CARBON 4 7 ( 2 0 0 9 ) 2 9 8 4 –2 9 9 2

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High power supercapacitors using polyacrylonitrile-based

carbon nanofiber paper

E.J. Raa,b, E. Raymundo-Piñeroa, Y.H. Leeb, F. Béguina,*

a
Research Centre on Divided Matter, CNRS-University, 1B rue de la Férollerie, 45071 Orléans, France
b
BK21 Physics Division, Center for Nanotubes and Nanostructured Composites, Sungkyunkwan Advanced Institute of Nanotechnology,
Sungkyunkwan University, Suwon 440-746, South Korea

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

Article history:
Received 23 January 2009
Accepted 24 June 2009
Available online 30 June 2009
Porous carbon nanofiber paper has been obtained by one-step carbonization/activation of
PAN-based nanofiber paper at temperatures from 700 to 1000 C in CO2 atmosphere. The
paper was used as supercapacitor electrode without any binder or percolator. At low tem-
perature, e.g., 6900 C, nitrogen enriched carbons with a poorly developed specific surface
area (SBET 6 400 m2/g) are obtained. In aqueous electrolytes, these carbons withstand high
current loads without a noticeable decrease of capacitance, and the normalized capaci-
tance reaches 67 lF/cm2. At 10 s time constant, the values of energy and power densities
are 3–4 times higher than for activated carbons (AC) presenting higher specific surface area.
By carbonization/activation at 1000 C, subnanometer pores are developed and
SBET = 705 m2/g. Despite moderate BET specific surface area, the capacitance reaches values
higher than 100 F/g in organic electrolyte. At high power densities, the nanofiber paper
obtained at 1000 C outperforms the energy density retention of ACs in organic electrolyte.
The high power capability of the carbon nanofiber papers in the two kinds of electrolytes is
attributed both to the high intrinsic conductivity of the fibers and to the high diffusion rate
of ions in the opened mesopores.
 2009 Published by Elsevier Ltd.

1. Introduction
Electrospinning of polymers is a very successful method for
preparing fibers with diameters from submicro- to nanometer
sizes. The fibers can be electrospun in the form of yarn,
aligned fibrous arrays, or paper [1–5]. In particular the spin-
ning of polyacrylonitrile (PAN) followed by stabilization and
carbonization results in carbon nanofibers [6]. The advanta-
ges of using PAN as precursor is the possibility of easily pre-
paring nanofiber based paper [4], which can be further used
as self-standing carbon electrodes for energy storage devices,
without using any binder as in the case of activated carbons
[7–9].
However, for being effectively used as electrodes for sup-
ercapacitors, these materials should fulfill some require-
ments as: (i) a high conductivity for assuring a high power
density; (ii) an adequate pore size distribution consisting
mainly of nanopores with an average pore size smaller than
1 nm enhancing capacitance either in organic or aqueous
electrolytes [10,11]; (iii) a large amount of surface functional-
ities that could undergo fast redox reactions in order to en-
hance the capacitance through pseudo-capacitive processes
when working in aqueous electrolytes [12,13]. As a conse-
quence, an adequate porosity must be generated in the
PAN-based carbon paper while keeping a high amount of het-
eroatoms and a high conductivity.
Chemical or physical activation of PAN-based carbon
materials has been already reported in the literature [8–
9,14–16]. In the case of chemical activation by ZnCl2 or KOH,
many by-products remain in the fibers [8] and almost all

* Corresponding author: Fax: +33 (0)238633796.

