CARBON 4 6 ( 2 0 0 8 ) 1 7 1 8 –1 7 2 6

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Hierarchical porous carbons with controlled micropores

and mesopores for supercapacitor electrode materials

Kaisheng Xia, Qiuming Gao*, Jinhua Jiang, Juan Hu

State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Various porous carbons were prepared by CO2 activation of ordered mesoporous carbons
Received 4 May 2008 and used as electrode materials for supercapacitor. The structures were characterized by
Accepted 20 July 2008 using X-ray diffraction, transmission electron microscopy and nitrogen sorption at 77 K.
Available online 26 July 2008 The effects of CO2 treatment on their pore structures were discussed. Compared to the pris-
tine mesoporous carbons, the samples subjected to CO2 treatment exhibited remarkable
improvement in textural properties. The electrochemical measurement in 6 M KOH electro-
lyte showed that CO2 activation leads to better capacitive performances. The carbon
CS15A6, which was obtained after CO2 treatment for 6 h at 950 °C using CMK-3 as the pre-
cursor, showed the best electrochemical behavior with a specific gravimetric capacitance of
223 F/g and volumetric capacitance of 54 F/cm3 at a scan rate of 2 mV/s and 73% retained
ratio at 50 mV/s. The good capacitive behavior of CS15A6 may be attributed to the hierar-
chical pore structure (abundant micropores and interconnected mesopores with the size
of 3–4 nm), high surface area (2749 m2/g), large pore volume (2.09 cm3/g), as well as well-
balanced microporosity and mesoporosity.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction large-scale applications of portable electronic systems and

Because of the depleting energy sources and increasing envi-
ronmental concerns caused by excessive relying on fossil
fuels, the electrochemical energy storage and conversion de-
vices, such as batteries, fuel cells and supercapacitors, are un-
der serious consideration as alternative energy/power
sources. Supercapacitor, also called electrochemical capaci-
tor, is a kind of novel device that stores electrical energy in
the electrode/electrolyte interface. Usually, supercapacitors
may be divided into two categories, namely, electrical dou-
ble-layer capacitors (EDLCs) and pseudocapacitors, which
are distinguished by their charge storage mechanisms. EDLCs
show an electrostatic attraction with accumulation of charges
at the electrode/electrolyte double-layer interfaces, while
pseudocapacitors exhibit faradic redox reactions. The devel-
opment of this kind of power sources is very useful for the
automotives, due to their high power density, excellent
reversibility, and long cycle life [1–3].
In recent years, efforts in developing better supercapacitor
electrode materials have gained considerable attention. Carbo-
naceous materials are widely used for supercapacitor elec-
trodes because of their relatively low cost, versatile existing
forms, large specific surface area, good electric conductivity,
and excellent chemical stability. Generally, the highly devel-
oped surface area and porosity are necessary for carbon elec-
trodes to obtain high specific capacitance [3–6]. Activated
carbons have been widely adopted as electrode materials for
supercapacitor [7–15]. Although super activated carbons with
very high surface areas and pore volumes have been obtained
by choosing suitable precursors and activation methods, the
pore structures are uncontrollable and the pores are mainly
contributed by micropores (<2 nm), which are not favorable

* Corresponding author: Fax: +86 21 52413122.

