Accepted Manuscript

Title: Preparation and characterization of high surface area

activated carbons from co-pyrolysis product of coal-tar pitch
and rosin

Author: Cheng Zeng Qilang Lin Changqing Fang Dongwei

Xu Zhichao Ma

PII: S0165-2370(13)00140-X
DOI: http://dx.doi.org/doi:10.1016/j.jaap.2013.06.010
Reference: JAAP 3012

To appear in: J. Anal. Appl. Pyrolysis

Received date: 4-4-2013

Revised date: 5-6-2013
Accepted date: 14-6-2013

Please cite this article as: C. Zeng, Q. Lin, C. Fang, D. Xu, Z. Ma, Preparation and
characterization of high surface area activated carbons from co-pyrolysis product
of coal-tar pitch and rosin, Journal of Analytical and Applied Pyrolysis (2013),
http://dx.doi.org/10.1016/j.jaap.2013.06.010

This is a PDF file of an unedited manuscript that has been accepted for publication.
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Preparation and characterization of high surface area activated carbons from

co-pyrolysis product of coal-tar pitch and rosin

a a, b, a a
Cheng Zeng , Qilang Lin *, Changqing Fang *, Dongwei Xu , Zhichao Ma

a
College of Materials Science and Engineering, Fuzhou University, Fuzhou 350116, PR China

b
College of Printing and Packing Engineering, Xi’an University of Technology, Xi’an 710048,

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PR China

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Abstract
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Co-pyrolysis product of coal-tar pitch and rosin was used as a precursor to prepare high
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surface area activated carbons (ACs) by KOH activation. The influences of AC precursor origin,

KOH/AC precursor weight ratio and activation time on the pore characteristics of the ACs were
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investigated, and meanwhile their electrochemical performance was studied. The results show
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that adding rosin results in a decrease in the C/H atomic ratio of AC precursor as well as a

significant increase in its mesophase content, which favors the porosity development in ACs

during KOH activation. The effect of adding rosin on the porosity characteristics of the ACs can

be illustrated by increases in the BET surface area from 1846 to 2847 m2/g and the total pore

volume from 1.09 to 1.57 cm3/g. In addition, the ACs possess good electrochemical performance,

as indicated by that they have a maximum specific capacitance of 203 F/g and exhibit good

Page 1 of 26
rectangular-shaped I-V curves in cyclic voltammetry.

Keywords: Activated carbon; Coal-tar pitch; Rosin; Chemical activation

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1. Introduction

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Activated carbons (ACs) with a highly developed surface area are widely used in numerous

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fields such as gas separation, solvent recovery, organic pollution removal and catalyst support

[1–3]. In recent years, there is a growing interest in the applications of ACs in the fields of gas
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storage and electric double-layer capacitors (EDLCs) [4]. Commercial ACs, which have a low

surface area and poor adsorption properties, cannot be applied to these fields and, therefore, it is
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necessary to fabricate high surface area ACs [5,6]. Up to now, mesocarbon microbeads (MCMB)
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and mesophase pitch have been considered to be the most suitable precursors for the production

of high surface area ACs by potassium hydroxide activation [7–11]. These ACs, which possess
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well-developed crystalline structure, high mesopore content, high electronic conductivity, good
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thermal stability, and satisfactory oxidation resistance [12–14], are especially suited for

applications in the fields of gas storage and EDLCs. However, the high cost of traditional MCMB
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and mesophase pitch restricts the development and application of these ACs.

MCMB and mesophase pitch are two kinds of carbonaceous mesophases prepared by

thermolysis (pyrolysis) of aromatic compounds such as pitch, coal tar and crude oil [15–17]. The

formation of carbonaceous mesophase generally involves nucleation, growth, and coalescence of

*mesophase spheres,
Corresponding which
authors. Telis&accompanied by simultaneous aromatic polymerization reactions;
Fax: +86-591-22866531

it is difficult
E-mail to control
address: the polymerization
linqilang@hotmail.com (Q.reactions at pyrolysis temperatures,
Lin), fcqxaut@163.com (C. Fang) leading to the high
2

Page 2 of 26
cost of MCMB and mesophase pitch [18]. As a solution, MCMB were prepared in high yield by

co-pyrolysis of coal-tar pitch and rosin in our previous work [19]; the co-pyrolysis product had

high mesophase content and low C/H atomic ratio as well as low cost. It is known that the

decrease in C/H atomic ratio of AC precursor is beneficial to the porosity development in ACs

[20,21]. Therefore, the co-pyrolysis product seems to be a suitable precursor for the low-cost

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production of high surface area ACs. In this paper, we attempted the preparation of ACs from the

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co-pyrolysis product by KOH activation, and then structures and electrochemical performance of

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the ACs were studied.