E-mail address: beguin@cnrs-orleans.fr (F. Béguin).
0008-6223/$ - see front matter  2009 Published by Elsevier Ltd.
doi:10.1016/j.carbon.2009.06.051
 CARBON 4 7 ( 20 0 9 ) 2 9 8 4–29 9 2
nitrogen functionalities are removed during the process [14].
During physical activation with steam [9], the reaction pro-
duces an increasing amount of mesopores (pore diameter
>2 nm) when increasing the activation temperature. In order
to obtain an adequate porous texture, the activation temper-
ature must be kept at low values which in turn lead to poor
conductive materials. As a consequence, such materials have
a limited applicability for high power density devices. By con-
trast, it is known that physical activation using carbon diox-
ide results in a more homogeneous development of porosity
within the carbon fibers than steam [17]. In addition, high
amounts of nitrogenated and oxygenated functionalities are
retained after activation of PAN-based materials by carbon
dioxide [15,16].
In this study, PAN-based nanofiber paper prepared by elec-
trospinning has been simultaneously carbonized and acti-
vated by one-step thermal treatment in CO2 atmosphere at
different temperatures. The series of self-standing electrodes
thereof prepared have been electrochemically characterized
in aqueous and organic electrolytes. The results show that
high power density supercapacitors can be obtained in all
the electrolytic media. In addition, these homologous series
allow to study the role of different surface functionalities on
capacitance in aqueous electrolytes.
2. Experimental
To fabricate polyacrylonitrile (PAN)-based nanofiber paper by
electrospinning, a 10% PAN (Aldrich) solution was prepared
in N,N-dimethylformamide (DMF: Aldrich). The polymeric
solution was brought into a syringe and ejected to form
nanofibers by applying a 20 kV bias between the syringe nee-
dle and a rotating collector. The paper thickness was con-
trolled by the total amount of electrospun polymer.
Typically, a thickness of 200 lm was obtained with 20 cc of
polymer solution after about 30 h of spinning time. The pre-
pared electrospun PAN nanofiber paper was placed in an elec-
tric furnace, heated up at a rate of 1 C/min and kept at 280 C
in air during 1 h for the oxidative stabilization of PAN [4]. After
stabilization, the paper was further heated under Ar atmo-
sphere at a rate of 10 C/min and finally soaked at
700–1000 C for four hours under CO2 atmosphere. The final
product is nanoporous carbon nanofiber paper.
Fig. 1 – (a) FESEM image of the electrospun PAN nanofiber paper and (b) FESEM image of the carbonized/activated PAN-based
nanofiber paper. The insets show the corresponding optical micrographs.
2985
The nanofibers morphology was analyzed by field emis-
sion scanning electron microscopy (FESEM: JSM6700F, Jeol).
The specific surface area was determined from the N2
adsorption isotherms at 77 K in the range of 10 6–1 atm
(Autosorb-1MP, Quantachrome) by applying the BET or the
DFT equations. The pore size distribution (PSD) was obtained
by applying the quenching solid differential functional theory
(QSDFT) to the N2 adsorption data [18]. The micropore (0.5–
2 nm) and the mesopore (>2 nm) volumes have been obtained
from the PSD. The ultramicropore (<0.7–0.8 nm) volume was
measured by CO2 adsorption at 273 K (Autosorb-1MP, Quanta-
chrome). The elemental surface composition of the carbon
nanofiber papers was analyzed by X-ray photoelectron spec-
troscopy (XPS-QUANTUM 2000, Physical electronics).
For the electrochemical investigations, two- or three-elec-
trode cells were built using a Teflon Swagelok construction
with a glassy fibrous separator and gold current collectors
for the aqueous media, and stainless steel current collectors
for the organic electrolyte. For the three-electrode cell exper-
iments, Hg/Hg2SO4 and Hg/HgO were used as reference elec-
trode in H2SO4 and KOH media, respectively, and a graphite
rod was the counter electrode. The electrochemical properties
were determined with a multichannel potentiostat/galvano-
stat (VMP, Biologic, France) in aqueous 1 mol L 1 H2SO4 and
6 mol L 1 KOH, and in 1 mol L 1 tetraethylammonium tetra-
fluoroborate (Et4NBF4) dissolved in acetonitrile. In the case
of the aqueous electrolytes, the cells were charged up to
1.0 V and the specific discharge capacitance was measured
in a wide range of current densities from 50 mA/g to 50 A/g.
In organic electrolyte, the cells were charged up to 2.3 V at
current densities from 100 mA/g to 50 A/g. Nyquist plots were
obtained for the two-electrode cells in the frequency range
from 100 kHz to 1 mHz at an open circuit voltage of 10 mV
by using a SOLATRON SI 1260 analyzer. The equivalent series
resistance was obtained at 10 kHz.
3. Results and discussion
3.1. Physico-chemical characterization of the PAN-based
carbon nanofiber paper
Fig. 1a shows a typical field emission scanning electron
microscopy (FESEM) image of the electrospun PAN nanofiber
2986 CARBON 4 7 ( 2 0 0 9 ) 2 9 8 4 –2 9 9 2