E-mail address: qmgao@mail.sic.ac.cn (Q. Gao).
0008-6223/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2008.07.018
 CARBON 4 6 ( 20 0 8 ) 1 7 1 8–17 2 6
for quick electrolyte ion diffusion. As a result, the capacitances
of the super activated carbons were much lower than that ex-
pected. In addition, the activated carbons have showed more
serious limitation for high power applications [1–3,8], which
is recognized as one of the main advantages of supercapacitors.
Therefore, besides the basic requirement of high surface area
and large pore volume, it is indispensable to have an appropri-
ate pore structure for ideal supercapacitor electrode material.
Recently, ordered mesoporous carbons [16–18] with con-
trollable pore structure have attracted much attention in many
fields. Several literatures have exhibited promising electro-
chemical capacitive properties of the mesoporous carbons as
supercapacitor electrode materials [19–31]. The good capaci-
tive behavior may be attributed to the numerous textural char-
acteristics of this kind of carbons. The ordered mesopore (2–
50 nm) channels facilitate the electrolyte ion diffusion in the
material, a noticeable volume of micropores (<2 nm) can pro-
vide abundant adsorbing sites for the ions, and the ratio of
microporosity over mesoporosity can be adjusted. However,
a recent study indicated that the expected advantages for
the templated mesoporous carbons over activated carbons as
supercapacitor electrodes were not obvious [32]. This is mainly
due to the limited surface area, typically in the range of 800–
1500 m2/g, and relatively low microporosity in the templated
mesoporous carbons. Significantly, Chmiola et al. have found
the anomalous capacitance increase when they used car-
bide-derived carbons at pore sizes less than 1 nm as an elec-
trode of supercapacitor in an organic electrolyte [33]. The
findings highlight the important role of micropores in
enhancement of capacitance. This work will lead to a better
understanding of ionic transport in narrow channels.
In order to further improve their capacitive performance,
some studies have focused on introduction of faradic pseu-
do-capacitance in the ordered mesoporous carbons [6,34–
36]. However, few literatures have resorted to tailor the pore
structure of the templated mesoporous carbon to improve
electrochemical performance. Ania and co-workers [37] syn-
thesized microporous templated carbon doped with nitrogen,
and found that the new material exhibits a large gravimetric
capacitance in aqueous media because of the electrochemical
activity of heteroatoms and the accessible porosity. Very
recently, Wang and co-workers [38] reported the electrochem-
ical performance of three-dimensional (3D) aperiodic hierar-
chical porous graphitic carbon, and discovered that the
hierarchical porous texture composed of macropores, mesop-
ores and micropores displays great potential for advanced
electrochemical capacitor applications.
The physical or chemical activation has been widely used
in preparation of activated carbons as an effective method to
increase the surface area and porosity of carbon materials.
However, there is little research investigating the activation
of templated carbons. We have reported the CO2 activation
of templated mesoporous carbons CMK-3 and CMK-1, and
the results showed that the specific surface area and volume
of both mesopores and micropores of the resultant carbons
were enhanced remarkably [39,40]. The more suitable porous
texture for supercapacitor application motivated us to further
explore their electrochemical capacitive behaviors. In this
work, we report the electrochemical performances of two
kinds of templated mesoporous carbons before and after acti-
1719
vation. The textural and electrochemical properties of the car-
bon materials are discussed in detail.
2. Experimental
2.1. Preparation of mesoporous carbons
Firstly, two kinds of ordered mesoporous carbons CMK-3 and
CMK-1 were prepared by replication from two-dimensional
hexagonal mesoporous silica SBA-15 and three-dimensional
cubic mesoporous silica MCM-48, respectively.
SBA-15 silica was prepared using the triblock copolymer,
EO20PO70EO20 (Pluronic P123), as the surfactant and tetraethyl
orthosilicate (TEOS, analytical reagent) as the silica source
[41]. The detailed synthesis route can be found in the litera-
ture [39]. MCM-48 silica was prepared by a room temperature
method [42]. The reactants for the synthesis were TEOS, dis-
tilled water, ethanol, cetyltrimethylammonium bromide
(CTAB) and NH3 Æ H2O [40].
The mesoporous carbon CMK-3 was synthesized using
SBA-15 as template and sucrose as carbon source. Briefly,
1.0 g of SBA-15 was impregnated with an aqueous solution
obtained by dissolving 1.25 g of sucrose and 0.14 g of H2SO4
in 5.0 g of deionized water. The mixture was then dried at
100 °C for 6 h, and subsequently at 160 °C for 6 h. The silica
sample, containing partially polymerized and carbonized su-
crose, was treated again at 100 and 160 °C after the addition of
0.8 g of sucrose, 90 mg of H2SO4 and 5.0 g of deionized water.
The sucrose/silica composite was then heated at 900 °C for 6 h
under nitrogen to complete the carbonization. The silica tem-
plate was removed by hydrofluoric acid (HF) at room temper-
ature. The carbon product thus obtained was filtered, washed
with deionized water and ethanol, and dried. Mesoporous car-
bon CMK-1 was obtained using the analogous incipient wet-
ness method. However, the concentrations of sucrose and
sulfuric acid differ from that in CMK-3. Briefly, CMK-1 was ob-
tained by impregnating 1.0 g MCM-48 as-prepared with 1.1 g
of sucrose, 0.12 g of H2SO4 and 4.3 g of deionized water, and
then with 0.65 g of sucrose, 80 mg of H2SO4 and 4.3 g of deion-
ized water in the second step.
The CO2 post treatment was subsequently adopted to tai-
