ACTA PHYSICO-CHIMICA SINICA

Volume 24, Issue 7, July 2008

Online English edition of the Chinese language journal

Cite this article as: Acta Phys. -Chim. Sin., 2008, 24(7): 1143−1148. ARTICLE

Surface Modification and Performance of Activated Carbon

Electrode Material
Yafei Liu, Zhonghua Hu*, Kun Xu, Xiangwei Zheng, Qiang Gao

Department of Chemistry, Tongji University, Shanghai 200092, P. R. China

Abstract: A commercial activated carbon was modified by surface treatment using three chemicals, nitric acid, hydrogen peroxide,
and ammonia, respectively. The modified carbons were characterized by N2 adsorption-desorption isotherms and FTIR spectroscopy.
The resultant carbon electrode-based electric double-layer capacitors (EDLCs) were assembled with 6 mol·L−1 KOH as the
electrolyte. The influence of surface modification on the performance of EDLCs was studied by galvanostatic charge-discharge,
cyclic voltammetry, and alternating current impedance. The surface modification resulted in no big decrease in specific surface area
and little decrease in average pore size, and introduced functional groups, such as hydroxyl, carbonyl, and amidogen, on the carbon
surface. These functional groups significantly improved the wettability and reduced the resistance of the activated carbon. As a result,
the specific capacitance of the carbon modified with 65% HNO3 reached 250 F·g−1, 72.4% higher than that of original carbon. The
leakage current of testing EDLCs decreased unexpectedly to 3−18 μA, only 0.8%−4.9% that of the original carbon electrode-based
EDLC (371 μA).

Key Words: Activated carbon; Electric double-layer capacitor; Surface modification; Electrode material; Specific capacitance.

Supercapacitor is an advanced device for energy storage,
which has been widely used in many fields, such as informa-
tion and technology, electric vehicle, aerospace, and military
equipments. The electrodes are the key component of a su-
percapacitor. Three kinds of materials, carbon, metal oxides,
and polymers are most used as electrode materials[1,2]. Among
these materials, only activated carbon is commercially applied
to supercapacitor, owing to its high surface area, good thermal
and electric conductivity, good anti-causticity, high stability,
low cost, and commercially available materials. Therefore, the
study on activated carbon as an electrode material is always a
hot topic in this area. For a carbon-based supercapacitor, the
electric energy is stored in the electric double-layer on the
carbon surface, so it is called the electric double-layer capaci-
tor (EDLC). In principle, the higher the surface area, the larger
the capacitance is. However, usually the specific capacitance
is not proportional to the surface area for activated carbon[3,4],
because both pore structure[5,6] and surface chemistry[7−10] of
carbon materials have influence on the formation of the elec-
tric double-layer. Surface modification to introduce functional
groups have a significant influence on the capacitive behavior
of carbon material[11].
Frackowiak et al.[12] reported that multiwalled carbon
nanotubes (MWCNTs) treated with 69% HNO3 at 80 °C re-
sulted in an increase in oxygen functional groups, which par-
ticipated in the redox and generated pseudocapacitance to in-
crease the specific capacitance from 80 to 137 F·g−1. Jurewicz
et al.[13] reported that introducing nitrogen containing func-
tional groups on a carbon surface through modification, with a
mixture of ammonia and air, increased the specific capacitance
of carbon material. Hu et al.[14] partially oxidized the
MWCNTs in air and subsequently treated it with a mixture of
H2SO4 and HNO3, and the specific capacitance increased by
175%. Although new carbon materials such as carbon nano-
tubes had application potential as electrode material, the com-
plicated procedure of preparation and high cost led to difficul-
ties in practical application.
In this article, a commercial activated carbon was modified
by surface treatment with oxidative and acidic, neutral oxida-
tive, and alkaline agent, that is, HNO3, H2O2, and NH3·H2O,

Received: January 14, 2008; Revised: March 19, 2008.

*Corresponding author. Email: huzh@mail.tongji.edu.cn; Tel: +8621-65982594.
The project was supported by the National Natural Science Foundation of China (50472089).