paper. The average diameter of the nanofibers is about
300 nm and they have a smooth surface [4]. The morphology
of the nanofiber paper in size of 30 cm · 40 cm is shown in the
inset picture. Fig. 1b presents the FESEM image of the PAN-
based nanofiber paper after carbonization/activation at
1000 C under CO2. The average diameter of the fibers was re-
duced to about 100 nm and their surface became rough. The
paper became black without alteration of its shape, as shown
in the inset.
The development of porosity in the nanofibers after the
CO2 treatment at different temperatures was analyzed by N2
and CO2 adsorption at 77 K and 273 K, respectively. The N2
adsorption isotherms are shown in Fig. 2a; the pore size dis-
tribution obtained from these isotherms is presented in
Fig. 2b; the evolutions of the pore volume, Brunauer–Em-
mett–Teller (BET) and DFT specific surface area are plotted
in Fig. 2c. The BET specific surface area increases slightly up
to a carbonization/activation temperature of 900 C and more
markedly at 1000 C reaching 705 m2/g. The DFT specific sur-
face area increases from 294 m2/g for the 700 C sample to
845 m2/g for the 1000 C one, in parallel to the increase of both
micropore and mesopore volumes with the treatment tem-
perature. The ultramicropore (d < 0.7–0.8 nm) volume in-
creases at 800 C in agreement with the fact that CO2 starts
to slightly react with carbon at such temperature [19]. At
higher temperatures, e.g., 1000 C, the micropores are broad-
ened and some mesopores are formed. As a consequence,
the ultramicropore volume detected by CO2 adsorption is
slightly reduced, whereas nanometer-size pores are devel-
oped. At temperatures higher than 1000 C, all the nanofibers
were completely burnt off.
The results of the surface XPS analysis of the PAN-based
carbon nanofibers are presented in Fig. 3. It can be observed
that the carbon content increases gradually when the carbon-
ization/activation temperature increases from 700 C to
1000 C. The electrospun PAN nanofibers contain 25 wt.% of
nitrogen and, during the carbonization/activation processes,
the values decrease noticeably from 13 wt.% at 700 C to
3 wt.% at 1000 C. On the other hand, the oxygen content is
kept almost constant at a value of 5 wt.% independently of
the treatment temperature. It can be observed that the oxy-
gen content exceeds the nitrogen one above 1000 C. It is
known that under mild pyrolysis, unstable functional groups
such as pyridones, protonated pyridinic-N, pyrrolic-N, and N-
oxides of pyridinic-N are converted to pyridinic-N which is
further transformed to N-oxides under CO2 atmosphere [20].
The latter are further removed by oxidative etching under
CO2 atmosphere at high activation temperature [15].