lor the textures (surface area, pore volume, pore size distribu-
tion, etc.) of carbons CMK-3 and CMK-1. In brief, the as-
prepared ordered mesoporous carbon was placed in the cen-
ter of a quartz tube in a tube furnace and heated (5 °C/min) to
950 °C under nitrogen, and then the gas stream was switched
to CO2 (50 cm3/min). After the activation procedure, the sam-
ple was cooled down to room temperature under nitrogen.
When CMK-3 carbon was subjected to CO2 treatment, sam-
ples CS15A2, CS15A4 and CS15A6 represented porous carbons
obtained after the treatment for 2, 4, and 6 h, respectively.
Correspondingly, the samples CS48A2, CS48A4 and CS48A6
were obtained using CMK-1 as the precursor.
2.2. Structural and textural characterization
Powder X-ray diffraction (XRD) patterns were recorded on a
Rigaku D/MAX-2250V diffractometer using Cu Ka radiation
(40 kV and 40 mA). The scanning rate was 0.8 deg./min for
the low-angle XRD measurements. Transmission electron
1720 CARBON 4 6 ( 2 0 0 8 ) 1 7 1 8 –1 7 2 6
microscopy (TEM) images were taken on a JEOL (JEM-2010)
microscope at an accelerating voltage of 200 kV. The samples
for TEM were prepared by ultrasonic dispersing the powder
products in ethanol, which were then deposited and dried
on a holey carbon film on a copper grid. Volumetric nitrogen
sorption studies were taken at 77 K using a Micromeritics
ASAP 2020 system. Before measurements, the samples were
degassed below 1.33 Pa at 90 °C for 1 h and heated (10 °C/
min) to 350 °C for 5 h. The specific surface area (SBET) was cal-
culated by the BET (Brunauer–Emmett–Teller) method in the
relative pressure range of 0.04–0.20. Total pore volume (Vt)
was calculated at relative pressure p/p0 = 0.98. The micropore
volume (Vmi) was determined by applying Dubinin–Radushke-
vich (DR) analyses on the corresponding isotherms in the rel-
ative pressure range from 10 4 to 10 2. Although applying DR
equation to N2 sorption has limitations with respect to calcu-
lating the micropore volumes, it is suitably used here for com-
parative analysis of micropore volume of a set of comparable
samples. The mesopore volume (Vme) was obtained by sub-
tracting the micropore volume from total pore volume. The
mesopore and micropore sizes of carbons were analyzed by
the Barrett–Joyner–Halenda (BJH) and Horvath–Kawazoe (HK)
methods, respectively. The average pore size (DA) was esti-
mated from the equation of 4Vt/SBET.
2.3. Electrochemical determination
To prepare the working electrodes, a mixture of porous car-
bon materials, polytetrafluoroethylene (PTFE) binder and
acetylene black with the weight percent ratio of 80:10:10
was dispersed in alcohol and pressed between two pieces of
nickel foam under 5 MPa. The mass of activated substance
in each electrode was about 10 mg. Then, the electrodes were
dried at 100 °C for 12 h. In our experiment the electrode thick-
ness is in the range of 450–500 lm. The active film can be ob-
tained by subtracting pressed nickel foil from the electrode
thickness. The results show that the thickness of active film
is in the range of 150–200 lm. Before electrochemical tests,
the electrodes were impregnated with electrolyte for 24 h.
The electrochemical behavior of the carbon electrode was
analyzed by cyclic voltammetry (CV) using a three-electrode
configuration in an electrolyte of 6 M KOH. A Pt wire and
Ag/AgCl were used as the counter and reference electrodes,
respectively. Cyclic voltammetry was performed on a CHI440
electrochemical workstation in the potential range of 1.0
to 0.1 V (vs. Ag/AgCl) with scan rate from 2 to 50 mV/s.
The specific gravimetric capacitance (Cg) of the carbon elec-
trode was calculated using integration of the voltammogram
within the potential range applied. The volumetric capaci-
tance (CV, capacitance per unit bulk volume of carbon) can
be obtained by multiplying the gravimetric capacitance at
the scan rate of 2 mV/s by bulk density.
3. Results and discussion
3.1. Structure and texture characterization by XRD and
TEM
Low-angle XRD patterns of the precursors and attempted CO2
treated samples were recorded to determine the structures.
As shown in Fig. 1, the synthesized mesoporous carbons
CMK-3 and CMK-1 exhibit highly ordered 2D hexagonal and
3D cubic periodic structures, respectively. The TEM micro-
graphs can further confirm the ordered pore arrangements.
The TEM image of CMK-3 viewed perpendicular to the direc-
tion of the hexagonal pore arrangement (Fig. 2a) clearly shows
the ordered pore structure with uniform pore size of about
4 nm. Correspondingly, the typical TEM micrographs of por-
ous carbon CMK-1 viewed from different directions are shown
in Fig. 2d and e. One can clearly observe the cubic regular ar-
ray of uniform pores in it. However, CO2 treatment leads to a
gradual decrease in the degree of regularity of the mesopore
arrangements. The intensity of low-angle XRD peaks of the
activated samples becomes weaker than that of the precur-
sors. As shown in Fig. 1a, the (1 0 0) peaks are reduced and
the (1 1 0) and (2 0 0) peaks can be hardly seen. When the acti-
vation time was prolonged to 6 h, no resolved XRD peak could
be observed, indicating the loss of long-range ordered pore
arrangements. Similar changes of XRD patterns can be ob-
served in Fig. 1b. The high-resolution TEM images distinctly
show the structural transformation of the carbon frame-
works. It can be seen from Fig. 2b and f that the primary struc-
ture of ordered pore arrangement is retained in samples
CS15A4 and CS48A4. But the images became obscure and
a (100 )
Intensity (a.u.)
(110 )
(2 00)
CMK-3
CS15 A2
CS15A 4
CS15A6
1 2 3 4 5 6
2θ ( deg. )
b (110 )
(211)
Intensity (a.u.)
CMK-1
CS48A2
CS48 A4
CS48A6
1 2 3 4 5 6
2θ ( deg. )
Fig. 1 – XRD patterns of the as-prepared mesoporous
carbons and those treated with CO2.
 CARBON 4 6 ( 20 0 8 ) 1 7 1 8–17 2 6 1721

