1680 Energy & Fuels 2006, 20, 1680-1684

KOH Activation of Needle Coke to Develop Activated Carbons for

High-Performance EDLC
Wenming Qiao,*,†,‡ Seong-Ho Yoon,‡ and Isao Mochida‡
State Key Laboratory of Chemical Engineering, East China UniVersity of Science and Technology, 130
Meilong Road, Shanghai 200237, China, and Institute for Materials Chemistry and Engineering, Kyushu
UniVersity, Kasuga, Fukuoka 816-8580, Japan
ReceiVed September 27, 2005. ReVised Manuscript ReceiVed April 7, 2006

Petroleum-based needle coke was activated by KOH to develop high-performance activated carbons as carbon
electrodes for an electric double-layer capacitor (EDLC). The effect of preparation parameters on the properties
of activated carbons was investigated, and their EDLC properties were measured in an organic electrolytic
solution. As-prepared activated carbons (NCD-ACs) exhibit large surface areas (400-2900 m2/g), high EDLC
capacitances (14-44 F/g), and low system resistances (8.3-18.7 Ω) on the basis of the anisotropic texture of
their precursor.

1. Introduction resistance of the EDLC system is an important factor that

Electric double-layer capacitors (EDLC) are very attractive
as a potential energy storage system because of their high energy
density, quick charge-discharge rate, low cost, maintenance-
free long life operation, and environmentally friendly energy
technology.1-4 For the application, activated carbons are
recognized as an essential component because of their large
surface area, highly porous structure, and good adsorption
property.5-7 Activated carbons with large surface areas and
suitable pore structure are expected to be applied as excellent
electrodic materials for developing EDLCs with high perform-
ance.8-12 Although many carbonaceous materials such as
phenolic resin, coal, biomass, pitch, and PVC were used as
precursors to develop electrodic materials, the precursors with
anisotropic textures were confirmed to be important and
promising for the application.13,14
On the one hand, an EDLC with a large capacitance is needed
for use in a variety of applications. On the other hand, the
* To whom correspondence should be addressed. Tel: 81-92-5837801.
Fax: 81-92-5837798. E-mail: qiaown@ cm.kyushu-u.ac.jp.
† East China University of Science and Technology.
‡ Kyushu University.
(1) Yoshida, A. Denki Kagaku 1998, 66 (9), 884.
(2) Conway, B. E. Electrochemical SupercapacitorsScientific Funda-
mentals and Technological Applications; Kluwer Academic/Plenum Pub-
lishers: New York, 1999; p 1.
(3) E. Frackowiak; Beguin, F. Carbon 2001, 39, 937.
(4) Nishino, A. J. Power Sources 1996, 60, 137.
(5) Momma, T.; Liu, X.; Osaka, T.; Ushio, Y.; Sawada, Y. J. Power
Sources 1996, 60 (2), 249.
(6) Tanahashi, I.; Yoshida, A.; Nishino, A. J. Electrochem. Soc. 1990,
137, 3052.
(7) Nakamura, M.; Nakanishi, M.; Yamamoto, K. J. Power Sources 1996,
60 (2), 225.
(8) Bonnefoi, L.; Simon, P.; Fauvarque, J. F.; Sarrazin, C.; Dugast, A.
J. Power Sources 1997, 79, 37.
(9) Qu, D. Y.; Shi, H. J. Power Sources 1998, 74, 99.
(10) Endo, M.; Kim, Y. J.; Ohta, H.; Ishii, K.; Inoue, T.; Hayashi, T.;
Nishimura, Y.; Maeda, T.; Dresselhaus, M. S. Carbon 2002, 40 (14), 2613.
(11) Lozano-Castello, D.; Cazorla-Amoros, D.; Linares-Solano, A.;
Shiraishi, S.; Kurihara, H.; Oya, A. Carbon 2003, 41, 1765.
