Electrochemistry Communications 10 (2008) 1809–1811

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

The superior electrochemical performance of oxygen-rich activated carbons

prepared from bituminous coal
Chuanxiang Zhang a,b, Donghui Long a, Baolin Xing b, Wenming Qiao a, Rui Zhang a, Liang Zhan a,
Xiaoyi Liang a, Licheng Ling a,*
a
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237, China
b
Henan Polytechnic University, Henan, Jiaozuo 454000, China

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

Article history: Oxygen-rich activated carbons (OAC) were prepared from bituminous coal through a quick KOH activa-
Received 25 August 2008 tion. OAC exhibited a moderately large surface area of 1950 m2/g, a relative wide pore size distribution,
Received in revised form 12 September good conductivity and very high oxygen content (up to 12 wt.%). Compared with high surface area acti-
2008
vated carbons prepared by the conventional KOH activation, OAC have superior capacitive behavior,
Accepted 12 September 2008
Available online 20 September 2008
power output and high energy density in electrochemical double layer capacitors (EDLC). OAC presented
a high specific capacitance of 370 F/g in 3 M KOH electrolyte at a low current density of 50 mA/g and still
remained 270 F/g even at a high current density of 20 A/g.
Keywords:
Activated carbon
Ó 2008 Published by Elsevier B.V.
Electrochemical double layer capacitors
Oxygen-rich
High power output
High energy density

1. Introduction Recently, Raymundo-Pinero et al. [13] reported that oxygen-rich

Electrochemical double layer capacitors (EDLC) are promising
high power energy sources for many different applications where
high power density, high cycle efficiency and long cycle life are
needed [1,2]. Among various available candidates of electrode for
EDLC, porous carbons are mostly investigated because of their
well-developed microstructure, good conductivity, excellent phys-
ico–chemical stability as well as low cost and accessibility [3–5].
However, capacitance performances of porous carbons are always
limited by electrochemical accessibility of pores that have a size
smaller than electrolyte ions, low inner-pore ionic transport or
insufficient surface wettability. In addition, their capacitance per-
formances are greatly influenced by the functional groups on the
surface of carbon networks through pseudo-capacitive effect. Thus,
tailoring porous structure and surface chemistry of activated car-
bons is crucial for EDLC optimization [6–10]. However, the meth-
ods to incorporate oxygen to carbon presented in the literature
were limited to modifications including oxidation in the gas or li-
quid phases to increase the concentration of surface oxygen
groups, most of which are unstable and may introduce poor cycle
performance, large leakage current and high internal resistance
of the EDLC [2,8,10–12].
carbon material prepared through carbonization of a seaweed bio-
polymer exhibited good electrochemical performances. This mate-
rial has high oxygen content (15 at.%) and poor developed porosity
(273 m2/g for the specific surface area). Considering that the surface
of carbon framework affords electrode/electrolyte interface for
charge accommodation, oxygen-rich activated carbons (OAC) with
high specific surface area should exhibit outstanding electrochem-
ical performances for EDLC. However, there is relatively little liter-
ature reported along this line as far as author’s knowledge.
Herein we developed an improved KOH activation method to
prepare oxygen-rich activated carbons with high specific surface
area using high oxygen content bituminous coals as carbon precur-
sors. By employing high heating rate and zero-holding activation
time, the obtained materials simultaneously possess high specific
surface area and high amounts of oxygen incorporated in the car-
bon framework. The electrochemical measurements showed that
the as-prepared carbons have much better specific capacitance as
an EDLC electrode than that of the super activated carbon prepared
by a conventional KOH activation.
2. Experimental
2.1. Preparation of activated carbon

* Corresponding author. Tel.: +86 21 64252934; fax: +89 21 64252924. Demineralized bituminous coal from Shenhua mine (China) was
E-mail address: lchling@ecust.edu.cn (L. Ling). milled and sieved to a given size form100 to180 lm, and mixed

1388-2481/$ - see front matter Ó 2008 Published by Elsevier B.V.