2. Experimental
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2.1 Raw materials
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Coal-tar pitch was purchased from Wuhan Steel Co., Ltd. (Wuhan, China). Rosin was
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supplied by Ninghua Forest Chemicals Co., Ltd. (Ninghua, China). The properties of pitch and

rosin used in this study can be seen in our previous study [19].
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2.2 Preparation of AC precursors

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Coal-tar pitch was mixed with certain amount of rosin in a cylindrical steel reactor equipped

with a motor driven stirrer. The stirrer was started at 100 °C at a speed of 50 rpm. The speed of
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the stirrer was raised to 240 rpm at 150 °C and maintained for 30 min under a nitrogen flow of

100 mL min−1. The pitch-rosin mixture sample was loaded into a Pyrex tube, and then heated up

to 450 °C at a rate of 5 °C min-1 under a nitrogen stream and kept for 2 h. The co-pyrolysis

product obtained was labeled CP0, CP5 and CP10 when the rosin content was 0 wt%, 5 wt% and

10 wt% of coal-tar pitch, respectively. The co-pyrolysis product was pulverized to < 0.2 mm

particle size and used as AC precursor.

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Page 3 of 26
2.3 Preparation of ACs

Chemical activation with KOH was carried out using a mechanical mixing method. The AC

precursor sample was mixed with KOH in the desired proportions. The sample was placed in a

corundum crucible, and heated in nitrogen atmosphere at a heating rate of 5 °C min-1 until the

desired carbonization temperature and maintained under these conditions for 1, 1.5 or 2 h. The

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treatments were carried out in a tube furnace with an inner diameter of 50 mm under a nitrogen

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flow of 30 dm3 h-1. The activated sample was neutralized with a 0.5 mol/L HCl solution to

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eliminate the residual alkali. After that, the sample was washed with hot distilled water (85 °C)

until the PH of the filtrating solution was adjusted to 6–7. Finally, the cleaned sample was dried
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in vacuum at 110 °C for 24 h, followed by grinding and sieving to < 0.2 mm particle size. The

resultant ACs were labeled following the scheme: three groups of numbers after AC precursor
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(CP0, CP5, or CP10) make reference to the chemical agent/AC precursor weight ratio,
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carbonization temperature, and residence time. Thus, CP0-5-850-1.5 refers the AC obtained from

the CP0 after activation with KOH, in a ratio to the CP0 (5:1), treated at 850 °C for 1.5 h. The
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activation yield (AY) of the AC was calculated:

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AY (%) = W1/W0 ×100, (1)

where W0 is the mass of AC precursor and W1 the mass of the AC.

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2.4 Preparation of electrode and cell capacitor

The electrode consisted of 80 wt% of AC, 10 wt% of acetylene black and 10 wt % PTFE

(polytetrafluoroethylene). Electrodes were punched out of activated carbon sheet, and the disc

electrodes (1.5 cm2) were then mounted onto a Ni-current collector in a Teflon cell holder. For

the cell capacitor construction, two disc electrodes were mounted face-to-face into the holder

with a separator in between. After the electrolyte solution of 6 M KOH was introduced, the
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Page 4 of 26
 capacitors were sealed. The capacitors were kept at room temperature for 24 h before

electrochemical measurements. The mass of the AC in a single electrode is about 12 mg.

2.5 Characterization

The carbon, hydrogen, and nitrogen weight percentages of samples were determined using a

Vario EL III elemental analyzer. The solubility in quinoline was determined according to ASTM

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D2318.

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The AC precursor sample was mounted in epoxy resin, and smoothed using fine grade

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silicon carbide paper, then polished using a cloth pad with alumina powder. Optical textures of

the sample were observed from the polished surfaces using DDM-300C polarized-light
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microscope. The mesophase content was determined using a point-counting procedure.