Fig. 2 – TEM images of samples: CMK-3 (a), CS15A4 (b), CS15A6 (c), CMK-1 (d, e) and CS48A4 (f).

the regular pore channels disappeared in parts. Especially in
sample CS15A6 (Fig. 2c), the ordered mesoporous domain
can be hardly seen, which is consistent with the XRD results.
It should be noted that the long-range ordering is lost, but the
interconnectivity of pores is still preserved.
3.2. Nitrogen sorption measurements of the porous
carbons
The nitrogen adsorption–desorption isotherms and corre-
sponding pore size distribution curves by the BJH method of
the precursors and activated porous carbons are shown in
Fig. 3. As shown in Fig. 3a, all carbons are found to be type
IV (based on IUPAC classification) isotherms for the typical
hysteresis loop in the mesopore range. We can see that the
adsorption at relative pressure below 0.1, which is ascribed
to micropore adsorption, increases along with increasing acti-
vation time. Along with the increase of relative pressure, stea-
dy increases in adsorption capacity were caused by the
monolayer/multilayer adsorptions of nitrogen molecules on
the mesopores. At relative pressure above 0.1, activated
samples show obviously more increment in N2 adsorption
1722 CARBON 4 6 ( 2 0 0 8 ) 1 7 1 8 –1 7 2 6

a
Quantity adsorbed (cm3 /g STP)
1400
c
1400
CS15A6

Quantity adsorbed ( cm /g STP)

1200 CS15A4 1200 CS48A6

1000 CS15A2 1000 CS48A4

3
800 800 CS48A2

600 CMK-3 600 CMK-1

400 400

200 200

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/Po) Relative pressure (P/Po)

1.4
b 1.4
d
CMK-1
1.2 CMK-3 1.2
CS48A2
CS15A2

dV/dW ( cm /(g nm))

dV/dW (cm3/(g nm))

CS48A4
1.0 CS15A4 1.0
CS48A6
CS15A6
0.8
3 3 0.8
dV /d W (cm3/(g nm)

2 0.6
0.6
1 CS 15A 6 0.4
0.4
0 0.2
0.2 0.5 1.0 1.5 2.0
Pore size(nm)
0.0
0.0
2 3 4 5 6
2 4 6 8 10 Pore size (nm)
Pore size (nm)

Fig. 3 – N2 adsorption/desorption isotherms (a, c) and the corresponding pore size distribution curves (b, d) of the porous
carbons.

