Materials Letters 87 (2012) 157161

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Supercapacitive properties of porous carbon nanobers via the

electrospinning of metal alkoxide-graphene in polyacrylonitrile
So Yeun Kim a, Bo-Hye Kim b,n, Kap Seung Yang a,b,c,nn, Kyoichi Oshida d
a

Department of Advanced Chemicals and Engineering, Chonnam National University, 300 Yongbong-dong, Buk-gu, Gwangju 500-757, Republic of Korea
Alan G. MacDiarmid Energy Research Institute, Chonnam National University, 300 Yongbong-dong, Buk-gu, Gwangju 500-757, Republic of Korea
c
Department of Polymer and Fiber System Engineering, Chonnam National University, 300 Yongbong-dong, Buk-gu, Gwangju 500-757, Republic of Korea
d
Department of Electronics and Computer Science, Nagano National College of Technology, Nagano 381-8550, Japan
b

a r t i c l e i n f o

abstract

Article history:
Received 29 February 2012
Accepted 21 July 2012
Available online 31 July 2012

The polar group SiOC introduction was made into the carbon nanobers, and the resulting carbon
nanober composite (CNFC) electrodes were evaluated as an electrochemical capacitor. Simple thermal
treatment of the electrospun nanobers from the blend solution of tetraethyl orthosilicate and
graphene with polyacrylonitrile introduced suitable micropores to accommodate many ions without
a pore creation step such as oxidative activation. The supercapacitor electrode prepared with 3 wt%
graphene showed high specic capacitance of 144.80 Fg  1, energy density of 18.4910.83 Whkg  1 in
the respective range of 40030,000 Wkg  1 in 6 M KOH aqueous solution. The specic capacitance and
energy density were 2 and 3 times higher, respectively, in comparison with pristine CNF.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
Electrospinning
Graphene
Tetraethyl orthosilicate
Carbon nanober composite
Supercapacitor

1. Introduction
Supercapacitors have been intensively investigated as primary
and/or backup energy storage systems because they can sustain
high power levels with long life cycles [17]. Various forms and
textures of porous carbons have been examined as possible
electrode materials for supercapacitors due to their stable physical and chemical properties, large specic surface area, controlled
pore structure, and high conductivity [812]. In recent years,
porous carbons with tunable structures, textures, and ordered
porosity have been successfully obtained by the template such as
mesoporous silica, porous coordination polymers (PCPs), and
metal-organic frameworks (MOFs) [1318]. The unique nature
of nanoporous structures has exhibited promising electrochemical capacitive properties as supercapacitor electrode materials
[1924]. Researchers have explored graphene-based composite
materials to improve the capacitance performance, due to superior electrical conductivities of graphene [2527]. Electrospinning
is a unique method capable of producing nanoscale bers from
both synthetic as well as natural polymers for numerous

n
Corresponding author at: Alan G. MacDiarmid Energy Research Institute,
Chonnam National University, Yong-Bong dong 300, 500-757 Gwangju, Republic
of Korea. Tel.: 82 62 530 0774; fax: 82 62 530 1779.
nn
Corresponding author at: Department of Polymer & Fiber System Engineering,
Chonnam National University, Yong-Bong dong 300, 500-757 Gwangju, Republic
of Korea. Tel.: 82 62 530 0774; fax: 82 62 530 1779.
E-mail addresses: bohye@chonnam.ac.kr (B.-H. Kim),
ksyang@chonnam.ac.kr (K.S. Yang).

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.07.093

applications [28]. The nonwoven web obtained from the electrospinning [29,30] has a high specic surface area from shallow
pores size, resulting in enhanced specic capacitance at elevated
current density for energy storage devices.
In this work, the highly spinnable polyacrylonitrile (PAN),
graphene, and tetraethyl orthosilicate (TEOS) as pore generator
were combined to prepare electrospun ber webs. The resulting
silicon-containing CNFCs were evaluated for electrode performances of a supercapacitor on the basis of pore characteristics
and unique microstructural features.

2. Experimental
The graphenes used in this study were xGNP-C750-grade
materials produced by XG Science, USA. Elemental analysis shows
that graphene composition was made as 88.68% carbon, 0.79%
hydrogen, 1.11% nitrogen, and 7.65% oxygen using the Mettler
method (Mettler-Toledo AG, Switzerland). Solution for electrospinning were prepared by dispersing the appropriate amount of
graphene (3 and 5 wt% relative to PAN and TEOS) in TEOS/PAN
with weight ratio of 1/9 in dimethylformamide (DMF). This
solution was fed into a positively charged spinneret attached to
an electrospinning apparatus. The electrospun ber web was
stabilized in air and then carbonized in N2 atmosphere at
800 1C. The samples were identied as TGP-3 and TGP-5, indicating concentrations of 3 and 5 wt% graphene. For the pristine
samples, TG, GP-3, and CNF samples were prepared according to
the ow diagrams in Fig. S1.