(12) Kim, Y. J.; Masutzawa, Y.; Ozaki, S.; Endo, M.; Dresselhaus, M.
S. J. Electrochem. Soc. 2004, 151 (6), E199.
(13) Mitani, S.; Lee, S. I.; Yoon, S. H.; Korai, Y.; Mochida, I. J. Power
Sources 2004, 133 (2), 298.
(14) Lee, S. I.; Mitani, S.; Yoon, S. H.; Korai, Y.; Mochida, I. Carbon
2004, 42 (11), 2332.
influences its electrochemical properties. Large resistance or
impedance inevitably results in an increase in power loss and
energy dissipation. So, minimizing resistance is clearly desirable
when constructing capacitors.
Needle coke is made from a highly aromatic feedstock such
as FCC (fluidized catalytic cracker) decent oil or coal-tar pitch
by a delayed coker. It is an important precursor for preparing
high-performance graphite electrodes for electric arc furnaces
because of its high density and good electrical conductivity that
originates from its optical anisotropy. It is possible to develop
high-performance carbon materials for EDLC from such a
precursor. It is well-known that carbon materials can be activated
through physical (H2O, CO2, air, etc.) or chemical methods
(ZnCl2, H3PO4, K2CO3, etc.). However, it has been found in
these methods that it is difficult to activate the anisotropic carbon
precursor into activated carbons with a large surface area.
Recently, alkali compounds such as NaOH and KOH have been
used as effective activating agents for developing activated
carbons with a large surface area.15-21 Thus, electrodic materials
with a high EDLC capacitance and a low system resistance may
be developed through using needle coke as a carbon precursor
and KOH as an activation agent.
In the present study, we tried to develop activated carbons
with a large surface area and good electric conductivity from
anisotropic petroleum-based needle coke through KOH activa-
tion. The effects of preparation parameters on the yield, surface
area, and crystallite structure of the resulting products were
investigated, and their EDLC properties such as the capacitance
and resistance were related with the surface area, porous
structure, and crystallite parameters.
(15) Marsh, H.; Crawford, D.; O’Drady, T.; Wennerberg, A. Carbon
1982, 20 (5) 419.
(16) Otawa, T.; Tanibata, R.; Itoh, M. Gas Sep. Purif. 1993, 7 (4), 241.
(17) Qiao, W. M.; Ling, L. C.; Zha, Q. F.; Liu, L. J. Mater. Sci. 1997,
32, 4447.
(18) Lillo-Ródenas, M. A.; Lozano-Castelló, D.; Cazorla-Amorós, D.;
Linares-Solano, A. Carbon 2001, 39 (5), 751.
(19) Frackowiak, E.; Delpeux, S.; Jurewicz, K.; Szostak, K.; Cazorla-
Amorós, D.; Béguin, F. Chem. Phys. Lett. 2002, 361 (1-2), 5.
(20) Xue, R. S.; Shen, Z. M. Carbon 2003, 41 (9), 1862.
(21) Wu, M. B.; Zha, Q. F.; Qiu, J. S.; Guo, Y. S.; Shang, H. Y.; Yuan,
A. J. Carbon 2005, 42 (1), 205.

10.1021/ef050313l CCC: $33.50 © 2006 American Chemical Society

Published on Web 05/19/2006
KOH ActiVation of Needle Coke for High-Performance EDLC Energy & Fuels, Vol. 20, No. 4, 2006 1681

Table 1. Elemental Analysis of Needle Coke and Its Activated Form

sample C (%) H (%) N (%) S (%) Oa (%) ash (%) VMb (%)
needle coke 95.63 3.08 0.26 0.31 0.72 0.03 5.6
NCD-AC4 95.30 0.27 0.10 0.30 4.03 0.05
a The amount of oxygen was calculated by difference: 100 - %C -

%H - %N - %S. b VM ) volatile material; this represents the weight

loss of needle coke when it was heat-treated at 850 °C under an Ar flow.