capacity than that of precursor CMK-3. This result shows that decreased after the activation except for sample CS48A6. It
the amount of mesopores increased. It is seen in Fig. 3b that a is noteworthy that the high BET surface area (2749 m2/g)
uniform pore size distribution centered at about 4 nm in all and micropore volume (0.96 cm3/g) are comparable to the
carbons except sample CS15A6, in which the small mesop- highest values ever reported for porous carbons [43,44]. More-
ores between 3 and 4 nm became the main other than over, the proportion between mesopore and micropore in the
micropores. The inset in Fig. 3b shows the micropore size dis- carbon materials is diverse. The volumes of mesopore are
tribution of sample CS15A6 calculated using the HK model higher than that of micropore in CMK-3 and its activated
assuming slit pore geometry. The curve exhibit a relatively samples. And the lowest mesoporosity (54%) exists in sample
sharp distribution of micropores dominated in the range CS15A6. In contrast, CMK-1 and its activated samples show
0.5–0.8 nm. Fig. 3c exhibits the isotherms of CMK-1 and the higher microporosity. We believe that an appropriate propor-
activated samples CS48A2, CS48A4 and CS48A6, which are tion between mesopore and micropore in porous carbon elec-
typical type I/II. Similarly, the CO2 treatment leads to a higher trodes is helpful for supercapacitor application.
adsorption capacity caused by increased micropore and small
mesopore sorption. The peak maxima of pore size distribu- 3.3. Cyclic voltammetry determination
tion by BJH method transfer from 2.4 nm in CMK-1 to about
2.0 nm in CS48A6. Typical cyclic voltammograms for the prepared porous car-
The textural characteristics of the various mesoporous bons in 6 M KOH aqueous electrolyte are shown in Fig. 4.
carbons are listed in Table 1. The specific surface area and to- The CV curves for pristine porous carbon CMK-3 and the
tal pore volume of the porous carbon increase remarkably CO2-activated samples at a scan rate of 2 mV/s are presented
after CO2 treatment. At the same time, a steady increase of in Fig. 4a, which shows a gradual increase in the induced cur-
micropore volume could be found for these carbons. The rent for the CO2 treated carbon electrodes. It can be observed
great enhancement is probably due to the activation opening that all the carbons present a quasi-rectangular voltammo-
the closed pores, drilling new narrow micropores and widen- gram shape at the low voltage scan rate, indicative of excel-
ing the pre-existent. As a result, the average pore diameter lent candidates as electrode materials for electrochemical
 CARBON 4 6 ( 20 0 8 ) 1 7 1 8–17 2 6 1723

Table 1 – Textural characteristic of ordered mesoporous carbons and their activated samples
Samples SBET (m2/g) Vt (cm3/g) Vmi (cm3/g) Vme (cm3/g) DA (nm)

CMK-3 984 1.09 0.37 0.72 4.6

CS15A2 1814 1.76 0.69 1.07 4.0
CS15A4 2110 2.01 0.79 1.22 4.0
CS15A6 2749 2.09 0.96 1.13 3.0
CMK-1 1788 1.06 0.53 0.53 2.4
CS48A2 2373 1.43 0.81 0.62 2.4
CS48A4 2741 1.73 0.94 0.79 2.5
CS48A6 2696 1.87 0.94 0.93 2.8

a 0. 6
c 0. 8

0. 6
0. 4
0. 4
0. 2

Current (A/g)
Current (A/g)

0. 2
0. 0
0. 0
-0 .2
-0 .2
-0 .4
CMK-3 -0 .4 CMK-1
-0 .6 CS15A2 CS48A2
CS15A4 -0 .6 CS48A4
-0 .8 CS15A6 CS48A6
-0 .8
-1.0 -0.8 -0.6 -0.4 -0.2 -1 .0 -0.8 -0 .6 -0.4 -0.2
Voltage (V) vs. Ag/AgCl Voltage (V) vs. Ag/AgCl

b d 12
12
8
8
4
Current (A/g)

4
Current (A/g)

0 0

-4 -4
2mV/s 2mV/s
-8 5mV/s 5mV/s
-8
10mV/s 10mV/s
-12 20mV/s 20mV/ s
50mV/s -1 2 50mV/s

-1.0 -0.8 -0.6 -0.4 -0.2 -1.0 -0.8 -0.6 -0.4 -0.2
Voltage (V) vs. Ag/AgCl Voltage (V) vs. Ag/AgCl