400
a 700°C
800°C
300 900°C
1000°C
cc/g

200

100

0
0 0.2 0.4 0.6 0.8 1
P/Po

0.8 1000 0.5

b 700°C c
Specific surface area (m /g)

0.7
800°C SDFT
Pore volume (cm /g)
2

800 Vultramicro 0.4

0.6 900°C SBET
dV (cc/nm/g)

1000°C
0.5
600 0.3
0.4

0.3 400 0.2

0.2
200 Vmicro 0.1
0.1 Vmeso

0 0 0
0.1 1 10 700 800 900 1000
Pore width (nm) CO2 treatment temperature (°C)

Fig. 2 – (a) N2 adsorption isotherms for the PAN-based nanofiber paper treated with CO2 at different temperatures; (b)
influence of the CO2 carbonization/activation temperature on the pore size distribution obtained from the N2 adsorption data
after applying the QSDFT equation; (c) evolution of the BET specific surface area, DFT specific surface area, ultramicropore,
micropore and mesopore volumes with the carbonization/activation temperature.
 CARBON 4 7 ( 20 0 9 ) 2 9 8 4–29 9 2 2987

100 tion, directly related with the porous texture, and the pseu-
25 do-capacitance.
Elemental contents (%)

The electrochemical properties of the carbon nanofiber pa-

80
20 per have been firstly investigated in three-electrode cells.
Carbon Fig. 4a and b show the cyclic voltammograms obtained for
60 the 900 C and 1000 C treated materials in two different elec-
15
Nitrogen trolytes: 1 mol L 1 H2SO4 and 6 mol L 1 KOH. The current was
40 10 converted to specific capacitance via C(F/g) = dQ/dV (1/m) =
dt/dV (I/m), where dV/dt is the potential scan rate and I/m is
20 5 the current per electrode mass [12]. Although the BET specific
Oxygen surface area of the 900 C CO2-treated electrode is very low
(376 m2/g) and half of that for the one treated at 1000 C
0 0
PAN Stabili- 700 oC 800 oC 900 oC 1000 oC (705 m2/g), the capacitance of the two materials is comparable
zation (Fig. 4a and b), independently of the electrolyte. If only the
EDL would contribute, a higher capacitance should be ex-
Fig. 3 – Evolution of carbon, nitrogen and oxygen contents pected for the sample treated at 1000 C. Whereas the amount
(wt.%) determined by XPS. of oxygenated surface functionalities is the same for the two
materials, the amount of nitrogen on the active surface of the
3.2. Electrochemical characterization in aqueous sample treated at 900 C is twice the value for the sample
electrolytes treated at 1000 C (see Fig. 3), indicating that the N-containing
groups of the material treated at 900 C can noticeable en-
Some surface functionalities can undergo fast redox reactions hance capacitance through a pseudo-faradaic contribution.
in aqueous electrolytes, giving rise to a pseudo-capacitive On the other hand, the capacitance values displayed in KOH
contribution [12–13,21–24]. In such a way, the capacitance electrolyte (Fig. 4b) are higher than the ones obtained in
value is the sum of the electric double-layer (EDL) contribu- H2SO4 (Fig. 4a), whatever the material, implying that the N-
containing surface functionalities are more active in basic
medium.
600 Fig. 5a shows the Nyquist plots for two-electrode capaci-
a (H2SO4)
tors built with the 900 and 1000 C treated carbons in both
Sp. capacitance (F/g)

400 aqueous electrolytes. The equivalent circuit consists of the

equivalent series resistance (ESR), the EDL capacitance, the
200
Faradaic charge transfer resistance and its corresponding
0 Warburg impedance element W [12]. In the case of H2SO4,
the ESR values are 0.36 and 0.2 X for 900 and 1000 C, respec-
-200 tively, as shown in Fig. 5b. These values are slightly increased
o to 0.6 and 0.37 X in the case of KOH, and a small ohmic drop
900 C
-400
o was observed up to a discharge current of 50 A/g. The War-
1000 C
-600 burg impedance region W at low frequency, which is associ-
ated to Faradaic reactions together with the kinetic leakage
-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 processes in the diffusion line, is represented by a 45 straight
Potential ( V vs Hg/Hg2SO4 ) line. This region is expanded for the 900 C carbon in both
electrolytes, with a higher expansion in the case of KOH.
These observations are strongly correlated with the increase
600 b (KOH) of the pseudo-capacitive contribution. The ideal vertical
Sp. capacitance (F/g)