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The morphology of the composites was characterized using an

FE-SEM (Hitachi, S-4700, Japan) equipped with EDX spectroscopy.
The surface functionality of the CNFCs was examined by FTIR
spectroscopy (Nicolet 200). Backscattering Raman measurement
was carried out with a Renishaw in Via-Reex at room temperature.
A HeNe laser was used giving a monochromatic red light of 633 nm
wavelength at a power of approximately 15 mW on sample surface.
XRD was obtained from ground-up samples of the bers, using a
D-Max-2400 diffractometer and CuKa radiation (l 0.15418 nm).
From the position of the (002) peak (2y) in XRD, the interplanar
spacing d(002) was determined using the Bragg equation [31]. From
the position and the full-width at half-maximum intensity of the
(002) peak, an attempt was made to estimate the crystalline height
Lc using the Scherrer equation [31]. The specic surface area was
analyzed by the BET method using an ASAP 2020 Physisorption
Analyzer (Micromeritics, USA). The full range of pore sizes over a
continuous scale was conrmed through density functional theory
calculations (DFT PLUS for Windows). The cell performances of the
supercapacitor were tested with two 2.25 cm2 CNF electrodes in a

6 M KOH aqueous solution. The capacitance of the electrodes was

galvanostatically measured with a WBCS 3000 battery cycler system
in the potential range of 01 V and at a current density of 1
20 mA cm  2.

3. Results and discussion

SEM images obtained at low and high magnication of the
various CNF composite webs are presented in Fig. 1. All of the
samples exhibited long and continuous cylindrical morphologies
with 100 300 nm of average diameter. The SEM images of GP-3
and TGP-3, shown in Fig. 1(a) and (c) revealed a smooth surface,
whereas the TGP-5 in Fig. 1(d) showed a bent shape with node or
joint due to the agglomeration of the graphene at high graphene
concentration. At high magnication, the morphologies of the TGP
became rougher and displayed a more porous appearance with
10  20 nm pores (Fig. 1(b)). The elemental mapping (Fig. 1(e))
represents the silicon element dispersion on the surface of the

Fig. 1. FE-SEM images showing (a) GP-3, (b) TP, (c) TGP-3, and (d) TGP-5, (e) highly magnied SEM image and the corresponding elemental mapping, and (f) EDX data of
individual ber.

S.Y. Kim et al. / Materials Letters 87 (2012) 157161

bers. The corresponding EDX spectrum indicates that the distribution of C, O, and Si elements in the ber (Fig. 1(f)), highlighting the homogeneous distributions of amorphous SiOC
and/or OSiO in the carbon matrix.
The IR spectra of CNF, TGP-3, and TGP-5 are shown in Fig. 2(a).
Three main features are observed in agreement with the literature: (i) in case of TGP-3, and TGP-5, the main bond of SiOC in
the range of 930 1215 cm  1 is composed of the CO bond and
SiO cross-link bond compared with CNFs [32]. (ii) the band at
1600 cm  1 is attributed to the CQC vibrations and (iii) the broad

159

band at ca. 3490 cm  1 is due to hydrogen bonded OH stretching

vibrations. From the XRD patterns (Fig. 2(b)) of TGP-3, TGP-5, and
TP, a broad peak located at 201301 is assigned as the d(002) layers,
representing the presence of disordered carbon structure and the
amorphous SiOC/SiOSi and disordered carbon phases [33].
The Raman spectra (Fig. 2(c)) of the TGP-3, TGP-5, and TP typically
show peaks in the range of 300500 and 13001600 cm  1,
respectively. In these Raman spectra there are two large peaks,
one is near 1338 cm  1 which is D peak from amorphous structures of carbon, another is near 1605 cm  1 which is G peak from

Fig. 2. (a) FTIR spectra of the TGP-3, TGP-5, and CNF, (b) XRD peaks, (c) Raman spectra of the TGP-3, TGP-5, and TP, (d) a plot for crystalline trend.

Fig. 3. (a) Nitrogen adsorptiondesorption isotherms and (b) pore size distributions determined by DFT calculations of TGP-3 and CNF.

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S.Y. Kim et al. / Materials Letters 87 (2012) 157161