2. Experimental Section
2.1. Preparation of Petroleum-Based, Needle-Coke-Derived
Activated Carbon (NCD-AC). NCD-AC was prepared through
the following processes: petroleum-based needle coke (raw mater-
ial: FCC decant oil), provided by Koa Oil Co. Ltd., was pulverized Figure 1. Anisotropic textures of needle coke.
to the required size (100-150 µm), mixed with KOH (KOH:coke
) 1-6), and activated at 750-900 °C for 1-4 h in a Ni pan placed Table 2. Effect of Activation Temperature on the Properties of
in a stainless steel tube reactor heated by a standing furnace in a NCD-ACsa
flow of Ar with a heating rate of 5 °C/min. After the activation activation yield SBET capacitance
was finished, the reactor was cooled to room temperature and then sample conditions (wt %) (m2/g) (F/g)
placed in a glovebox in a flow of nitrogen. The resulting products
NCD-AC7 750 °C × 1 h 74 1400 28.5
were taken out and carefully washed with dilute HCl and then NCD-AC4 800 °C × 1 h 67 2454 42.3
distilled water to remove the remained residual KOH, K2CO3, K2O, NCD-AC8 850 °C × 1 h 66 2205 38.4
K, etc.; they were finally dried at 110 °C to obtain activated carbons. NCD-AC9 900 °C × 1 h 65 2325 40.3
2.2. Characterization of Needle Coke and NCD-ACs. 2.2.1. a KOH:coke ) 4.
BET Surface Area and Pore Structure of NCD-ACs. BET surface
area (calculated from relative pressure from 0.05 to 0.35) and total Table 3. Effect of Activation Time on the Properties of NCD-ACsa
pore volume (calculated at a relative pressure of 0.98) of NCD-
ACs were measured through nitrogen adsorption isotherm at a low activation yield SBET capacitance
sample conditions (wt %) (m2/g) (F/g)
temperature of 77 K (FISONS Instruments, Sorptomatic 1990
adsorption analyzer). Micropore volume and pore size distribution NCD-AC10 800 °C × 0.5 h 71 2198 38.5
of NCD-ACs were evaluated by using t-plots and the Horvath- NCD-AC4 800 °C × 1 h 67 2454 42.3
Kawazoe (H-K) method, respectively. NCD-AC11 800 °C × 2 h 63 2200 38.0
NCD-AC12 800 °C × 4 h 60 2215 38.2
2.2.2. XRD of Needle Coke and its ActiVated Forms. Crystallite
parameters of needle coke and its activated forms were analyzed a KOH:coke ) 4.
by an X-ray diffractometer with Cu KR radiation (Rigaku geiger-
flex). The interspacing d002 of NCD-ACs was calculated according of 5.6%. The optical microscopy of needle coke proved its
to the Bragg equation. anisotropic domain structure, as shown in Figure 1.
2.2.3. EDLC Property of Some Commercial ActiVated Carbons After needle coke was activated by KOH, the resulting
and NCD-ACs. The carbon electrode was prepared according to activated carbon, such as NCD-AC4, exhibited a similar carbon
an 8:1:1 (wt) AC:PTFE:CB composition, in which AC stood for
activated carbon, PTFE (polytetrafluoroethlyene) was used as a
content to its precursor but a higher oxygen content of ca. 4%,
binder, and CB (Ketjen carbon black, EC-600JD) was used as a originating from the activating agent. The small amount of ash
conductive agent. The capacitor cell was composed of two carbon of NCD-AC4 (only 0.05%) indicates that residual KOH, K2O,
electrodes sandwiched by a separator and contained an organic K, and K2CO3 can be completely removed through a careful
electrolytic solution of 1 M Et4NBF4/PC. The charging voltage and washing using HCl and water.
discharging current were 2.7 V and 2.4 mA, respectively (Toyo 3.2. Activation of Needle Coke To Develop Activated
system, Toscat-3100K). The dimension of the carbon electrode was Carbons with Large Surface Area. 3.2.1. Effect of ActiVation
13 mm (diameter) × 0.2 mm (thickness). The EDLC capacitance Temperature on the Properties of NCD-ACs. Table 2 sum-
was calculated according to the reference.22 The system resistance marizes the effect of activation temperature on the yield, surface
of the EDLC cell was calculated by the formula R ) ∆V/I (∆V )
area, and EDLC capacitance of the resulting products. The
sudden voltage drop when the EDLC system is discharged; I )
discharging current). activation at a low temperature of 750 °C resulted in a high
yield but a small surface area. The activation at a temperature
higher than 800 °C decreased the surface area. The suitable
3. Results activation temperature is 800 °C, at which the maximum surface
3.1. Some Properties of Petroleum Needle Coke. Table 1 area of 2454 m2/g was obtained, providing a capacitance of 42.3