Copyright © 2008, Chinese Chemical Society and College of Chemistry and Molecular Engineering, Peking University. Published by Elsevier BV. All rights reserved.
Chinese edition available online at www.whxb.pku.edu.cn
 Yafei Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(7): 1143−1148

respectively, to improve its electrochemical properties and to testing capacitor cell. KOH solution of 6 mol·L−1 was used as
serve as an electrode material for the supercapacitor. The in- the electrolyte. The details were described elsewhere[15].
fluence of the modification conditions on the electrochemical
1.4 Electrochemical measurement of supercapacitor
performance of carbon electrode-based EDLCs was investi-
gated. The relationship between the surface chemistry of car- The performance of testing supercapacitors was studied by
bon and electrochemical performance of the corresponding galvanostatic charge-discharge using a battery-test apparatus
carbon electrode-based supercapacitor was studied. (PCBT-100-8D, LISUN, China). The gravimetric specific ca-
pacitance (C, F·g−1) was calculated by the following formula:
1 Experimental
4 I d Δt
C= ⋅ (1)
1.1 Materials and agents mw ΔU
where Id, Δt, and ΔU are the discharge current, discharge time,
Coconut shell-based activated carbon (AC) was supplied by and difference of voltage in the time of Δt during discharge,
Taiyuan Activated Carbon Manufacture, China. Polytetra- respectively; m is the total mass of the two electrodes, and w is
fluoroethylene (PTFE), graphite (G) powder, and polypropyl- the mass fraction of activated carbon in the electrode.
ene (PP) films were of reagent grade. Nickel foam was from The equivalent series resistance (ESR) of supercapacitor (R)
Changsha Liyuan Company, China. Chemicals H2O2, HNO3, was calculated by formula (2):
NH3·H2O, KOH, HCl, and ethanol were all of analytical grade. R=ΔUb/Id (2)
1.2 Surface modification and characterization of where ΔUb is the voltage drop at the very beginning of the
activated carbons discharge.
The stability and reversibility of the capacitor were investi-
The commercial activated carbon (AC-0) powder under 180 gated by cyclic voltammetry; the impedance spectrum and
mesh was used as the starting material and treated by HNO3, leakage current were studied by using an Electrochemical
H2O2, and NH3·H2O, respectively, at 65 °C in a water bath for Work Station (CHI660A, Shanghai Chenhua Equipment Co.,
1 h under magnetic stirring. The modification conditions and China) at room temperature. From voltammogram, the gra-
the names of the carbon samples are listed in Table 1. vimetric specific capacitance was also calculated by formula
The activated carbon samples were characterized by nitro- (3):
gen adsorption at 77 K (Tristar3000, Micromeritics, USA). C=4I/(vmw) (3)
The specific surface area, micropore and mesopore volumes, where I is the responded current of plateau and v is the sweep
pore size, and pore size distribution were estimated by the rate. To avoid decomposition of the aqueous solution, the
BET model, t-plot, and BJH method according to the nitrogen voltammetry was performed in the potential range of 0−1.0 V.
adsorption isotherms. FTIR spectroscopy (Nexus912A, The ac (alternating current) impedance was measured in the
Thermo Nicolet, USA) was used to investigate the functional frequency range from 0.01 Hz to 100 kHz with the ac pertur-
groups on the carbon surface. bation of 10 mV. The leakage current of the capacitor was de-
termined by recoding the current−time (I−t) curve at a con-
1.3 Preparation of carbon electrode and assemblage of
stant potential of 1.0 V.
supercapacitor
2 Results and discussion
Activated carbon (AC) powder was wetted by ethanol, then
mixed with graphite (G) and polytetrafluoroethylene (PTFE) 2.1 Surface area, porosity, and surface characteristic of
in a mass ratio of mAC:mG:mPTFE=8:1:1. The disc-type carbon activated carbons
electrodes were prepared and extruded to the current collector
of Ni foam. Sandwich-type capacitors were assembled with N2 adsorption-desorption isotherms of original activated
two carbon electrodes separated by polypropylene film in a carbon AC-0 and modified carbons AC-3, AC-5, and AC-6 are
presented in Fig.1. As seen from Fig.1 that the adsorption pla-
Table 1 Modification conditions of activated carbons teau decreases to some extent for modified samples; but there
is almost no change in the shapes of the adsorption isotherms.
Sample Chemicals w(chemcials) (%)
All isotherms are of typical type-I according to the IUPAC
AC-0 − −
classification. Desorption branches have hysteresis loop (H3
AC-1 HNO3 15
type) at relative pressures higher than 0.4, suggesting a wide
AC-2 HNO3 30
pore size distribution and the existence of mesopores. The N2
AC-3 HNO3 65
adsorption isotherms of the other modified carbons are located
AC-4 H2O2 15
between AC-0 (the highest plateau) and AC-3 (the lowest pla-
AC-5 H2O2 30
teau) (not shown).
AC-6 NH3·H2O 15
The changes in specific surface area and pore structure of
 Yafei Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(7): 1143−1148

