

40
20

AC-PTFE

(b)

AC-PVDF

0
0

20

40

60

80

Floating time / h

100

120

20

40

60

80

100 120

Floating time / h

Fig. 8. Capacitance (a) and internal resistance (b) of AC/AC capacitors with PTFE and PVDF binders plotted versus oating time at 1.6 V and room temperature in 1 molL1
NaNO3 .

(a)

(b)

AC-PTFE

1600

Specific current / mA g-1

Specific current / mA g-1

Q. Abbas et al. / Electrochimica Acta 140 (2014) 132138

1200

800

400

137

AC-PVDF

1600

1200

800

400

0
0

20

40

60

80

100

120

140

20

Floating time / h

40

60

80

100

120

140

Floating time / h

Fig. 9. Leakage current prole of AC/AC capacitors with PTFE (a) and PVDF (b) binders plotted versus oating time at 1.6 V and room temperature in 1 molL1 NaNO3 .

resistance with oating time. For the freshly prepared devices, the
capacitance values are higher by 15 Fg1 when using AC-PTFE
electrodes (Fig. 8a). After 120 h of oating, the capacitance of the
AC-PTFE/AC-PTFE capacitor has slightly decayed by about 14%. By
contrast, the capacitance decay is much more pronounced for the
capacitor containing AC-PVDF electrodes. A difference between the
two binders is also found when the internal resistance is plotted
versus the oating time (Fig. 8b); the resistance increases faster
for the system operating with AC-PVDF electrodes. Such dramatic
ESR increase and capacitance fading for the AC-PVDF electrodes is
related to the higher potential reached by the positive electrode,
as shown in Fig. 6b, giving rise to a larger irreversible di-oxygen
evolution together with carbon oxidation [21]. Considering the
generally accepted end-of-life criteria of supercapacitors, i.e. capacitance decay by 20% or resistance increase by 100% [21], the PTFE
and PVDF-based capacitors are out of usage after approximately 60
and 40 h of oating at 1.6 V, respectively. Even if the AC-PTFE/ACPTFE capacitor performs better than the AC-PVDF/AC-PVDF one, it
is obvious that for keeping a good state-of-health it should not be
cycled at voltage higher than 1.5 V.
Since redox phenomena may be involved in the ageing of the
AC/AC capacitors in 1 molL1 NaNO3 , it is interesting to plot the
leakage current to discriminate between the two binders. The leakage current recorded on the two kinds of capacitors during the
repeated two-hour sequences of potentiostatic oating at 1.6 V is
shown in Fig. 9. When the capacitors are charged up to 1.6 V, there
is a steep increase of current, and then the current drops rapidly
within the initial few minutes of potentiostatic oating at 1.6 V.

AC-PTFE
AC-PVDF

(a)

200

AC-PVDF
AC-PTFE

(b)

100

Capacitance / F g-1

Capacitance / F g-1

150

Such rapid decay in current is generally attributed to the reorganization of the ionic species in the electrical double-layer and within
the diffusion layer until reaching the equilibrium state [19,21]. It
is also described as a transition from stronger to weaker interaction of the electrode with i) the double layer and ii) the diffusion
layer, resulting in regress of the ionic species to the bulk solution [22]. For the capacitor with AC-PTFE electrodes (Fig. 9a), the
leakage current traces remain nearly identical during the successive oating periods, suggesting a negligible contribution of side
reactions, such as oxidation of positive carbon electrode, evolution
of gases and corrosion of current collectors. By contrast, with the
AC-PVDF based capacitor (Fig. 9b), the initial current is higher than
with AC-PTFE and it continuously increases up to 90 h. This increase
is attributed to surface reactions requiring higher current at the
positive electrode, due to the higher maximum potential reached
by this electrode. After 90 h, a sudden increase in current can be
seen with the AC-PVDF based capacitor, and can be correlated
to the capacitance drop (Fig. 8a) and resistance increase (Fig. 8b)
during the same period of time. This can be due either to the
creation of heterogeneous oxygenated functionalities on the
positive carbon electrode [23] or to the corrosion of the positive current collector, both phenomena leading to a signicant
increase in resistance values. However, after opening the cells
which operated at 1.6 V with AC-PVDF electrodes, we could not
detect any corrosion of the stainless steel collectors. Hence, it is
likely that the high potential reached by the positive electrode
in this system causes essentially oxidation of the carbon surface.