summarizes the elemental composition of needle coke. The F/g.
chemical composition of its activated form (NCD-AC4) is also 3.2.2. Effect of ActiVation Time on the Properties of NCD-
included in this table. ACs. Table 3 summarizes the effect of activation time on the
Needle coke contains carbon (95.6%), hydrogen (3.1%), yield, surface area, and EDLC capacitance of the resulting
nitrogen (0.3%), sulfur (0.3%), and oxygen (0.7%, by differ- products. It was difficult to obtain a large surface area but high
ence). Its heat treatment at 850 °C in air provided a very small yield (up to 71%) with a short activation time; a long activation
amount of ash (mainly oxides of residual catalyst metals in FCC time also decreased the surface area to some extent, and resulted
decant oil), only 0.03%, whereas its carbonization at 850 °C in in a decrease in yield because of excess burnoff of carbon
Ar exhibited a high yield (94.4%) with a volatile material release materials. An activation time of 1 h gave the largest surface
area and highest capacitance.
(22) Qiao, W. M.; Korai, Y.; Mochida, I.; Hori, Y.; Maeda, T. Carbon 3.2.3. Effect of the Ratio of KOH to Needle Coke on the
2002, 40 (3), 351. Properties of NCD-ACs. Figures 2 and 3 show adsorption
1682 Energy & Fuels, Vol. 20, No. 4, 2006
Figure 2. Adsorption isotherms of NCD-ACs.
isotherms and pore size distributions of NCD-ACs. The NCD-
AC was obtained under KOH:coke ratios from 1 to 6 (activation
temperature, time, and heating rate are 800 °C, 1 h, and 5 °C/
min, respectively.). NCD-AC exhibits an adsorption isotherm
of type I according to IUPAC. The adsorbed amount to nitrogen
of NCD-AC largely increases with increasing ratio from 1 to
6. The adsorbed amounts of NCD-ACs 1-3 hardly increase at
a relative pressure higher than 0.2, indicating they have
microporous carbons. However, the adsorbed amounts of NCD-
ACs 4-6 slightly increase, implying they contain major
micropores and some mesopores.
NCD-AC1 exhibits porous structures smaller than 15 Å,
whereas NCD-AC6 does exhibit an increase in pore size
between 15 and 40 Å, as shown in Figure 3; this indicates that
large micropores and even mesopores increase with an increas-
ing activation extent.
Figure 3. Pore size distributions of NCD-ACs.
Qiao et al.
Table 4 summarizes the effect of the KOH:coke ratio on the
yield, surface area, pore volume, EDLC capacitance, IR drop,
and resistance of the resulting products. With an increase in
the KOH:coke ratio from 1 to 6, the surface area enlarges from
400 to 2900 m2/g and the pore volume increases from 0.22 to
1.61 mL/g, but the yield decreases from 90 to 56%. A higher
ratio than 6 decreases the surface area of the resulting NCD-
AC. In the table, it is observed that NCD-ACs with a low
activation extent (NCD-ACs 1-3) show very small IR drops
from 0.02 to 0.06 V, corresponding to resistances of 8-25 Ω,
and their EDLC capacitances vary from 14 to 30 F/g. The
maximum surface area is obtained at a ratio of 6, whose
capacitance reaches a maximum of 44 F/g and whose IR drop
is ca. 0.45 V, corresponding to a resistance of 187 Ω.
The reproducibility of activated carbons (NCD-AC4 series)
is listed in Table 4. NCD-AC4 series exhibit similar results
(yield, surface area, pore volume, capacitance, IR drop, etc.),
indicating they have good reproducibility.
3.3. XRD of NCD-ACs. Figure 4 shows XRD profiles of
as-received needle coke and its activated forms. As-received
needle coke shows a sharp peak of d002 at 2θ ) 26.09° and
gives a interspacing value of 0.341 nm, indicating its pseudogra-
phitic arrangement of ordered domains of graphene layers.
Activation of needle coke leads to a broader d002 peak with a
shift to a smaller diffraction angle. With the KOH:coke ratio
from 1 to 3, the activation extent is deepened, and NDC-ACs
show enlarged interspacings of 0.361, 0.369, and 0.389 nm,
respectively. No d002 diffraction peak is observed at a ratio
higher than 4, as shown in Figure 4, indicating the structural
change of needle coke from pseudographitic to amorphous after
severe KOH activation.
4. Discussion
KOH is very effective for developing porosity from needle
coke. The maximum surface area of NCD-AC reaches 2900
m2/g after KOH activation. NCD-AC shows a maximum EDLC
KOH ActiVation of Needle Coke for High-Performance EDLC Energy & Fuels, Vol. 20, No. 4, 2006 1683

