Materials Chemistry and Physics 124 (2010) 504–509

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Activated carbon with high capacitance prepared by NaOH activation

for supercapacitors
Bin Xu a,∗ , Yufeng Chen b , Gang Wei b,∗ , Gaoping Cao a , Hao Zhang a , Yusheng Yang a
a
Research Institute of Chemical Defense, Beijing 100191, China
b
College of Material Science & Engineering, Beijing University of Chemical Technology, Beijing 100029, China

a r t i c l e i n f o a b s t r a c t

Article history: Activated carbons with high volumetric capacitance are prepared from apricot shell by optimizing the
Received 6 January 2010 carbonization temperature prior to NaOH activation to balance the porosity and density. The carboniza-
Received in revised form 1 June 2010 tion temperature has a marked effect on both the pore structure and the electrochemical performances
Accepted 5 July 2010
of the activated carbons. As the carbonization temperature increases, the specific surface area and gravi-
metric capacitance of the carbons decrease, while the apparent electrode density increases. Moderate
Keywords:
carbonization at 500 ◦ C results in not only high gravimetric capacitance (339 F g−1 ) but also high apparent
Microporous materials
electrode density (0.504 g cm−3 ), and hence a highest volumetric capacitance of 171 F cm−3 in 6 mol L−1
NaOH activation
Electrochemical properties
KOH aqueous electrolyte is obtained. The activated carbons also show good rate capability.
Supercapacitor © 2010 Elsevier B.V. All rights reserved.

1. Introduction ture and electrochemical performances of the carbons. Usually, by

In recent years, supercapacitors have been used in a variety
of fields, such as memory backup, electric vehicles, uninterrupted
power sources, digital telecommunication system and electronic
devices, due to their high power density and long cycle life [1–3].
Compared with second batteries, the main disadvantage of the
supercapacitors is their low energy density [4,5], which is an obsta-
cle for their extensive applications. Therefore, it is desire to develop
advanced carbons with high capacitance to improve the energy
density of supercapacitors [6]. Most of the literatures express
capacitance as F g−1 . As we know, the higher the density of the
carbon, the larger the weight ratio of active material to the capac-
itor with a certain volume, and hence the higher energy density
of the capacitor. Therefore, from the view of practical application,
the volumetric capacitance which is the product of the gravimetric
capacitance and the apparent density of the electrodes is of great
importance [7].
Various carbons with high surface area such as activated car-
bons, activated carbon fibers, carbon aerogels, template carbons,
carbide-derived carbons and carbon nanotubes have been widely
investigated as electrode materials for supercapacitors [8–15].
Among these carbons, activated carbons prepared by alkali (KOH or
NaOH) activation have attracted great interests in supercapacitors
as they possess high surface area. Numerous works [15–20] have
focused on the effect of the activation conditions on the microstruc-
∗ Corresponding authors. Fax: +86 10 66705840.
E-mail addresses: xubinn@sohu.com (B. Xu), weigangmail@263.net (G. Wei).
increasing the amount of alkali, elevating activation temperature
or prolonging activation time, the gravimetric capacitance of the
carbons can be enhanced due to the enhanced surface area, at the
cost of decreased density. For example, activated carbons prepared
with 4–6 times KOH or NaOH of precursor can present a super
high surface area over 3000 m2 g−1 , resulting in a high gravimetric
capacitance over 300 F g−1 in aqueous electrolytes. However, as a
high density is often in contradiction with a very developed porous
structure, the volumetric capacitance of these carbons is generally
not satisfactory because of their poor density. Therefore, it is very
important that the preparation conditions of the carbons should
be optimized to balance the porosity and density to maximum the
volumetric capacitance.
The preparation of activated carbons by alkali activation usu-
ally involves two steps, the carbonization of the precursor under an
inert atmosphere and the activation of the char with KOH or NaOH.
As a starting material for activation reaction, the nature of the car-
bonized char, such as the primary porosity, carbon content and the
crystallite structure, can largely predetermine the porous structure
of the final activated carbons. So the carbonization conditions, one
of the most important are the carbonization temperature, are also
very important to control the microstructure of the carbons.
Compared with KOH, NaOH is a better choice as activation agent
due to its lower cost and weaker corrosion [21]. Apricot shell is an
agricultural byproduct abundant in the north of China, and it can
be easily activated to form porous structure than coconut shell.
In the present work, activated carbons are prepared from apricot
shell by NaOH activation for supercapacitors. We focus on the effect
of carbonization temperature on the microstructure and electro-

0254-0584/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.07.002
 B. Xu et al. / Materials Chemistry and Physics 124 (2010) 504–509 505

chemical performances of the carbons in aqueous electrolytes. By

optimizing the carbonization temperature to balance the porosity
and the density, microporous activated carbon with a high volu-
metric capacitance of 171 F cm−3 in aqueous electrolytes has been
obtained with a small amount NaOH at a lower activation temper-
ature.