400 behavior behind the W region indicates that the total area
of the internal structure of the porous carbon electrode is
200 completely wetted by both electrolytes. This is an advantage
of the nanofiber morphology compared to the granular or
0
flake ones as it has been previously reported for polyaniline-
-200 based electrodes [25].
Two electrode capacitors have been built with the materi-
-400
900 oC
als prepared at 800, 900 and 1000 C in 6 mol L 1 KOH and
1000 oC 1 mol L 1 H2SO4. Due to its high resistance, the material pre-
-600
pared at 700 C (see Fig. 5b) was not further studied. Fig. 6
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 shows the values of gravimetric capacitance obtained in a
Potential ( V vs Hg/HgO ) voltage range between 0 and 1.0 V in both media. The values
of capacitance are higher in 6 mol L 1 KOH than in 1 mol L 1
Fig. 4 – Three-electrode CV curves of the 900 C and 1000 C H2SO4, independently of the CO2-treatment temperature, in
CO2-carbonized/activated samples at a scan rate of 2 mV/s correlation with the results obtained in three electrode cells
in (a) 1 mol L 1 H2SO4 and (b) 6 mol L 1 KOH. (Fig. 4a and b). When increasing the carbonization/activation
2988 CARBON 4 7 ( 2 0 0 9 ) 2 9 8 4 –2 9 9 2

temperature, the specific surface area and the EDL contribu-

a 5 5
H2SO4 KOH tion increase while the amount of surface functionalities
and the pseudo-capacitive contribution decrease. In such a
900 oC
4 4 way, the total capacitance is only slightly depending on the
1000 oC
treatment temperature. The gravimetric capacitance obtained
3 3 with the 800 C carbonized/activated nanofiber paper is lower
- Z" ( Ω)

than expected due to the resistivity of the electrodes (see Fig-

ure 5b) which is still too important. Despite the low specific
2 2 surface area of the 900 C treated material and thanks to the
pseudo-faradaic contribution of surface functionalities,
1 1 capacitance values as high as 200 F/g in H2SO4 and 240 F/g
W region
W region in KOH can be obtained. Such values are significantly higher
than for commercial activated carbons with higher specific
0 0
0 1 2 3 0 1 2 3 surface area and micropore volume. For example, an
activated carbon (AC, Norit Super 50) with a SBET = 1400 m2/g
Z' ( Ω ) (Vmicro = 0.57 cm3/g and Vmeso = 0.17 cm3/g) and a similar
amount of oxygenated functionality (O = 5.9 wt.%, see
Table 1), demonstrates capacitance values of only 119 F/g in
b 100 93.8 Ω H2SO4 H2SO4 and 99 F/g in KOH. These results confirm that the nitro-
genated functionality present on the surface of the PAN-
80 KOH based carbon nanofiber paper is the responsible of the addi-
tional pseudo-capacitance, being more active in KOH than
RS ( Ω )

60 51.5 Ω in H2SO4 medium.

Furthermore, the normalized capacitance has been calcu-
40 lated by dividing the gravimetric capacitance either by the
BET specific surface area (SSA) or by the DFT SSA. Values as
7.45 Ω
high as 63 lF/cm2 using the BET SSA or 38 lF/cm2 using the
20 1.69 Ω 0.36 Ω 0.20 Ω
0.37 Ω DFT SSA are obtained in the case of the 900 C carbonized/
0.60 Ω
pyrolyzed material in 6 mol L 1 KOH. According to the litera-
0 ture, the normalized capacitance estimated from the BET
700 800 900 1000 SSA ranges around 10 lF/cm2 when only the double-layer
mechanism is involved [12], meaning about 0.05 electrons
CO2 treatment temperature (ºC)
per atom of accessible surface. The values of 63 lF/cm2 and
38 lF/cm2 correspond to 0.31 and 0.19 electrons per atom,
Fig. 5 – (a) Nyquist plot in the range of 10 mHz–100 kHz and
respectively, confirming that an other mechanism, a pseu-
(b) equivalent series resistances at 10 Hz in H2SO4 and KOH
do-faradaic charge transfer, takes place.
electrolytes as a function of the carbonization/activation
In order to determine which functionalities are responsi-
temperature.
ble of the important pseudo-capacitive character of these
materials, the XPS data were carefully analysed. Table 1 pre-
sents the proportions of the different nitrogen contributions
obtained from the deconvolution of the N1s peak. It can be
noticed that the amount of quaternary nitrogen (NQ) is con-
Normalized capacitance ( μF/cm2)