Table 4. Effect of the KOH:Coke Ratio on the Properties of NCD-ACs

pore volume capacitance
sample ratio yield (wt %) surface area (m2/g) total (mL/g) micro (mL/g) F/g µF/cm2 IR drop (V) R (Ω) d002 (nm)
needle coke 0.341
NCD-AC1 1 90 400 0.22 0.20 14.0 3.50 0.02 8.3 0.361
NCD-AC2 2 80 1123 0.63 0.57 29.2 2.60 0.04 16.7 0.368
NCD-AC3 3 76 1412 0.81 0.71 29.6 2.10 0.06 25.0 0.389
NCD-AC4 4 67 2454 1.38 1.25 42.3 1.72 0.20 83.3
NCD-AC4-2 4 68 2400 1.32 1.24 42.0 1.75 0.18
NCD-AC4-3 4 67 2470 1.40 1.27 41.8 1.69 0.22
NCD-AC4-4 4 66 2450 1.36 1.25 42.1 1.72 0.20
NCD-AC5 5 61 2759 1.46 1.28 43.0 1.56 0.40 166.6
NCD-AC6 6 56 2906 1.61 1.39 44.0 1.51 0.45 187.5
commercial ACs
CACa 1500 18.6 1.24 0.57 237.5
OG15Ab 1553 25.2 1.62 0.31 129.2
Maxsorbc 2972 40.0 1.35 0.38 158.3
a Coconut-shell activated carbon. bPitch-based activated carbon fiber. c Green-coke activated carbon through KOH activation.