Textural characterization of the ACs was performed by N2 adsorption at 77 K in a

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micromeritics ASAP 2020 apparatus. The BET surface area (SBET) was determined from
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isotherms using the Brunauer-Emmett-Teller equation (BET). Total pore volume (Vtot) was

defined as the volume of liquid nitrogen corresponding to the amount adsorbed at a relative
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pressure of P/P0=0.99. The micropore volume (Vmic) was obtained from application of
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Dubinin-Radushkevich (DR), and the mesopore volume (Vmes) was calculated as the difference

between Vtot and Vmic. The pore size distribution was calculated from N2 adsorption isotherm by
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Berrret-Toyner-Hslena (BJH) method.

For the electrochemical analysis, charge–discharge tests were performed at a constant

current density of 10 mA·cm-2 in the potential range of 0–1.2 V, and cyclic voltammetry (CV)

measurements were performed between -1 V to 0 V with scanning rate from 5 mV/s to 40 mV/s.

All the electrochemical measurements were conducted at ambient temperature. Specific

capacitance of the single electrode was calculated from the CV curves according to the following
5

Page 5 of 26
equation:

C
 idV , (2)
SmV

where C is the specific capacitance (F/g), i is the instantaneous current, V is the potential (V), S is

the potential scanning rate (V/s), and m is the mass of active material on one electrode (g).

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3. Results and discussion

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3.1 Properties of AC precursors

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Fig.1 illustrates the SEM images of the AC precursors (CP0, CP5, and CP10). It is found that

the three AC precursors all contain a certain number of irregular particles with sizes of 50–200
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μm. The particles of the CP0 exhibit sharp edges and corners (Fig.1a). However, the particles of
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the CP5 and the CP10 have no obvious edges and corners (Fig. 1b–c). The facts indicate that the

rosin addition results in decreased hardness of the AC precursor. The reason for this is related to
ed

the characteristics of the AC precursors. The optical textures of the AC precursors before
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pulverization were given in our previous work [19]; the CP0 had a content of bulk mesophase

with various morphologies, whereas the CP5 contained a high content of irregular-shaped
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mesophase and the CP10 had a relatively high content of MCMB. Therefore, the high mesophase
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contents of the AC precursors (CP5 and CP10) seem to be responsible for the formation of the

particles without obvious edges and corners after pulverization.

Table 1 shows the main properties of the above AC precursors. It can be seen that the AC

precursor possesses lower C/H ratio with an increase in added rosin content from 0 to 10 wt%,

showing a decrease in its aromaticity. Moreover, the quinoline insoluble (QI) content of the AC

precursor decreases with increasing added rosin content. The AC precursor had higher

Page 6 of 26
cycloparaffin content with increasing added rosin content [19]. It is generally accepted that the

high cycloparaffin content is beneficial in the formation of soluble mesophase constituents during

the pyrolysis of pitch. This should be responsible for the decrease in the QI content of the AC

precursor with increasing added rosin content. Furthermore, it can be observed that the CP5 and

CP10 have much higher mesophase content that CP0, which confirms that the rosin addition

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contributes to the development of carbonaceous mesophase. Compared with the CP5, the CP10 has

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lower mesophase content. The reason for this is related to its lower C/H ratio and higher

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cycloparaffin content, which could reduce the polymerization velocity for hydrogenation of

coal-tar pitch upon pyrolysis [15].

3.2 Porosity of ACs

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3.2.1 Effect of AC precursor origin
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The AC precursor (CP0, CP5, or CP10) was mixed with the KOH in a 5:1 KOH/AC precursor
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weight ratio, and then the mixture was treated at 850 °C for 1.5 h to obtain the resultant AC. The

adsorption-desorption isotherms and the inset corresponding pore size distribution profile for the
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ACs were given in Fig.2. It can be observed in the isotherms that the ACs from CP5
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(CP5-5-850-1.5) and CP10 (CP10-5-850-1.5) have a wider knee and a higher N2 adsorption

capacity than the AC from CP0 (CP0-5-850-1.5). In addition, the pore size distribution profile
Ac

shows that the CP10-5-850-1.5 owns more micropores and mesopores than the CP0-5-850-1.5.