300 80
stant independently of the carbonization/activation temper-
Sp. capacitance (F/g)

ature, whereas the amount of pyridine (N6) and pyridone

250 or pyrrole (N5)-type contribution decreases when increasing
60 the treatment temperature. Taking into account that the
oxygen content is nearly the same for all the materials
200 (see Fig. 3), it seems interesting to correlate the decrease of
normalized capacitance at high treatment temperature with
40
the decrease of nitrogen functionalities other than quater-
150
KOH nary. In this sense, Fig. 7 shows that the normalized capaci-
H2SO4 tance of the materials prepared at 800, 900 and 1000 C
100 20 increases with the total nitrogen content in KOH medium,
800 900 1000 confirming the results previously obtained with activated
CO2 treatment temperature (ºC) carbons prepared from PAN/pitch blends in various propor-
tions [23]. The same tendency is observed when the values
Fig. 6 – Influence of the carbonization/activation of normalized capacitance are plotted versus the total
temperature on the gravimetric and normalized capacitance amount of N6 + N5 functionalities, indicating that the N6 or
measured from 2-electrode experiments at a discharge N5 nitrogen at the edges of the graphitic layers is mainly
current of 50 mA/g in H2SO4 and KOH electrolytes. responsible of the pseudo-capacitance rather than the NQ
 CARBON 4 7 ( 20 0 9 ) 2 9 8 4–29 9 2 2989

Table 1 – XPS elemental composition of the carbon nanofiber papers and mass percentages of the different nitrogen
functionalities obtained from the deconvolution of the N1s peak. Data obtained on an activated carbon (AC, Norit Super 50)
are included for comparison purposes.
a a a a
Sample C1s wt.% O1s wt.% N1s wt.% N6 398.5 ± N5 400.5 ± NQ 401.2 ± NO 402.9 ±
0.2 eV wt.% 0.2 eV wt.% 0.2 eV wt.% 0.2 eV wt.%

PAN700 82.0 5.7 12.3 5.7 4.3 1.6 0.7

PAN800 85.2 4.9 9.9 4.2 3.3 1.7 0.6
PAN900 88.3 4.8 6.9 2.3 2.2 1.7 0.6
PAN1000 91.8 4.9 3.3 0.6 0.7 1.8 0.3
AC 94.1 5.9 – – – – –
a N6: pyridine; N5: pyridone/pyrrole; NQ: quaternary nitrogen; NO: oxidized nitrogen.
Normalized Capacitance (µF/cm2)

250
70
a

Sp. capacitance ( F/g)

200
60

150
50

100 900 oC with KOH

40
1000 oC with KOH
wt%N6+N5 900 oC with H2SO4
30 50
AC with H2SO4
wt%Ntotal 1000 oC with H2SO4
20 0
0 2 4 6 8 10 12 0 10 20 30 40 50
Current density (A/g)
wt%N
Fig. 7 – Normalized capacitance in KOH electrolyte as a 10
function of the total amount of nitrogen (wt.% total) and of
b
Energy density (Wh/kg)