a porous structure. Another factor, namely the gasification of

Figure 4. XRD profiles of needle coke and its activated forms. (a)
Needle coke, (b) NCD-AC1, (c) NCD-AC2, (d) NCD-AC3, (e) NCD-
AC4, and (f) NCD-AC6.
capacitance of 44 F/g, according to two-electrode measurements
in an electrolytic solution of 1 M Et4NBF4/PC.
Up until now, the mechanism of KOH activation has not been
clearly understood.18,23-25 A generally accepted view is that
KOH dehydrates to transform into K2O at 400 °C; the resulting
K2O is reduced into metallic potassium by carbon at a high
temperature to develop a porous structure. Metal K then
intercalates into pseudographitic layers to develop the porosity
after the activated product is carefully washed using HCl and
water to completely remove residual K, K2O, K2CO3, and KOH,
which were proved to be in the resulting activated products by
subsequent XRD measurements. Metallic potassium was also
observed in the wall of the reactor. When the potassium and its
compounds were removed from the resulting activated products
by washing, pseudographitic lamellae could not return to their
previous nonporous structure but instead remained apart to create
the microporosity necessary for large surface area values. The
total KOH activation mechanism was suggested by Linares-
Solano’s group,24 which is the following
6KOH + C ) 3K + 3H2 + K2CO3
The reaction of K2O with carbon and K intercalation in
pseudographitic layers are two important factors for developing
carbon, should be considered, because as much as 5.6% volatile
material is present during the carbonization of the carbon
precursor. The gasification is beneficial for introducing some
micropores.
The optimum preparation condition is a temperature of 800
°C for 1 h to develop NCD-ACs. A KOH:coke ratio higher than
4 is necessary for a surface area larger than 2000 m2/g and a
capacitance greater than 40 F/g. A large surface area is
responsible for a large capacitance, whereas NCD-ACs of highly
porous structure exhibit an increased IR drop in the EDLC
system, corresponding to an increase in the system resistance.
Compared with several commercial ACs with similar surface
areas, as summarized in Table 4, NCD-ACs not only exhibit
higher capacitances per weight and per area but also provide
lower IR drops and resistances of the EDLC cell system.
With the increase in the KOH:coke ratio, EDLC capacitances
of the resulting products are improved and their IR drops are
enlarged. When the discharge starts, the sudden potential drop
(IR drop) can be attributed to the resistance of electrolytes and
the inner resistance of ion diffusion in micropores.26,27 The latter
usually has a larger contribution to the total IR drop. Highly
porous structures not only provide a high surface area and
capacitance but also improve the IR drop because ion diffusion
in micropores significantly influences the formation of electric
double layers, and the diffusion resistance increases with the
extent of porosity development.
IR drop is closely related to the electrical conductivity of
electrodic materials, too. Carbon with ordered graphitic struc-
tures should exhibit a good electrical conductivity and contribute
a low IR drop. A high degree of activation possibly results in
the destruction and rearrangement of the layer alignments and
decreases the ordered structures because of the enlarged d002
value, thus reducing the electrical conductivity of NCD-ACs.
As a result, the IR drop of NCD-ACs in the EDLC system is
increased.
The surface composition (e.g., oxygen functional groups) of
the carbons plays a role in pseudocapacitance in EDLC with
an inorganic electrolytic solution. In the organic case, a similar
result has not been reported. It is certain that oxygen content
(23) Marsh, H.; Yan, D. S.; O’Grady, T. M.; Wennerberg, A. Carbon
1984, 22 (6), 603.
(24) Lillo-Ródenas, M. A.; Cazorla-Amorós, D.; Linares-Solano, A.
Carbon 2003, 41 (2), 267.
(25) Yoon, S. H.; Lim, S. Y.; Song, Y.; Ota, Y.; Qiao, W, M.; Tanaka,
A.; Mochida, I. Carbon 2004, 42, 1723.
(26) Liu, X.; Osaka, T. J. Electrochem. Soc. 1997, 144 (9), 3066.
(27) Teng, H.; Chang, Y.; Hsieh, C. Carbon 2001, 39 (13), 1981.
1684 Energy & Fuels, Vol. 20, No. 4, 2006
may decrease the electrical conductivity of carbon materials.
However, in the inorganic electrolytic case, suitable hydrophilic
functional groups are beneficial for wetting the surface and pore
wall of carbon. In the organic electrolytic case, a hydrophobic
surface should be beneficial to the application. In the activation
of the carbon precursor, oxygen is inevitably introduced in
carbon, which possibly originates from KOH. The increase of
oxygen functional groups provokes the decrease in the electrical
conductivity of carbon to some extent. The post-treatment, such
as hydrogen reduction at a low temperature, may be a good
choice for removing the groups and retaining a large surface
area.
Interestingly, compared with commercial ACs with similar
surface areas from isotropic precursors, NCD-ACs exhibit better
EDLC performances with a higher capacitance per weight or
Qiao et al.
area and a smaller IR drop, indicting their better electrical
conductivity, which originates from their anisotropic precursor.
5. Conclusion
Petroleum-based needle coke is an excellent precursor for
preparing high-performance ACs with high yield (ca. 67%),
large surface area (2450 m2/g), large capacitance (42 F/g), and
good electrical conductivity (IR drop ) 0.2 V; resistance ) 83
Ω). It is found that the IR drop of the EDLC cell increases
with the enlargement of the interspacing of NCD-AC and the
improvement of its surface area. NCD-AC may be a promising
candidate for electrodic material for energy storage.
EF050313L