doi:10.1016/j.elecom.2008.09.019
1810 C. Zhang et al. / Electrochemistry Communications 10 (2008) 1809–1811

with KOH at a weight ratio of 1:4. The mixtures were activated in a
nickel reactor at 700 °C without any holding time with a high heat-
ing rate of 20 °C/min under nitrogen flow. Then the reactor was
cooled to room temperature. The as-prepared products were
washed with distilled water and then dried at 110 °C. In addition,
activated carbons (AC) prepared by a conventional activation
method were also obtained by using a similar procedure, but dif-
ferent heating rate (5 °C/min) and holding time (700 °C for 1 h).
2.2. Characterization
Elemental compositions of the samples were determined using
an elemental analyzer (Vario EL III, Elementar Instruments, Inc.,
Germany). The surface chemistry was analyzed by X-ray photo-
electron spectroscopy (XPS, Kratos Axis Ultra DLD). The wettability
of the sample was analyzed by wicking kinetic measurement under
Thermo Cahn DCA315 analyzer. Nitrogen sorption isotherms were
measured using a Micrometrics ASAP 2010 analyzer at 77 K. Pore
size distributions of activated carbons were evaluated by using
density functional theory (DFT). Crystallite structure of activated
carbons was analyzed by a Rigaku D/max 2550 X-ray diffractome-
ter with Cu Ka radiation. Powder special resistance was measured
under KQ-1 powder resistance automatic instrument.
2.3. Electrochemical measurements
The capacitor electrodes were made in form of pellets com-
posed of 85 wt.% carbon, 5 wt.% polytetrafluoroethlyene and
10 wt.% acetylene black. The capacitor cell was composed of two
carbon electrodes sandwiched by a separator and contained in an
electrolytic solution of 3 M KOH. Galvanostatic charge/discharge
cycling, cyclic voltammetry (CV) and electrochemical impedance
spectroscopy (EIS) were conducted on an electrochemical analyzer
system (Arbin, USA).
3. Results and discussion
3.1. Structural characteristics
The results of elemental analysis in Table 1 show that the KOH
activation process is a key factor to determine the oxygen content.
The high oxygen content of 12.3 wt.% was retained in OAC obtained
through the quick activation, while only 5.2 wt.% oxygen was re-
tained in AC. The ratios of oxygen to carbon were slightly higher
than that obtained by elemental analysis, indicating that oxygen
was enriched on surface of carbon frameworks. The results of
deconvolution of the O1s peak show that the relative amount of
carbonyl (18 at.%), quinone and hydroxyl (28 at.%) groups in OAC
is higher than that in AC, AC enriched mainly in anhydride
(44 at.%) and carboxylic oxygen (15 at.%).
The suitable quantity of oxide groups can enhance the surface
wettability by electrolyte to OAC [11,12,14]. Relative wetting con-
tact angles of the two samples were measured in 3 M KOH aqueous
solution using the Washburn theory, and the results confirmed
that OAC exhibit a lower relative contact angle of 10° than that
of AC (65°). The improved surface wettability of OAC should in-
crease an efficient utilization of the exposed surface for charge
storage.
The nitrogen sorption isotherms of OAC and AC (Fig. 1) are char-
acteristic of a microporous material. OAC exhibit a moderately
large surface area of 1950 m2/g, a total pore volume of 1.1 cm3/g.
However, AC prepared by the conventional activation has a much
larger surface area (up to 3134 m2/g), a higher total pore volume
(up to 1.8 cm3/g). The DFT pore size distributions for two samples
(shown in Fig. 1 inset) are similar, which can be divided into two
regions: (1) ultrafine micropores (<1 nm), and micropores (1–
2 nm), (2) small mesopores (2–6 nm).
Generally, oxygen atoms on the carbon framework could de-
crease electric conductivity of the material. However, powder spe-
cific resistivity of OAC with 15% oxygen was measured about
28 X cm, which is smaller than that of AC with 5% oxygen
(35 X cm).This could be attributed to the well-developed porosity
of AC which results in the decrease of conductivity. The microcrys-
tal structures of the two samples were also characterized by XRD.
The definite d002 peak at 26.3° was observed for OAC, whereas no
diffraction peaks could be found for AC. Such result could also sug-
gest that OAC with the localized graphitic units should have better
electronic conductivity than AC in which the graphitic structure
was severely etched by KOH [15].
3.2. Electrochemical characteristics
The cyclic voltammograms of OAC are presented in Fig. 2 for dif-
ferent voltage scan rates. The voltammograms of the carbon main-
tained the desired rectangular shape at voltage scan rates of 5 mV/
s. When the voltage scan rate was increased to 50 mV/s, a rectan-
gular shape can still remained, indicating excellent capacitive
behavior even at high current intensity. Such excellent property
of OAC benefit from its small equivalent series resistance
(0.23 X) which should come from a combination of a high elec-
tronic conductivity of electrode materials and a low ionic resis-
tance of the electrolyte within the pores of OAC which exhibit a
large portion of mesopores.
The specific capacitances from galvanostatic charge/discharge
measurements were shown in Fig. 3a. As comparison, the most
popularly applied activated carbon, Maxsorb (BET surface area is
1973 m2/g) was used as a reference. The retention rates of specific
capacitance of three samples are similar. However, OAC possess