Fig. 4 – Cyclic voltammograms for the CMK-3 (a), CMK-1 (c) and their activated porous carbons at 2 mV/s, as well as CS15A6 (b)
and CS48A4 electrodes (d) at different scan rates.

double-layer capacitor. Moreover, the effects of voltage scan
rates on the capacitive behavior of these porous carbons were
also investigated. Fig. 4b presents the CV curves for sample
CS15A6 at various scan rates changing from 2 to 50 mV/s.
As the scan rate increased, the CV curves became gradually
depressed but still maintained a less rectangular shape. This
means that the CS15A6 electrode would be suitable for quick
charge–discharge operations. The CV curves for CMK-1 and
the treated carbon materials can be found in Fig. 4c and d.
There is also an increase in the induced current caused by
CO2 treatment; however, the enhancement was not as high
as that of the 2D ordered mesoporous carbon CMK-3. Simi-
larly, it can be seen from Fig. 4d that the CS48A4 electrode
also shows good capacitive behavior even at a high scan rate.
The calculated specific gravimetric capacitances and volu-
metric capacitances for all porous carbons are listed in Table
2. The relationship between the retained capacitance ratio
and voltage scan rate is plotted in Fig. 5. Obviously, there
are notable increases in specific capacitance caused by CO2
treatment for both 2D ordered porous carbon CMK-3 and 3D
ordered porous carbon CMK-1. The better electrochemical
performance of the resultant porous carbons could be
1724 CARBON 4 6 ( 2 0 0 8 ) 1 7 1 8 –1 7 2 6

Table 2 – Capacitances at different voltage scan rates for ordered mesoporous carbons and their activated carbon
electrodes

Samples Cg/SBET(F/m2) CV(F/cm3) Cg at different voltage scan rates (F/g)

2 mV/s 5 mV/s 10 mV/s 20 mV/s 50 mV/s

CMK-3 0.117 43 115 113 107 102 92

CS15A2 0.085 48 154 148 142 134 118
CS15A4 0.078 47 164 157 151 143 127
CS15A6 0.081 54 223 206 194 182 162
CMK-1 0.092 57 164 154 145 133 108
CS48A2 0.079 54 187 175 166 153 127
CS48A4 0.070 50 192 178 169 158 134
CS48A6 0.066 44 178 169 160 151 129

g is in the highest values for mesoporous carbons reported

a by other groups [26–32], even though, the performance of
Ratio of retained capacitance (%)

100
CS15A6 at high-rate operation is inferior to HPGC [38] re-
CMK-3
ported by Wang et al., possibly due to the unconspicuous
CS15A2
CS15A4 macropores in CS15A6. It should also be noted that the thick-
90 CS15A6 ness of the active film in supercapacitor electrodes may influ-
ence the result of high-rate CV test. In our experiment, the
thickness of active film is in the range of 150–200 lm, which
80 is a little thicker than the appropriate value 100 lm. The rela-
tively thick active film may also lead to the decreasing of re-
tained capacitance ratio. Therefore, it is necessary to
prepare much thinner electrode in future work. Due to the
70
3D interconnected mesopores, larger surface area, and higher
micropore proportion, CMK-1 electrode exhibits higher spe-
0 10 20 30 40 50 cific capacitance value of 164 F/g than that of CMK-3 at
Scan rate (mV/s) 2 mV/s. However, when the scan rate increased from 2 to
50 mV/s, the retained ratio is only 66%. This is believed to
be attributed to the unfavorable ionic diffusion in smaller
b
Ratio of retained capacitance (%)

100 mesopores in 3D cubic mesoporous carbon CMK-1 [30,31].