the amount of pyridinic, pyridonic and pyrrolic nitrogen

(wt.%N5 + N6). AC with H2SO4
10 sec
quaternary nitrogen located inside the graphitic layers. The
900 oC with KOH
same conclusions can be stated from the results obtained 1
1000 oC with KOH
in acidic medium. However, the lower values of capacitance
in comparison with the basic electrolyte indicate that the 900 oC with H2SO4 1 sec
nitrogenated functionalities are less active when decreasing 1000 oC with H2SO4
the solution pH.
The power capability of the PAN-based nanofiber paper has 10 100 1000 10000
been investigated by galvanostatic charge/discharge cycling at Power density (W/kg)
different current densities. Fig. 8a represents the gravimetric
discharge capacitance of the 900 C and 1000 C treated mate- Fig. 8 – (a) Gravimetric capacitance vs discharge current
rials at current densities from 50 mA/g to 50 A/g in the two density and (b) Ragone plot of the carbon nanofiber papers
aqueous electrolytes. The capacitance values rapidly decrease in H2SO4 and KOH electrolytes. The commercial activated
at low discharge current and become stable above 1 A/g. The carbon AC (Norit Super 50) is shown as reference.
reduction of capacitance is less than 30% of the initial value,
independently of the carbonization/activation temperature
and electrolyte. It is noteworthy that the capacitance is main- The Ragone plot also shows that a high power density can
tained above 150 F/g even at a high discharge current of 50 A/g. be extracted without a significant degradation in the energy
This is in high contrast with the severe capacitance drop of the density (Fig. 8b). At 10 s time constant, the energy density is
commercial activated carbon AC which reaches more than around 6.0 Wh/kg and the power density around 4.0 kW/kg,
75% at high current density (Fig. 8a). This high power stability against 1.5 Wh/kg and 1.1 kW/kg, respectively, for the acti-
with the PAN-based nanofibers is ascribed to their conductiv- vated carbon AC commercialized for supercapacitors.
ity and to their structural/textural advantage. The small The cycling evolution of capacitance at a high current den-
amount of opened mesopores favors the access of ions to sity of 1 A/g also demonstrates a low fading in both electro-
the active surface [13] making the charges transfer easier. lytes after about 5000 cycles, although the stability is
2990 CARBON 4 7 ( 2 0 0 9 ) 2 9 8 4 –2 9 9 2

250 2.5
120
Sp. capacitance (F/g)

100
200 2.0

- Z" ( Ω )
80
60

Voltage
40
150 1.5 20
0
900 oC with KOH 0 20 40
100 1.0 Z' ( Ω )
1000 oC with KOH 500 mA/g
900 oC with H2SO4 200 mA/g
50 0.5
1000 oC with H2SO4 1000 mA/g
0 0.0
0 1000 2000 3000 4000 5000 0 200 400 600
Cycle number Time (sec)
Fig. 9 – Cycling evolution of capacitance measured at 1 A/g Fig. 11 – Voltage–time curves obtained at different values of
discharge current in H2SO4 and KOH aqueous electrolytes. discharge current density for a two-electrode cell based on
the 1000 C treated carbon in organic electrolyte. The inset
shows the Nyquist plot.
slightly better in the case of the KOH solution (Fig. 9). These
results indicate a high reversibility of the redox reactions tak- after treatment at 1000 C, there is a widening of the
ing place on the active surface of the electrodes. The lower micropores as presented in Fig. 2b. Capacitance values high-
stability in H2SO4 could be ascribed to the formation of sulfo- er than 100 F/g can be obtained with the 1000 C-treated
nate (–SO3H) or sulfate (–OSO3H) groups on the surface of the
carbon materials [26].
120
a
3.3. Electrochemical performance in an organic electrolyte
Sp. capacitance (F/g)

100
PAN-based nanofiber paper
The PAN-based carbon nanofiber paper has been also
80
implemented in two electrode capacitors using an organic
electrolyte. Since the storage mechanism in this case is
60
based on the formation of the electric double-layer, the por- AC
ous nanotexture is the main parameter to be taken into ac-
40
count. In this sense, the capacitance of the carbon
materials prepared at temperatures 6900 C was almost
20
negligible (see for example in Fig. 10 the CV of the material
treated in CO2 at 900 C). For these materials, the porosity is
0
essentially constituted of ultramicropores (see Fig. 2b), most 0 10 20 30 40 50
of them having a size <0.6 nm, i.e. being smaller than the
Current density (A/g)
size of the desolvated Et4N+ cation (0.68 nm). By contrast,