Table 1
Elemental and XPS analysis of the samples

Sample Elemental analysis XPS analysis

C H N Oa O/C C N O O/C
(wt.%) (wt.%) (wt.%) (wt.%) (at./ (at.%) (at.%) (at.%) (at./
at.) at)
Coal 79.3 4.9 0.9 14.3 – – – – –
OAC 83.4 3.3 0.4 12.3 0.11 82.4 0.5 12.4 0.15
AC 92.2 1.5 0.6 5.2 0.04 91.9 0.6 5.3 0.05
Fig. 1. Nitrogen adsorption-desorption isotherms and the resulting DFT pore size
a
O by difference. distributions (inset) of the samples.
 C. Zhang et al. / Electrochemistry Communications 10 (2008) 1809–1811
Fig. 2. Cyclic voltammograms for OAC in 3 M KOH at different voltage scan rates.
the largest specific capacitance in the test range although AC has
the highest surface area. It is noted that the specific capacitance
of the OAC can still remain as high as 270 F/g at the high current
density of 20 A/g, which should be the largest value at high current
density for porous carbon electrodes as far as authors know. In
addition, only 7.2% of the initial capacitance (from 320 to 297 F/
g) of OAC is lost after 5000 cycles at a current density of 1 A/g, indi-
cating the capacitor has also a good cycle life. The high supercapac-
itor performance of OAC can also be observed in the Ragone plot
Fig. 3. Electrochemical performance of the samples: (a) Gravimetric capacitances
against current density and (b) Ragone plot.
1811
presented in Fig. 3b. The energy and power densities were calcu-
lated from the galvanostatic cycling of a supercapacitor charged
up to 0.9 V at current densities from 50 mA/g to 20 A/g. With the
increase of power output, the energy densities of OAC only de-
crease a little, the extractable energy of the supercapacitor is still
up to 7.6 Wh/kg while power densities close to 10 KW/kg, which
shows that OAC have excellent electrochemical properties of high
energy density and power output, therefore very promising for
application in the scenarios where high power output as well as
high energy capacity is required.
The excellent electrochemical performance of OAC could be as-
cribed to the following characteristics. Firstly, moderately large
surface area for OAC affords enough electrode/electrolyte inter-
faces for charge accommodation. Secondly, the presence of oxygen
enhances the surface wettability of OAC to ensure a sufficient uti-
lization of the exposed surface for charge storage. Thirdly, presence
of oxygen in carbon network may afford stable pseudo-capacitance
through faradaic charge-transfer reactions. Fourthly, the wide pore
size distribution decreases the inner-pore ion-transport resistance
and the diffusion distance. Lastly, good electronic conductivity
leads to a lower electron transport resistance on the carbon
framework.
4. Conclusion
Oxygen-rich activated carbons were prepared by a quick KOH
activation process (high heating rate and no holding activation
time) using bituminous coal as precursor. The obtained materials
presented excellent performance as an EDLC electrode due to its
high oxygen content, high specific surface area, wide pore size dis-
tribution and good electronic conductivity. Such oxygen-rich acti-
vated carbons offer a great potential in EDLC capacitors,
particularly for applications where high power output and high en-
ergy density are required. Considering that the abundance and low
price of bituminous coal and easy process for preparation, this kind
of activated carbon is a suitable electrode material for EDLC
industry.
Acknowledgement
The authors gratefully acknowledge the financial support of the
National Natural Science Foundation of China (50672025,
50730003).
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