90
80
70
60
0 10
Scan rate (mV/s)
Fig. 5 – The dependence of retained capacitance ratio of the
porous carbon electrodes on voltage scan rates.
ascribed to their higher surface area and micropore volume,
and more suitable pore structure. When the scan rate in-
creased from 2 to 50 mV/s, the specific capacitance of CMK-
3 decreased from 115 to 92 F/g with a retained ratio of 80%.
In contrast, sample CS15A6 shows a little depressed ratio of
73%, with values dropping from 223 to 162 F/g. The high ratio
is the obvious superiority of this kind of porous carbon over
super activated carbon [30]. The capacitive capacity of 223 F/
CMK-1 Compared with that of CMK-3, the improvement of the elec-
CS48A2 trochemical capacitive performances of CMK-1 caused by
CS48A4 CO2 treatment is lower. The highest value of 192 F/g occurred
CS48A6
in sample CS48A4 with a little increased retained capacitance
ratio of 70%. Although carbon CS48A4 has a comparable spe-
cific surface area with CS15A6, the specific capacitance is dis-
tinctly low. It may correlate with the difference of pore
volume and pore size distribution between them. Besides,
the volumetric capacitances increased from 43 for CMK-3 to
54 F/cm3 for CS15A6 with increasing activation time, whereas
the capacity decreased from 57 for CMK-1 to 44 F/cm3 for
CS48A6 (Table 2). Obviously, sample CMK-1 with moderate
20 30 40 50
surface area shows the highest volumetric capacitance. It
suggests that huge surface area is not necessary to pursue
large volumetric capacitance.
It is clear that sample CS15A6 exhibited the best electro-
chemical behavior. The superior performance can be ascribed
to its following characteristics. Firstly, the hierarchical pore
structure in the carbon electrode is crucial for supercapacitor
application. The abundant micropores play an essential role
for optimizing the electrical double-layer surfaces and then
strengthen the value of capacitance. Our result indicates that
the more microporous sample CS15A6 showed the best per-
formance. Therefore, the micropore volume is the main
parameter to manage to reach high gravimetric capacitance.
In addition, the interconnected mesopores with the size of
 CARBON 4 6 ( 20 0 8 ) 1 7 1 8–17 2 6
3–4 nm provide a good charge propagation and ability for high
current loads. Secondly, its specific surface area as high as
2749 m2/g and pore volume as large as 2.09 cm3/g lead to a
superior ability for quick charge accumulation, thus remark-
ably improving the electrochemical performance of superca-
pacitors. However, it is unadvisable to pursue too huge
surface area or pore volume for their negative effect on volu-
metric capacitance. Thirdly, a well-balanced micro/mesopo-
rosity in CS15A6 is also helpful. It was reported that very
high mesopores proportion is even harmful for optimal
capacitor operation [28]. At the same time, a certain amount
of mesopores can provide low-resistant pathways [38] and
short distance for ions through the porous particles. Never-
theless, if we can design the pore length of carbon materials,
a totally microporous carbon with short pore length is also a
promising supercapacitor electrode material. Besides, the
specific capacitance per unit surface area (Cg/SBET) at 2 mV/s
is calculated (Table 2) to investigate the efficiency of the BET
surface area for charge accumulation. The CO2 treatment
leads to lower values in both series of activated porous car-
bons. Because the content of defects increased greatly and
the channels became a little disordered in the resultant car-
bons, the transmission rates of the electrolyte ions in the
channels would be lower. Further work is in process to facili-
tate the transmission rates of the electrolyte ions.
4. Conclusions
Novel electrode materials for supercapacitor were developed
by CO2 activation of ordered mesoporous carbons CMK-3
and CMK-1. Compared with that of the untreated carbons
CMK-3 and CMK-1, the CO2-activated carbons showed vari-
able porous textures and remarkable enhancements in the
specific surface area and volume of both mesopores and
micropores at the expense of ordered pore structures. As to
the electrochemical capacitor application, 2D hexagonal
CMK-3 was superior to 3D cubic CMK-1. The carbon electrode
material CS15A6, which was obtained after CO2 treatment for
6 h at 950 °C using CMK-3 as reaction precursor, exhibited the
best electrochemical behavior with a specific gravimetric
capacitance of 223 F/g and volumetric capacitance of 54 F/
cm3 at 2 mV/s in 6 M KOH electrolyte and 73% retained ratio
at 50 mV/s. Besides, the good performance at high current
loads is the obvious superiority of this kind of porous carbon
over super activated carbon. Correlating the capacitive behav-
ior with textural characteristics, we ascribed the excellent
electrochemical properties to hierarchical pore structure
(abundant micropores and interconnected mesopores with
the size of 3–4 nm), high surface area (2749 m2/g), large pore
volume (2.09 cm3/g), and well-balanced micro/mesoporosity
in sample CS15A6.
Acknowledgements
This work was financially supported by Chinese National Sci-
ence Foundation (No. U0734002), ‘‘Project of One Hundred
Outstanding Talents’’ of Chinese Academy of Sciences and
Shanghai Nanotechnology Promotion Center (No.
0652nm025).
1725
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