Porosity characteristics and activation yields of the ACs were summarized in Table 2. The

CP5-5-850-1.5 has the highest specific surface area and pore volume, whereas the CP10-5-850-1.5

possesses the largest mesopore percentage. This indicates that the origin of AC precursor has a

great effect on the porosity characteristics of the ACs. The AC precursors (CP5 and CP10) have

higher contents of carbonaceous mesophase and lower C/H ratio than CP0, which favors the
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Page 7 of 26
porosity development in ACs [20]. Compared with the CP5-5-850-1.5, the CP10-5-850-1.5 has a

larger average pore diameter and a lower specific surface area. This can be explained by the fact

that CP10 has a higher number of MCMB with smaller size [19], which would lead to an increase

in the activation efficiency of KOH, thus contributing to the pore enlargement. When a certain

number of enlarged pores are formed in the AC, its specific surface area would decrease.

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3.2.2 Effect of KOH/AC precursor weight ratio

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The study of the influence of the KOH/AC precursor weight ratio on the activation process

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was carried out by mixing samples of the CP10 with KOH in 3:1, 5:1, and 7:1 KOH/CP10 weight

ratios, maintaining 850 °C as the activation temperature and 1.5 h as residence time in all cases.
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The N2 adsorption-desorption isotherms and the inset corresponding pore size distribution profile

of the resultant ACs were shown in Fig.3. It is found that the shapes of the N2
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adsorption-desorption isotherms are varied dramatically with the increase of KOH/CP10 weight
ed

ratio. Meanwhile, a great enhancement of N2 adsorption capacity can be achieved by increasing

the KOH/CP10 weight ratio. The pore size distribution profile reflects that the KOH/AC precursor
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weight ratio has a great effect on the development of mesopores. The mesopore volume of the AC
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significantly increases with increasing KOH/CP10 weight ratio. Porosity characteristics and

activation yields of the ACs were summarized in Table 2. The activation yield of the AC is
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decreased from 64 % to 35 % when the KOH/pitch weight ratio KOH/pitch weight ratio increases

from 3:1 to 7:1. In addition, the AC possesses high surface area, high micropore volume and

considerable mesoporisty when the KOH/CP10 weight ratio is higher than 5:1. It can be seen that

both the surface area and the pore volume of the AC increase continuously with the KOH/CP10

weight ratio and reach the maximum values at a ratio of 7:1. Similar results were obtained by

Ahmadpour and co-worker [22]. Pore widening normally begins when there are a number of
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Page 8 of 26
opened pores in the structure, therefore, it starts to be significant when the chemical ratio is

reasonably high [23–25].

3.2.3 Effect of activation time

The influence of activation time on the texture of the resultant ACs was studied through

activation of the samples for different time (1 h, 1.5 h, and 2.0 h), maintaining the KOH/CP10

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weight ratio (7:1) and the activation temperature (850 °C) constant. Fig.4 shows the N2

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adsorption-desorption isotherms and the inset corresponding pore size distribution profile of the

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ACs. When the activation time is 1 h, the isotherms of the ACs show the major adsorption below

P/P0 = 0.1 and the minimum adsorption in the P/P0 range of 0.1–1.0, indicating the ACs are
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mainly microporous. When the activation time is 1.5 h, the isotherms of the ACs show a linear

increase in adsorption until P/P0 = 0.4 after the marked adsorption below P/P0 = 0.05, and then a
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gradual increase in adsorption after P/P0 = 0.4. In addition, the pore size distribution profile
ed

shows that the AC possesses more developed pore structure and wider pore size distribution with

increasing activation time. Porosity characteristics and activation yields of the ACs were
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summarized in Table 2. It can be observed that the activation yield of the AC decreases with
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increasing activation time, which is due to the results of KOH etching at high temperatures.

Compared with textural parameters of the CP10-7-850-1.5, the specific surface area and
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micropore volume of the CP10-7-850-2.0 decrease unobviously, and their mesopore volume and

average pore diameter increase slightly. This indicates that most KOH have been depleted when

the activation time is 1.5 h.