2. Experimental

2.1. Preparation and characterization

The apricot shell produced from north China was used as the starting mate-
rial. The apricot shell was heated to the carbonization temperature and pyrolyzed
for 1 h in a tubular furnace under the protection of nitrogen (99.999%). Then the
char and sodium hydroxide were mixed with a weight ratio of 1:2, heated up
to 700 ◦ C and the activation was continued for 1 h. After activation, the samples
were washed with 0.5 mol L−1 HCl, hot water and distilled water in sequence to
remove the residual alkali completely, followed by drying at 120 ◦ C for 12 h, then
the final activated carbons were obtained. The carbonization temperature varied in
the range of 400–800 ◦ C. The carbonized char and the activated carbon prepared Fig. 1. Thermogravimetric curve for apricot shell in flow of nitrogen gas.
with carbonization temperature T ◦ C were labeled as CT and ACT, respectively.
The thermogravimetric analysis (Dupont 1090B) was employed to investigate
the thermal decomposition behavior of the pristine apricot shell under the protec-
tion of nitrogen (99.999%). The temperature increased from room temperature to
1000 ◦ C with a ramping rate of 10 ◦ C min−1 . The specific surface area and pore struc-
ture of the carbons were determined by nitrogen adsorption/desorption isotherms
at 77 K (Quantachrome NOVA 1200). The specific surface area was calculated by the
conventional BET (Brunauer–Emmett–Teller) method. The pore size distribution of
micropore and mesopore were obtained by HK (Horvath–Kawazoe) method and BJH
(Barrett–Joyner–Halenda) method, respectively.

2.2. Electrochemical measurments

In order to evaluate the electrochemical performances of the as-prepared acti-

vated carbons in supercapacitors, a mixture of 87 wt% of the activated carbon, 10 wt%
of acetylene black and 3 wt% of PTFE binder was pressed into pellets with a thickness
of ∼0.3 mm as electrodes. Button-type capacitor was assembled with two carbon
electrodes separated by polypropylene membrane using 6 mol L−1 KOH aqueous
solution as electrolytes.
The cyclic voltammetry (CV) was recorded on an electrochemical workstation
Solartron 1280B. The galvanostatic charge/discharge test was carried out on an Arbin
cell tester in 0–1 V. The specific capacitance (C) of a single carbon electrode was
determined with the formula C = 2It/Vm, where I is the discharge current, t is the
discharge time, V is the potential change in discharge and m is the mass of the
active material in a single electrode.

Fig. 2. Nitrogen (77 K) adsorption isotherms of the apricot shell-based activated

3. Results and discussion carbons.

3.1. TG analysis of the apricot shell

Fig. 1 shows the thermogravimetric analysis results of the apri-
cot shell. The dramatic weight loss occurs at 200–400 ◦ C with the
sharp peaks at 296 and 384 ◦ C, resulted in a carbon residue of 38.0%
at 400 ◦ C. As the temperature increases over 400 ◦ C, the weight
loss becomes very slowly. The carbon residue decreases to 31.5%
at 500 ◦ C and 25.6% at 700 ◦ C.
In order to investigate the effect of the carbonization tem-
perature on the followed activation process, the yield of the
carbonization in tubular furnace is also measured. With the
increase of the carbonization temperature, it decreases slightly
from 29.1% at 400 ◦ C to 26.2% at 600 ◦ C, then 23.2% at 800 ◦ C. It
indicates that the non-carbon atoms in apricot shell can be almost
eliminated by pyrolyzing at 400–900 ◦ C for 1 h.
3.2. Porous texture characterization of the activated carbon
A series of activated carbons were prepared by carbonized
the apricot shell at temperatures ranging from 400 to 900 ◦ C,
and subsequent activated at 700 ◦ C for 1 h with a weight ratio of
NaOH/C = 2:1, which is a mild activation condition. The nitrogen
adsorption isotherms at 77 K for the activated carbons are shown
in Fig. 2. The isotherm shapes of the carbons produced with dif-
ferent carbonization temperatures are very similar. After a sharp

Table 1
Porosity characterizations of the apricot shell-based activated carbons prepared by NaOH activation.