50
0
-50
-100

100

-100

-150
-200
0.0

0.2

0.4

U/V

0.6

0.8

0.0

0.4

0.8

1.2

1.6

U/V

Fig. 10. Cyclic voltammograms (2 mVs1 ) up to 0.8 V (a) and 1.6 V (b) for AC/AC capacitors with AC-PTFE and AC-PVDF electrodes in 1 molL1 NaNO3 realized after oating
at 1.6 V for 120 h.

138

Q. Abbas et al. / Electrochimica Acta 140 (2014) 132138

Cyclic voltammograms (CVs) were recorded after oating the

AC-PTFE and AC-PVDF based capacitors at 1.6 V for a total of 120 h
(Fig. 10). The AC-PTFE/AC-PTFE capacitor displays a nearly rectangular shape of CV up to 0.8 V, while the capacitive current of the
AC-PVDF/AC-PVDF starts to decrease from 0.4 V (Fig. 10a). When
comparing the two systems, this decrease of capacitive current is
even more marked when the voltage is raised up to 1.6 V. Once
more, this is an indication that the electrodes manufactured with
PTFE undergo lesser ageing than the PVDF-based ones. Knowing
that, at voltage of 1.6 V, the AC-PVDF positive electrode is more
oxidized than the AC-PTFE one (Fig. 6), one might anticipate that
the pore volume is more reduced in the case of AC-PVDF electrodes
due to the blockage of pore entrances by oxygenated groups. Hence,
if the pore volume of AC-PVDF is more reduced by these groups
than in the case of AC-PTFE, one can attribute the important narrowing of the AC-PVDF/AC-PVDF voltammogram to the saturation
of porosity by the ions of the electrolyte [24]. The comparison of
Figs. 1 and 10 for the AC-PTFE/AC-PTFE capacitor indicates clearly a
little narrowing of the CV after oating for 120 h at voltage as high
as 1.6 V, suggesting that the electrodes are not much aged by the
use of such conditions.
4. Conclusion
We have demonstrated that the performance of AC/AC symmetric capacitors in 1 mol L1 NaNO3 depends on the nature of the
binder, although using the same mass of PTFE and PVDF in the
manufacture of electrodes. Electrodes are less microporous than
the pristine carbon powder, and the loss of porosity is more important with PVDF which seems to block more the small micropores
than does PTFE. Consequently, higher capacitance is achieved with
AC-PTFE electrodes due to their higher microporous volume as
compared to AC-PVDF ones. The difference of porosity between the
two types of electrodes has a noticeable impact on the potential
window of the positive electrode, and the latter operates at lower
potentials when PTFE is used, limiting by this way the oxidation
of carbon even when the capacitor operates at voltage as high as
1.6 V. Accelerated ageing together with the plot of leakage current
measured during oating conrm a better state-of-health of the ACPTFE/AC-PTFE capacitor. Overall, PTFE seems to be a better binder
for electrodes of capacitors operating in salt aqueous electrolytes.
Hence, these results conrm that the performance of supercapacitors might differ depending on the selected binder, and
discussions relating the capacitance performance to the textural parameters of the pristine carbon may be biased by a change
of porosity when realizing electrodes. Therefore, it is highly recommended to take into account the gas adsorption data of the
electrodes instead of the original powder. However, it should not
be systematically extrapolated that PTFE is a better binder than
PVDF. Indeed, the change of porosity by the binder and the diffusion of ions in the pores may depend on the physicochemical
characteristics of the carbon material and nature of the electrolyte.
Acknowledgments
The Foundation for Polish Science is acknowledged for supporting the ECOLCAP project realized within the WELCOME program,

co-nanced from the European Union Regional Development Fund.

Norit is acknowledged for providing the activated carbon and
Arkema for the PVDF Kynar binder. Timcal is also acknowledged
for providing the carbon black.
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