3.3 Electrochemical performance

The four ACs (CP0-5-850-1.5, CP5-5-850-1.5, CP10-5-850-1.5, and CP10-7-850-1.5) were

used to prepare electrodes, and their typical CV curves are shown in Fig.5. The voltage sweep
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Page 9 of 26
range was from -1 V to 0 V and the scanning rates were 5, 10, 20 and 40 mV/s. It is known that

achieving rectangular-shaped CV curves over a wide range of scanning rates is the ultimate goal

in EDLCs. This behavior is important for practical applications involving high energy and power

density. The four CV curves show typical capacitor-like characteristics in the form of almost

rectangular cyclic behavior, and redox peaks were not observed. This suggests that the ACs show

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a good capacitor performance in a voltage range of -1 V to 0 V. The facts indicate that the

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charge-discharge responses of the electric double layer are highly reversible. At the same

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scanning rate, more ideal capacitive behavior was observed for the CP10-7-850-1.5 with a steeper

current change at the switching potential, showing better rectangular-shaped I-V curves. The
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slower changes at the switching potentials in the CV measurement of the CP0-5-850-1.5 stem

from the slower reorganization of the double layer, owing to the higher content of micropores and
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slower ionic motions in the micropores [26].
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The specific capacitance at a scanning rate of 5 mV/s was calculated according to Eq. (2).

The measured specific capacitances of CP0-5-850-1.5, CP5-5-850-1.5, CP10-5-850-1.5 and

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CP10-7-850-1.5 are 108, 172, 180 and 203 F/g, respectively. This indicates the rosin addition is
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beneficial to increase the specific capacitance of the AC. It is found that the surface area and pore

volume of the ACs increase significantly after adding the rosin, and especially their average pore
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diameter and mesopore volume are further enhanced with increasing rosin content. The

CP5-5-850-1.5 has the highest surface area (2847 m2/g) and pore volume (1.57 cm3/g), and the

CP10-7-850-1.5 possesses the largest mesopore volume (0.88 cm3/g), which should be responsible

for the high specific capacitances of the two ACs. In general, the specific capacitance of carbon

material is linked to the electrical conductivity, the surface area, the porosity of the carbon, the

accessibility of the electrolyte for penetrating into the carbon pores and the electrolyte properties
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Page 10 of 26
[27,28]. Micropores with small diameter may not be accessible to electrolyte solution, and the

ions cannot enter those pores, thus, the surface area of those non-accessible micropores will not

contribute to the total double-layer capacitance of the material [29].

Fig.6 shows the charge-discharge profiles of the electrodes from the above four ACs. It is

found that their chronopotentiograms were triangular, indicating a typical behavior of capacitive

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electrodes. The electrodes from the three ACs (CP5-5-850-1.5, CP10-5-850-1.5, and

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CP10-7-850-1.5) have much higher charge and discharge times than that from CP0-5-850-1.5. It is

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known that the charge or discharge time, especially discharge time, is proportional to the

capacitance of AC. Compared with CP0-5-850-1.5, they possess a higher surface area and
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mesopore volume, leading to the formation of larger effective surface area, and thus have longer

discharge time. In addition, a certain voltage drop can be observed in the charge-discharge profile
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of the electrodes from CP5-5-850-1.5. This is mainly due to the presence of the internal resistance
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of the capacitor [30].

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4. Conclusions
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This study has demonstrated that the co-pyrolysis product of coal-tar pitch and rosin was a

suitable precursor for the low-cost production of high surface area activated carbons (ACs) by
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KOH activation. The adding rosin results in a decrease in the C/H atomic ratio of the AC

precursor as well as a significant increase in its mesophase content. The effect of AC precursor

origin on the porosity characteristics of the ACs can be illustrated by increases in the BET surface

area from 1846 to 2847 m2/g, the total pore volume from 1.09 to 1.57 cm3/g and the average pore

diameter from 1.81 to 2.39 nm. In addition, the main factor affecting the porosity characteristics

of the ACs is the KOH/AC precursor weight ratio. It is recommended that a KOH/AC precursor
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Page 11 of 26
weight ratio of 7:1, an activation temperature of 850 °C and a residence time of 1.5 h are the

optimum parameter values for producing high surface area ACs with good electrochemical

performance. The resulting AC has the maximum specific capacitance of 203 F/g and exhibit

good rectangular-shaped I-V curves in cyclic voltammetry.

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Acknowledgements

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The authors gratefully acknowledge financial support form the National Natural Science

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Foundation of China (Grant No.51272045) and the Natural Science Foundation of Fujian

Province of China (Grant No.2010J01280).