Samples Carbonization temperature (◦ C) BET Surface area (m2 g−1 ) Pore volume (cm3 g−1 )

Total Micro Meso

AC400 400 2335 0.984 0.797 0.187

AC500 500 2074 0.861 0.801 0.060
AC600 600 1992 0.829 0.792 0.037
AC700 700 1605 0.664 0.638 0.026
AC800 800 1342 0.559 0.496 0.063
506 B. Xu et al. / Materials Chemistry and Physics 124 (2010) 504–509
Fig. 3. Pore size distribution of the activated carbons, (a) micropore size distribution
by HK method; (b) mesopore size distribution by BJH method.
increase to p/p0 = 0.1, adsorption saturation has already reached
and the plateau is flat. According to IUPAC classification, all the
carbons exhibit type I isotherms, characteristic of microporous
materials. However, the saturated adsorption volume of the car-
Fig. 4. XRD profiles of apricot shell-based char carbonized at different temperatures.
bons decreases with the increase of carbonization temperature,
implying the decrease of the pore volume.
As listed in Table 1, carbonization temperature has marked
effects on the porosity parameters of the activated carbons.
The BET surface area of the carbon AC400 reaches as high
as 2335 m2 g−1 . As the carbonization temperature increases, it
decreases to 1992 m2 g−1 at 600 ◦ C, and then 1342 m2 g−1 at 800 ◦ C.
The pore volume of the carbons also shows a decreasing trend,
from 0.984 cm3 g−1 at 400 ◦ C to 0.469 cm3 g−1 at 800 ◦ C. With the
increase of carbonization temperature, both the BET surface area
and pore volume decrease remarkably, indicating a negative effect
of the increased carbonization temperature on the porosity devel-
opment of the NaOH activated carbons. The sample AC400 has the
highest mesopore volume 0.187 cm3 g−1 , which accounts for only
about 19% of the total pore volume. For the other samples, the meso-
pore volume is negligible comparing with the micropore volume,
indicating highly microporous materials.
Fig. 3 shows the pore size distribution calculated from the
adsorption/desorption isotherms using two different methods:
HK method for microporous region (<2 nm) and BJH method for
mesoporous region (2–50 nm). The mesopores are negligible. The
micropores of all the samples distribute in 0.8–1.8 nm with a peak at
1.0 nm. With the increase of carbonization temperature, the inten-
sity peak weakens, implying a decreased pore volume.
In order to explain the above-mentioned influences of the
carbonization temperature on the activation process, XRD was
employed to investigate the crystalline structure of the char
obtained at different carbonization temperatures. As shown in
Fig. 4, XRD patterns of all the samples are very similar. All the
samples show two broadened peaks, (0 0 2) diffraction at 25◦ and
(1 1 0) diffraction at 43◦ , indicating amorphous carbons. However,
some nice distinctions can be found after careful observation. As the
carbonization temperature increases, the peak representing (0 0 2)
diffraction slightly sharpens and upshifts, and the peak represent-
ing (1 1 0) diffraction becomes more recognizable, which indicates
a more ordered structure, though the structure of all the chars are
far from graphitized structure.
The mechanism of NaOH activation is known as that some active
sites in the char are selectively etched by strong corrosive NaOH
at high temperature to create porous structure [22]. In the car-
bonization process, the resulting chars become richer in carbon
and the fundamental porous structure is built through eliminating
non-carbon atoms. Meanwhile, the crystal structure of the char is
rearranged, resulting in a kind of well-ordered structure. The rear-
rangement hinders the subsequent activation reactions with NaOH
Fig. 5. Galvanostatic charge/discharge profiles of the apricot shell-based activated
carbons in 6 mol L−1 KOH at a current density of 50 mA g−1 .
 B. Xu et al. / Materials Chemistry and Physics 124 (2010) 504–509
to create porous structure [23]. As the non-carbon atoms in apri-
cot shell can be basically eliminated by pyrolyzing at 400–900 ◦ C
for 1 h, the influence of the carbonization temperature may focus
on the rearrangement of the crystal structure. The higher the car-
bonization temperature, the more ordered the crystal structure of
Fig. 6. The gravimetric capacitance (a), electrode apparent density (b) and volumet-
ric capacitance (c) of the apricot shell-based activated carbons in 6 mol L−1 KOH as
a function of carbonization temperature.
507
the char, and hence more difficult of the char to be etched by NaOH
to create adequate porosity. This is why the surface area and pore
volume of the carbons decrease with the carbonization tempera-
ture increases.
3.3. Electrochemical performances of the activated carbon
Galvanostatic charge–discharge was performed to determine
the capacitance of the apricot shell-based activated carbons
in 6 mol L−1 KOH aqueous electrolytes. Fig. 5 shows the
charge/discharge profiles of the capacitors at a current density of
50 mA g−1 . The linear voltage–time dependence demonstrates the
typical capacitive behavior of the cell. The specific capacitance of
the carbons at the current density of 50 mA g−1 is plotted in Fig. 6(a).
Clearly, the apricot shell-based carbons are capable of providing
high double layer capacitance. The capacitance of AC400 reaches