Fig.1 Nitrogen adsorption-desorption isotherms of activated carbons
carbons before and after modification are listed in Table 2. It
was evident that the modification caused a decrease in specific
surface area and pore volume, and few changes in average
pore size and microporous ratio, indicating that the highly mi-
croporous characteristics of the carbon were not changed after
modification. The reasons could be, first, the activated carbon
adsorbed the molecules or ions of modifying agents, which
occupied some active sites and pore volume; second, the pro-
duced functional groups on the carbon surface reduced pore
size, even blocked partial micropores. Besides, it was found
that the higher the concentration of the chemical agent was,
the larger the decrease in specific surface area and pore vol-
ume. However, the external surface areas hardly changed. The
results suggested that the modification had more influence on
the micropore surface area and volume. The oxidation with
high concentration of chemicals caused a collapse of partial
pores; the oxygen-containing groups introduced could block
some micropores[16], so that there was a more evident decrease
in the specific surface area and pore volume as shown in Table
2 for samples AC-1, AC-2, and AC-3 treated with HNO3,
AC-4 and AC-5 treated with H2O2.
The FTIR spectra of carbon samples before and after modi-
fication are shown in Fig.2. It was found that the band at 1570
cm−1, which was assigned to asymmetrical stretching vibration
of −COO−, disappeared after modification. For samples AC-3
and AC-4 modified by HNO3 and H2O2, respectively, the
broad band at 3430 cm−1 assigned to −OH stretching vibration,
enhanced obviously; new bands appeared at 1264, 1640, and
Fig.2 FTIR spectra of activated carbons before and after
modification
669 cm−1, assigned to stretching vibration of C−O, >CO, and
out-of-plane bending vibration of −OH, suggesting that the
carbonyl content increased and −OH was introduced on the
carbon surface. For the sample AC-6 modified by ammonia,
new bands appeared at 3450, 1640, 1263, and 800 cm−1, which
belonged to N−H stretching vibration, −NH2 scissoring vibra-
tion, C−N stretching vibration, and −NH2 out-of-plane bend-
ing vibration, respectively. The results suggested that the sur-
face modification significantly changed the surface chemistry
of carbon and introduced new functional groups on the carbon
surface.
2.2 Performance of the EDLCs with activated carbon
electrodes
2.2.1 Galvanostatic charge-discharge and specific
capacitance
The galvanostatic charge-discharge was performed for the
carbon electrode-based EDLCs. They exhibited quite similar
shapes for the charge-discharge curves, but were different in
durability of charge-discharge. Fig.3 shows representatively
4-cyclic charge-discharge curves of the original carbon AC-0
capacitor and modified carbon AC-3 capacitor at a current
density of 3 mA·cm−2. Although both curves have the shape of
an isosceles triangle, the details are different. In each cycle of
charge-discharge, the time of charge for AC-0 was longer than
that of discharge, whereas, for AC-3, discharge time was very

Table 2 Specific surface area and pore structure of activated carbons

2 −1
Sample SBET/(m ·g ) Sext/(m2·g−1) Smic/(m2·g−1) Vtot/(cm3·g−1) Vmic/(cm3·g−1) Vmic/Vtot (%) D/nm