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Fabrication of hollow core carbon spheres with hierarchical nanoarchitecture for ultrahigh

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ip
electrical charge storage, J. Mater. Chem. 22 (2012) 19031–19038.

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[27]A.B. Fuertes, F. Pico, J.M. Rojo, Influence of pore structure on electric double layer

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capacitance of template mesoporous carbons, J. Power Sources 133 (2004) 329–336.

[28]D.Y. Du. Studies of the activated carbons used in double layer supercapacitors, J. Power

Sources 133 (2002) 403-411.

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[29]C.X. Zhang, R. Zhang, B.L. Xing, G. Cheng, Y.B. Xie, W.M. Qiao, L. Zhan, X.Y. Liang,
M
L.C. Ling, Effect of pore structure on the electrochemical performance of coal-based
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activated carbons in non-aqueous electrolyte, New carbon Mater. 25 (2010) 129–133.

[30]M. Yamagata, S. Ikebe, K. Soeda, M. Ishikawa, Ultrahigh-performance nonaqueous electric

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double-layer capacitors using an activated carbon composite electrode with alginate, RSC
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Adv. 3 (2013) 1037–1040.

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15

Page 15 of 26
Figure captions

Figure 1 Optical textures of the three AC precursors. (a) CP0, (b) CP5, (c) CP10.

Figure 2 N2 adsorption-desorption isotherms and the inset corresponding pore size

distributions for the ACs prepared at 850 °C from the different AC precursors (CP0, CP5,

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and CP10).

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Figure 3 N2 adsorption-desorption isotherms and the inset corresponding pore size

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distribution profile for the ACs prepared at 850 °C from the CP10 in different

KOH/CP10 weight ratios (3:1, 5:1, and 7:1).

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Figure 4 N2 adsorption-desorption isotherms and the inset corresponding pore size

distribution for the ACs prepared from the CP10 at 850 °C for different activation time
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(1 h, 1.5 h, and 2.0 h).
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Figure 5 CV curves at various scanning rates for the capacitors prepared with different ACs.

(a) CP0-5-850-1.5, (b) CP5-5-850-1.5, (c) CP10-5-850-1.5, (d) CP10-7-850-1.5

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Figure 6 The charge-discharge curves of the four AC electrodes.

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(a) CP0-5-850-1.5, (b) CP5-5-850-1.5, (c) CP10-5-850-1.5, (d) CP10-7-850-1.5

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16

Page 16 of 26
Table captions

Table 1 Main properties of the AC precursors.

Table 2 Porosity characteristics and activation yields of the ACs prepared from the co-pyrolysis

products by KOH activation.

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Page 17 of 26
Table 1

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Table 1

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Main properties of the AC precursors

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Sample Elemental analysis (wt%)
C/H QI (%) MC (%)
C H N

M
CP0 93.10 3.86 1.24 2.01 57.41 63.18

d
CP5 92.42 4.07 1.22 1.89 48.38 92.46

CP10 91.98
te 4.19 1.17 1.83 42.06 87.09
ep
MC: mesopahse content

C/H: the atomic ratio of C to H

c

QI: quinoline insolubles

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Page 18 of 26
Table 2

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Table 2

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Porosity characteristics and activation yields of the ACs prepared from the co-pyrolysis products by KOH activation.

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Sample SBET (m2/g) Vtot(cm3/g) Vmic(cm3/g) Vmes(cm3/g) MP(%) D(nm) AY(%)

CP0-5-850-1.5 1846 1.09 0.79 0.30 27.5 1.81 41.6

M
CP5-5-850-1.5 2847 1.57 1.11 0.46 29.3 2.20 43.0

d
CP10-5-850-1.5 2270 1.36 0.9 0.46 33.8 2.39 40.8

CP10-3-850-1.5 1628
te0.90 0.85 0.05 5.6 1.34 64.5
ep
CP10-7-850-1.5 2360 1.91 1.03 0.88 46.1 3.24 43.0

CP10-7-850-1.0 1855 1.28 0.92 0.34 26.6 1.84 55.1

c

CP10-7-850-2.0 2304 1.89 0.99 0.90 47.6 3.32 40.7

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MP: mesopore percentage

D: average pore diameter

AY: activation yield

Page 19 of 26
Figure 1

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Figure 1

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(a) (b) (c)