348 F g−1 , which is a very high value for capacitors. As the car-
bonization temperature increases, the capacitance of the carbon
shows a decreasing tendency and drops to 319 F g−1 at 600 ◦ C and
235 F g−1 at 800 ◦ C. The decreased capacitance of the carbon is
attributed to their decreased surface area.
Contrary to the gravimetric capacitance, the apparent den-
sity of the carbon electrodes shows an increasing tendency with
the increase of the carbonization temperature (Fig. 6(b)). The
apparent density of the carbon from the char carbonized at
Fig. 7. (a) Cyclic voltammetry of activated carbon (AC500) in 6 mol L−1 KOH at dif-
ferent scan rates; (b) specific capacitance based on activated carbon (AC500) as a
function of scan rate.
508 B. Xu et al. / Materials Chemistry and Physics 124 (2010) 504–509
400 ◦ C is 0.462 g cm−3 . It increases to 0.518 g cm−3 at 600 ◦ C and
0.648 g cm−3 at 800 ◦ C. The higher carbonization temperature dete-
riorates the activity of the char during NaOH activation, resulting
in the decreased surface area but increased apparent density of the
activated carbon.
The volumetric capacitance is the product of gravimetric capac-
itance and the apparent electrode density of the carbon. The
opposite influence of carbonization temperature on the capaci-
tance and apparent density of the carbon makes the volumetric
capacitance showing a tendency as plotted in Fig. 6(c). It increases
from 161 F cm−3 at 400 ◦ C to 171 F cm−3 at 500 ◦ C, then decreases
slightly with the further increase of the carbonization temper-
ature. The volumetric capacitance of all the carbons is higher
than 152 F cm−3 , which is much higher than the previous reported
nitrogen-containing carbons (110–120 F cm−3 ) [24] and carbide-
derived carbons (140 F cm−3 ) [25]. This value is also higher than
98 F cm−3 for the commercial carbon Maxsorb-3 with a super
high surface area of 3200 m2 g−1 , which presents high gravimetric
capacitance (320 F g−1 ) but poor electrode density (0.306 g cm−3 )
[9]. A moderate carbonization temperature of 500 ◦ C facilitates to
balance the developed porous structure and the high density to
obtain the optimized volumetric capacitance as high as 171 F cm−3 ,
a promising value for supercapacitors.
Rate capability is an important feature of the supercapacitors.
The rectangular cyclic voltammograms of the activated carbons
over a wide range of scan rates reflect the ability of the super-
Fig. 8. The gravimetric capacitance (a) and volumetric capacitance (b) of the apricot
shell-based activated carbons in 6 mol L−1 KOH as a function of current density.
capacitors to cycle at high current densities, almost perfect for
supercapacitors [15]. As an example, the capacitor with AC500
electrodes exhibits a quick charge propagation evidenced by the
regular box-like voltammograms up to a scan rate of 100 mV s−1
(Fig. 7(a)). As shown in Fig. 7(b), the capacitance decreases slightly
with the increase of scan rate. As the scan rate rises to 100 mV s−1 ,
the capacitance can remain 226 F g−1 , almost 70% of that measured
at 1 mV s−1 (336 F g−1 ). The slight capacitance decay at higher scan
rates implies the good rate performance of the activated carbons.
The dependence of the specific capacitance on the current den-
sity is shown in Fig. 8. As the charge–discharge current density
increases, the capacitance decreases slightly, indicating that these
carbons allow rapid ion diffusion. It is found that a moderate car-
bonization temperature facilitates to obtain carbons with both
higher gravimetric capacitance and higher volumetric capacitance
at large current density. The sample AC500 has a better rate capabil-
ity. As the current density increases from 50 mA g−1 to 5000 mA g−1 ,
its capacitance can remain 205 F g−1 and 103 F cm−3 , very attractive
values for supercapacitors.
4. Conclusions
Activated carbons with high volumetric capacitance have been
prepared from apricot shell by optimizing the carbonization tem-
perature prior to NaOH activation. The carbonization temperature
has marked effect on the microstructure and the electrochemical
performances of the activated carbons. As the carbonization tem-
perature increases, the more ordered crystal structure of the char
hinders the subsequent activation reactions with NaOH to create
porous structure, resulting in the decrease of the surface area and
the gravimetric capacitance but the increase of the apparent elec-
trode density. Therefore, the carbonization temperature has to be
optimized to balance the porosity and the density of the carbon
to obtain higher volumetric capacitance. A moderate carboniza-
tion temperature (500 ◦ C) results in higher gravimetric capacitance
(339 F g−1 ) and higher apparent electrode density (0.504 g cm−3 ),
and hence a highest volumetric capacitance of 171 F cm−3 . The
AC500 also shows better rate capability. Its capacitance remains
205 F g−1 (103 F cm−3 ) even when the current density increases to
5000 mA g−1 .
Acknowledgements
Financial support for this work was provided by the National
High Technology Research and Development Program (863 Pro-
gram, 2006AA11A165) and the National Science Foundation of
China (NSFC, 50802112 and 20633040).
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