AC-0 931 15 916 0.469 0.439 93.5 2.01

AC-1 862 10 852 0.428 0.406 94.7 1.99
AC-2 858 11 847 0.429 0.404 94.2 2.00
AC-3 817 10 807 0.406 0.385 94.9 1.98
AC-4 900 13 887 0.450 0.424 94.1 2.00
AC-5 879 13 866 0.440 0.415 94.3 2.00
AC-6 920 14 906 0.461 0.433 93.9 2.00
SBET: BET specific surface area; Smic: micropore surface area; Sext: external surface area; Vtot: total volume; Vmic: micropore volume; D: average pore diameter
 Yafei Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(7): 1143−1148
Fig.3 Cyclic charge-discharge curves of electric double-layer
capacitors (EDLCs) AC-0 and AC-3
close to that of charge, reflected by a better symmetric trian-
gle-shape, indicating higher coulombic efficiency and the ac-
cumulation of charges based mainly on the electric double-
layer. Besides, it was found that the potential drop (IR drop)
was very small at the very beginning of discharge, indicating
that carbon electrodes contacted well with electrolyte solution,
the ESR calculated by formula (2) was as small as 0.3 Ω.
The specific capacitances of carbon as a function of dis-
charge current were calculated according to formula (1) as
shown in Fig.4. It was clear that the modification significantly
increased the specific capacitance. Indeed, the higher the con-
centration of HNO3 or H2O2, the higher the specific capaci-
tance was. At 3 mA·cm−2, the specific capacitance of AC-0
was 145 F·g−1 only, whereas, that of AC-3 and AC-2 reached
250 and 218 F·g−1, increased by 72.4% and 50.3%, respec-
tively. Although the specific surface area of modified carbons
was smaller than that of original carbon, the former had a
large specific capacitance, suggesting that the surface area was
not the sole factor influencing the specific capacitance, surface
chemistry of carbon could play an important role. As shown in
the FTIR spectra, the surface chemistry of carbon changed
obviously after modification. The carboxyl groups decreased,
whereas, carbonyl, hydroxyl, and amidogen groups were in-
troduced on the carbon surface. These functional groups in-
creased polarity and improved the hydrophilicity or wettability
of the carbon surface, thus enhancing the adsorption of elec-
trolyte ions on the carbon surface and increasing the effective
surface area for the formation of electric double-layer capaci-
Fig.4 Specific capacitance of carbon electrode at various
current densities
tance. In addition, these surface functional groups could cause
reversible redox that generated pseudocapacitance. Therefore,
the combined effect of enhanced hydrophilicity and redox of
functional groups remarkably increased the specific capaci-
tance of modified carbons. It could be concluded that hy-
droxyl, carbonyl, and quinine groups were of benefit to the
formation of the electric double-layer, whereas, the carboxyl
groups had a negative influence. The result was consistent
with that of Nian and Teng[16].
In general, the specific capacitance of a porous electrode
decreased with increasing discharge current, due to the diffu-
sion effect of electrolyte ions in the pores, especially in the
small micropores, where the diffusion resistance was large, for
the transportation of ions to the electrode surface. Because all
the investigated carbons were highly microporous materials,
the diffusion effect could not be neglected. The specific ca-
pacitance of carbons decreased significantly with increasing
current density from 3 to 5 mA·cm−2, especially for the modi-
fied carbons, as their average pore size was smaller than that
of the original carbon, suggesting that the pore size was a
dominant factor for the formation of an electric double-layer.
However, as the current density increased from 5 to 60
mA·cm−2, the specific capacitance of the original carbon de-
creased smoothly by 17.2%, whereas, the modified carbons
AC-3 and AC-5 decreased by 12.9% and 15.1% only, sug-
gesting that surface functional groups played a positive role,
to counteract the negative influence of the diffusion effect.
The results showed that the surface-modified carbons retained
a large capacitance at high current densities. The results dem-
onstrated that the modified carbon electrode-based EDLCs
had not only high energy density, but also high power density.
2.2.2 Cyclic voltammogram
The cyclic voltammograms of EDLCs as a function of po-
tential sweep rate are shown in Fig.5. All voltammogram
curves are very close to a rectangle shape and exhibit good
symmetry, indicating typical capacitive characteristics[17]. The
voltammogram curve of AC-3 is bulgy with a wide potential
range (0.1−0.8 V) because of both contributions of EDL and
 Yafei Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(7): 1143−1148
Fig.5 Cyclic voltammograms of EDLCs AC-0 and AC-3 at
different sweep rates
faradaic capacitance. The reversible redox reactions of func-
tional groups introduced on the carbon surface might occur to
generate pseudocapacitance during charge-discharge, so that
the total capacitance of the supercapacitor was increased. The
responded currents of the AC-3 capacitor at different sweep
rates were always much larger than that of AC-0, suggesting
that the surface modification significantly enhanced the ca-
pacitive behavior of the carbon. The voltammogram curves of
other modified carbon capacitors were similar to those of
AC-3. Repeated cyclic voltammograms had almost no change
in shape, indicating a good reversible characteristic of
charge-discharge and the high stability of carbon electrode
materials.
2.2.3 Leakage current and ac impedance
Leakage current is a very important parameter of a super-