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d
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ep
c

Fig.1 SEM images of the three AC precursors. (a) CP0, (b) CP5, (c) CP10
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Page 20 of 26
Figure 2

Figure 2

1100
CP0-5-850-1.5
1000 CP5-5-850-1.5

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900 CP10-5-850-1.5

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800

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700
V (cm /g STP)

600

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Differential pore volume (cm3/g)

1.2
500
3

1.0

400 0.8

300
0.6

0.4
an
200 0.2
M
0.0
100
1 2 3 4 5 6
Pore size (nm)
0
0.0 0.2 0.4 0.6 0.8 1.0
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P/P0

Fig.2 N2 adsorption-desorption isotherms and the inset corresponding pore size

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distributions for the ACs prepared at 850 °C from the different AC precursors (CP0,
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CP5, and CP10).

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Page 21 of 26
Figure 3

Figure 3

1200 CP10-3-850-1.5
CP10-5-850-1.5

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CP10-7-850-1.5

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1000

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800
V (cm /g STP)

600

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Differential pore volume (cm3/g) 1.0
3

0.8
400

200
an 0.6

0.4

0.2
M
0.0
0
1 2 3 4 5 6
Pore size (nm)

0.0 0.2 0.4 0.6 0.8 1.0

ed

P/P0
Fig.3 N2 adsorption-desorption isotherms and the inset corresponding pore size
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distribution profile for the ACs prepared at 850 °C from the CP10 in different
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KOH/CP10 weight ratios (3:1, 5:1, and 7:1).

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Page 22 of 26
Figure 4

Figure 4

CP10-7-850-1.0

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1200

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CP10-7-850-1.5
CP10-7-850-2.0
1000

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V (cm /g STP)

800

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600
Differential pore volume (cm /g)

1.2
3

1.0

400 0.8

0.6
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0.4
200
M
0.2

0.0
0 1 2 3 4 5 6
Pore size (nm)
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0.0 0.2 0.4 0.6 0.8 1.0

P/P0
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Fig.4 N2 adsorption-desorption isotherms and the inset corresponding pore size

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distribution for the ACs prepared from the CP10 at 850 °C for different activation time

(1 h, 1.5 h, and 2.0 h).

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Page 23 of 26
Figure 5

Figure 5

0.06 0.06
(a) (b)
0.04 0.04

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-2
0.02 0.02

Current /A·cm
-2

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Current /A·cm

0.00 0.00

-0.02 -0.02

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-0.04 5 mV/s -0.04 5 mV/s
10 mV/s 10 mV/s
20 mV/s 20 mV/s
-0.06 40 mV/s -0.06 40 mV/s

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-0.08 -0.08
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential /V Potential /V

0.06

0.04
(c)
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0.04
(d)
M
0.02 0.02
-2
-2

Current /A·cm
Current /A·cm

0.00 0.00

-0.02 -0.02
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-0.04 5 mV/s -0.04 5 mV/s

10 mV/s 10 mV/s
-0.06 20 mV/s -0.06 20 mV/s
40 mV/s 40 mV/s

-0.08 -0.08
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-1.0 -0.8 -0.6 -0.4 -0.2 0.0 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential /V Potential /V

Fig.5 CV curves at various scanning rates for the capacitors prepared with different ACs. (a)
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CP0-5-850-1.5, (b) CP5-5-850-1.5, (c) CP10-5-850-1.5, (d) CP10-7-850-1.5

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Page 24 of 26
Figure 6

Figure 6

1.4

1.2

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1.0
Potential /V

0.8

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0.6
d

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b c
0.4 a

0.2

0.0
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0 100 200 300 400 500 600
M
Time /s

Fig.6 The charge-discharge curves of the four AC electrodes. (a) CP0-5-850-1.5, (b)
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CP5-5-850-1.5, (c) CP10-5-850-1.5, (d) CP10-7-850-1.5

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ce
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Page 25 of 26
Highlights

► Low-cost activated carbons (ACs) can be prepared from coal-tar pitch and rosin.

► Co-pyrolysis product of coal-tar pitch and rosin is a suitable AC precursor.

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► Adding rosin favors the porosity development in ACs during KOH activation.

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► The ACs have high surface area as well as good electrochemical performance.

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Page 26 of 26