50
200 b
PAN-based nanofiber paper
Energy density (Wh/kg)
Sp. capacitance (F/g)

AC
100 10

0
10 sec
CO2 treatment at 900 oC
1 sec
-100
1
10 100 1000 10000
0.0 0.5 1.0 1.5 2.0 2.5 Power density (W/kg)
Voltage (V)
Fig. 12 – (a) Specific capacitance vs discharge current density
Fig. 10 – CV curves of the 900 C and 1000 C treated carbons and (b) Ragone plot in organic electrolyte. The results
at a scan rate of 2 mV/s in 2-electrode cells built in organic obtained with the activated carbon AC (Norit Super 50) are
electrolyte. shown for comparison.
 CARBON 4 7 ( 20 0 9 ) 2 9 8 4–29 9 2
material, indicating that the pore size distribution is well
adapted. The cyclic voltammograms present an almost rect-
angular shape characterizing the good capacitive behavior
of this material (Fig. 10).
For the 1000 C-treated material, the linear voltage–time
(V–t) discharge response indicates a purely EDL mechanism
without kinetics limitations (Fig. 11). The initial ohmic drop
is negligible even at current densities as high as 1 A/g, dem-
onstrating a high conductivity of the cell based on this mate-
rial. The impedance plot in the inset gives an ESR of 3.4 X for
the self-standing nanofiber paper, which is still lower than
7.6 X for AC electrodes where 5 wt.% of acetylene black per-
colator was added. Due to the high conductivity and special
morphology of the PAN-based nanofiber paper electrodes,
when increasing the discharge current density, the specific
capacitance retention (Fig. 12a) is exceptional in comparison
with the behavior of a commercial activated carbon (AC).
Specific capacitance values as high as 70 F/g are still kept
at 50 A/g in comparison with the complete loss of capaci-
tance for AC at current densities around 10 A/g. The Ragone
plot in Fig. 12b demonstrates a high power capability of the
PAN-based carbon nanofiber paper. In the time range from 1
to 10 s, it outperforms the activated carbon AC of higher spe-
cific surface area. Hence, the special structure and nanotex-
ture of the PAN-based carbon nanofiber papers open new
vistas for the development of high power EDLCs in organic
electrolyte.
4. Conclusions
Self-standing carbon electrodes were obtained by one-step car-
bonization/activation of PAN-based carbon nanofiber paper
under CO2. The supercapacitors based on these materials are
able to operate at high power density both in aqueous and in or-
ganic electrolytic media, while keeping high values of energy
density. The PAN-based nanofiber paper presents moderate
to low specific surface area and it also contains nitrogenated
and oxygenated surface functionalities. In aqueous electro-
lytes, the functional groups are involved in redox reactions giv-
ing a high pseudo-faradaic contribution. In particular, the N
functionalities located at the edges of the graphitic layers pres-
ent the highest activity. In organic electrolyte, the well adapted
pore size distribution of the 1000 C obtained carbon, with
nanometer size pores and a moderate amount of mesopores,
is at the origin of a high capacitance and a high power capabil-
ity. The high power stability obtained in both electrolytic media
is ascribed to the structural/textural advantage of the PAN-
based nanofibers. They combine (i) opened mesopores which
enhance ions diffusion to the active surface; (ii) a high electri-
cal conductivity which makes the interfacial charge transfers
easier. These materials present a new route for developing high
power supercapacitors.
Acknowledgements
This project was supported by the MOE through STAR-faculty
and in part by the KOSEF through CNNC at SKKU. Norit (The
Netherlands) is acknowledged for providing the reference
activated carbon.
2991
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