capacitor. It is usually caused by the combined effect of elec-
trolyte resistance, impurity, and impedance of the electrode
materials. The capacitors were fully charged, and then kept at
a constant potential and the currents were recorded as a func-
tion of time. Usually, after 5 RC (response current) time, a
stable current was obtained as the leakage current. Fig.6
shows the current−time curve of EDLCs with carbon elec-
trodes before and after modification. At the beginning, the
current decreased sharply with increasing time. Shortly the
current became a stable value for AC-3, whereas, the current
of the original carbon EDLC decreased much more slowly,
and the current plateau was higher than that of AC-3. The
Fig.6 Leakage current of EDLCs with carbon electrode before
and after modification by nitric acid
modification with HNO3, H2O2, and NH3·H2O improved the
hydrophilicity and wettability of the carbon surface. Further-
more, HNO3 removed inorganic impurities, which was one of
the reasons for the self-discharge of electrode materials[18]. It
is reported that the leakage current increased with increasing
carboxyl groups, but it had no direct relationship with total
oxygen-containing groups[19]. As shown in the previous sec-
tion, the modification introduced hydroxyl, carbonyl, and
amidogen groups on the carbon surface; meanwhile, it reduced
the carboxyl groups significantly. As a result, the leakage cur-
rent decreased extraordinarily.
The leakage currents of EDLCs AC-0, AC-1, AC-2, AC-3,
AC-4, AC-5, and AC-6 are 371, 3, 12, 13, 18, 12, and 10 μA,
respectively. The leakage currents of the modified carbon ca-
pacitors decreased unexpectedly, 0.8%−4.9% that of the
original carbon. It was much lower than 49 μA, a low leakage
current reported in literature[20]. It is well known that a small
leakage current can greatly improve the performance of a su-
percapacitor.
Alternating current (ac) impedance is one of the important
methods to study the electrochemical property of electrodes
and capacitors. It is a complex impedance spectrum. The
imaginary part of the impedance is plotted as a function of the
real part, to compose the impedance spectrum, the so-called
Nyquist plot. The capacitance or pseudocapacitance on the
electrode interface relates directly to the current responded,
which is dependent on the ac potential imposed. The capaci-
tance can be calculated by the imaginary part of the imped-
ance spectrum according to formula (4).
1
Z' ' = − (4)
2 πfC
where f is the applied frequency, Z′′ is the imaginary imped-
ance. Fig.7(a) shows the Nyquist plots of the carbon electrode-
based capacitors. The impedance spectra of surface modified
carbons AC-3, AC-4, and AC-6 capacitors are almost the same.
They have no visible semicircle, a linear part with an angle of
45° in the middle-high frequencies (Warburg impedance, in-
dicating the diffusion-limited characteristic of electrolyte ion
transportation in porous electrodes) and an almost vertical line
to the Z′ axis in the low frequencies, indicating good capaci-
 Yafei Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(7): 1143−1148
Fig.7 AC impedance spectra of activated carbons before and
after modification
(a) Nyquist plots of EDLCs, (b) capacitance vs frequency
tive character. On the contrary, the AC-0 capacitor has a com-
pressed semicircle with large radius in the high frequencies,
and Warburg impedance and an acclivitous line from middle
to low frequencies, suggesting a poorer capacitive behavior.
As seen from Fig.7(b), the specific capacitance increases sig-
nificantly for modified carbons, especially AC-3. Because the
modification introduced the functional groups and improved
the hydrophilicity of the carbon surface, this decreased the re-
sistance between electrode and electrolyte and increased the
efficiency of charge-transfer and mass- transfer on the elec-
trode/electrolyte interface. The results agreed well with that
from the galvanostatic charge-discharge.
3 Conclusions
A commercial activated carbon was modified by surface
treatment using nitric acid, hydrogen peroxide, and ammonia,
respectively. The results showed that the modification resulted
in no big decrease in the specific surface area; the higher the
concentration of the chemical agent, the larger the decrease
was. The average pore size decreased very slightly. The modi-
fication significantly changed the surface chemistry of the
carbon. The original carboxyl groups decreased, new oxygen-
containing carbonyl and hydroxyl groups were introduced by
modification with HNO3 and H2O2; and amidogen groups
were produced by modification with ammonia on the carbon
surface.
As a result, the wettability of the carbon surface increased,
which significantly improved the electrochemical behavior of
the modified carbons. The highest specific capacitance of the
modified carbon reached 250 F·g−1, and increased by 72.4%
compared with that of the original carbon. The leakage current
of the modified carbon-based capacitors decreased unexpect-
edly, the smallest was only 3 μA, less than 1% of that of the
original carbon. Alternating current impedance spectrum
showed that the modification evidently improved the charac-
teristic of frequency response of the carbon electrode, thus the
specific capacitance of the carbons increased. The modifica-
tion of the surface treatment with common chemicals is a sim-
ple and effective process, thus it is a promising route to pro-
duce high performance and cost-effective carbon electrode
materials for the supercapacitor.
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