graphitic structures of carbon [34]. The broad band appeared

between 300 and 500 cm  1 might be due to a contribution from
the amorphous SiOC-related structure [35]. Fig. 2(d) summarizes the interlayer spacing d002, crystalline height Lc from
XRD and the crystalline width La (La 4.4/R, R is the ratio of the
integrated intensity of D peak to G peak, nm) from the Raman
spectra [36]. With adding the graphene, a decrease in d002 and
increase in Lc and La are also observed, indicative of the formation
of more ordered carbons [33]. It is expected that the incorporation
of the graphene can inuence the electrochemical performance by
the pp interaction between carbon layers, and graphene can
reduce the energy loss during chargedischarge.
Nitrogen adsorptiondesorption isotherms and the corresponding pore size distribution curves by the DFT method of
the samples are shown in Fig. 3. The adsorption isotherms of TPG3 and CNF show typical type I behavior indicating high microporosity, and the adsorption of nitrogen was nearly complete at a
low relative pressure, P/P0 o0.1 (Fig. 3(a)). The pore size distributions of all carbon materials were determined by density functional theory (DFT) and are shown in Fig. 3(b). According to the
pore size distributions, 60  80% of the micropores in TGP-3 were
ultramicropores with diameters less than 0.6 nm. The narrow
micropores and mesopores are developed for the TGP-3 materials.
Alternatively, CNF presented a broader distribution of micropore
sizes, and an average diameter of 1.4 nm was observed. These
results suggested that the presence of ultramicropores with
diameters less than 0.6 nm leads to selective ion adsorption
[18,37] and well-dispersed mesopores can provide pathway for
fast transportation of the electrolyte ions [11,38].
The pore characteristics of various CNFCs were investigated by
nitrogen adsorption measurements at 77 K, as shown in Table S1.
The specic surface area decreased from 437.64 m2/g for TPG-3 to
313.16 m2/g for TGP-5. At higher graphene concentration, the
reduction of the specic surface area could be resulted from the
aggregation of graphenes and less effective to contribution to
create pores. Furthermore, the surface area of TP is higher than
that of GP-3, because TEOS acts as a catalyst for the creation of
micropores on the outer surface of CNFCs. TEOS trapped in
electrospun nanobers can be transformed into its hydrated form
(i.e., Si(OEt)4  nH2O). During the stabilization process, silanol
(Si(OH)x) is produced by the hydrolysis of SiOEt bonds into Si
OH bonds. Extensive condensation of SiOH leads to the formation
of amorphous OSiO and/or SiOC with gas evolution (e.g., CO,
CO2, H2, CH4, H2O, etc.), which leads to a porous structure [39]. An
increase in electrical conductivity was observed, from 0.24 S/cm
for CNF to 0.35 S/cm for TP to 0.38 S/cm for GP-3, with adding
graphene in Table S1.
The porous CNFC electrodes were cut into rectangles and were
attached to nickel foam to evaluate the capacitance of the
material in a two-electrode system and 6 M KOH (aq) electrolyte.
Cyclic voltammograms (CVs) obtained at a scan rate of 25 mVs  1
are presented in Fig. 4(a). The TGP-3 electrode shows a much
larger quasi-rectangular shape than the other samples, whereas
the GP-3 electrode shows a rectangular and symmetric shape.
This result represents the expansion of the electrical double-layer
region because TGP-3 has heteroatoms (nitrogen, oxygen and
silicon), a large surface area with moderate porosity, and good
electrical conductivity. The symmetric cell assembled with the
CNFCs electrode was subjected to measure specic capacitances
in the voltage range of 01.0 V with varying discharge current
densities from 1 to 20 mA cm  2 in aqueous electrolytes
(Fig. 4(b)). The capacitance of the cells decreased as the current
densities increased, due to the internal resistance of the electrodes. The TGP-3 web electrode had a greater specic capacitance at
all current densities than the other electrodes, which was attributed to the higher electrical conductivity and the larger specic

Fig. 4. Electrochemical test of SiOC based CNFCs in KOH (aq) electrolyte;

(a) CVs at a scan rate of 25 mVs  1, (b) specic capacitances as a function of a
various current densities, (c) Ragone plots.

surface area of TGP-3. This same trend of power and energy

performance, which indicates a good behavior in specic capacitance, was also evaluated with a Ragone plot. Fig. 4(c) shows
Ragone plots of the CNFC web electrodes. The TGP-3 web
electrode exhibits high energy density of 18.4910.83 Whkg  1
in the power density range of 40030,000 W/kg; in comparison of

S.Y. Kim et al. / Materials Letters 87 (2012) 157161

the energy density of 2.06.0 Whkg  1 for the pristine CNF in the
same power density range.

4. Conclusion
We successfully prepared electrodes in combining the advantageous properties of PAN, TEOS and graphene precursors in the
electrospinning process, followed by suitable stabilization and
carbonization, to form CNFC electrodes for supercapacitors with
enhanced energy and power densities. The TGP-3 web electrode
showed the best performance in electrochemical tests for EDLC.
The electrodes of the EDLC improved not only in the specic
capacitance but also in the energy density; from the specic
capacitance of 60.0 F/g, energy density of 6.0 Whkg  1 of the CNF,
to 144.80 F/g and 18.49 Whkg  1, respectively, at the composite
bers of 3 wt% of graphene. The introduction of TEOS and
graphene into the PAN solution modied the morphological
structure, resulting in increases in specic surface area electrical
conductivity leading to the enhancement of the electrochemical
performances of CNF composites.

Acknowledgments
This research was supported the National Research Foundation
of Korea(NRF) Grant (NRF-2010-616-D00018) and the Ministry of
Education, Science and Technology (MEST) (K2090100172510E0100-09700).

Appendix A. Supporting information

Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.matlet.2012.07.093.

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