CARBON 4 9 ( 2 0 1 1 ) 3 3 9 5 –3 4 0 3

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Highly porous electrospun polyvinylidene fluoride (PVDF)-

based carbon fiber

Ying Yang 1, Andrea Centrone 2, Liang Chen, Fritz Simeon, T. Alan Hatton,
Gregory C. Rutledge *
Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA

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

Article history:
Received 13 February 2011
Accepted 7 April 2011
Available online 19 April 2011
Porous poly(vinylidene fluoride) fibers were prepared by electrospinning from solutions in
dimethylformamide, poly(ethylene oxide) (PEO) and water. The PVDF fiber mats were then
converted into electrospun carbon fiber paper using a low temperature chemical stabiliza-
tion treatment (‘‘dehydrofluorination’’) followed by carbonization at 1000 C. The resulting
self-supporting carbon fiber paper exhibits unusually high surface area, in excess of
380 m2/g as measured by the nitrogen adsorption method, and a hierarchical pore struc-
ture. The largest pores are formed by the interstices between fibers; intermediate-sized
pores arise from liquid–liquid phase separation during electrospinning to form polymer-
rich and solvent-rich domains within the fibers; the smallest pores form upon decomposi-
tion of the PEO during carbonization. The electrospun carbon paper performs well as an
electrode for driving the redox chemistry of ferrocene/ferrocenium. This is attributed to
the high surface area of the electrode and the ease of diffusion of the redox-active species
within the porous structure. The ratio of the dehydrofluorination agent (1,8-diazabicy-
clo[5.4.0]undec-7-ene) to vinylidene fluoride during dehydrofluorination was found to be
the key to retaining the as-spun pore morphology during carbonization. The structure
and morphology were further characterized by Scanning Electron Microscopy, Energy Dis-
persive X-ray Spectroscopy, X-ray diffraction, and Raman spectroscopy.
 2011 Elsevier Ltd. All rights reserved.

1. Introduction carbon fibers depend on the choice of precursor. Rayon and

Carbon fiber materials are attracting scientific and technolog-
ical interest for their existing and potential commercial appli-
cations as catalyst supports [1], electrochemical probes [2],
energy storage electrodes in supercapacitors [3] and in redox
flow batteries [4]. In principle, any fibrous material with a car-
bon backbone can potentially be used as a precursor for such
carbon fiber materials. The mechanical properties, as well as
the thermal and electrical conductivities of the resulting
polyacrylonitrile (PAN) are used as precursors for most of
the commercial carbon fibers [5], although other precursors
such as pitch [6], phenolic resins [7], and poly(vinylidene fluo-
ride) (PVDF) [8] have also been reported.
One of the challenges in using carbon fiber materials as
electrodes for driving electrochemical reactions, as in the
redox flow battery [9], is to increase the number of active sites
on the electrode, since these heterogeneous electron transfer
processes occur only at the interface between the solid

* Corresponding author.
E-mail address: rutledge@mit.edu (G.C. Rutledge).
1
Current address: Department of Electrical Engineering, Tsinghua University, Beijing 100084, China.
2
Current address: Center for Nanoscale Science and Technology, 9 National Institute of Standards and Technology, Gaithersburg, MD
20899-6203, USA.
0008-6223/$ - see front matter  2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2011.04.015
3396 CARBON 4 9 ( 2 0 1 1 ) 3 3 9 5 –3 4 0 3
electrode and the redox chemistry-containing phases. For a
given electrode, the density of the active sites is a character-
istic of the material. Increasing the surface area of the elec-
trode with a suitable hierarchical pore structure is one
strategy to improve the electrode performance. Electrospin-
ning is a general method to form continuous polymer fibers
with diameters in the submicron to nanometer range in a
nonwoven mat with substantial surface area [10]. The nonwo-
ven mat can subsequently be converted into electrospun car-
bon fiber paper (ECP). Carbon nanofibers with a solid interior
and smooth surface are usually obtained, with surface areas
generally around 1–50 m2/g [5].
In order to attain electrospun carbon fibers with larger sur-
face areas, several research groups have attempted to pro-
duce porous carbon fibers from different bicomponent blend
electrospun fibers, followed by selective extraction of one of
the blend components in a second process step. For example,
45/55 w/w PAN/poly(vinyl pyrrolidone) (PVP) fibers [11], 95/5
w/w PAN/polystyrene (PS) fibers [12] and 85/15 w/w PAN/
cellulose acetate(CA) fibers [12] have been used to prepare
porous PAN nanofibers upon removal of PVP, PS or CA
domains, respectively, by solvent extraction. The fibers
retained a high density of pores after thermal treatment.
Porous carbon fibers have also been derived by electrospinning
emulsions of poly(methyl methacrylate) (PMMA) in a continu-
ous phase of PAN and DMF, followed by oxidation and carbon-
ization processes to pyrolyze the PMMA component [13].
Rather than using a selective solvent to extract one com-
ponent from a bicomponent electrospun polymer fiber after
the fibers are formed, porous polymer fibers can be produced
from polymer blends or solutions directly during the electros-
pinning process by means of a liquid–liquid phase separation
that occurs when the solution shifts from a stable single
phase to a two-phase region of the phase diagram. Humidity
has been used as a non-solvent to induce phase separation
during electrospinning, with consequent effects on the fiber
surface morphology [14]. Such behavior is typical of polycar-
bonate (PC) [15,16], poly-L-lactic acid (PLLA) [15], PS [17], and
PMMA [18] electrospun from low boiling point solvents. Qi
et al. reported that porous PLLA fibers can be produced from
a mixed solvent of low boiling point dichloromethane (sol-
vent) and high boiling point butanol (nonsolvent) combined
in a 60/40 ratio [19]. Surface pores on electrospun PS, PVC
and PMMA fibers were produced from high boiling point sol-
vent DMF in a high humidity environment [20].
In this work, we demonstrate a general strategy to make
porous fiber electrode materials by electrospinning directly
from a solution composition of Polymer A/Polymer B/Sol-
vent/Non-solvent. Furthermore, if two polymers with differ-
ent thermal stability are chosen, a carbon paper with a
hierarchical pore structure can be created. The largest pores
are formed by the interstices between fibers, while the inter-
mediate sized pores are formed within the fibers themselves
by the phase separation into polymer-rich and solvent-rich
domains that occurs during the electrospinning process. Re-
dox-active species can diffuse easily into the inner pores of
such electrodes. The smallest pores are formed by the ther-
mal decomposition of one of the two polymer components
in the polymer-rich domains during chemical treatment or
carbonization. This paper reports our findings on testing this
concept by electrospinning poly(vinylidene fluoride) (PVDF),
followed by stabilization and carbonization. The morpholo-
gies of the fibers thus obtained are characterized, and the
electrochemical behavior of the ferrocene redox couple is
studied to evaluate the performance of the carbon fiber paper
as an electrode.
2. Experimental
2.1. Preparation of porous PVDF fiber
Solef 1015 poly(vinylidene fluoride) (PVDF) was kindly pro-
vided by Solvay Solexis Inc. Poly(ethylene oxide) (PEO)
(Mv = 2000 kg/mol) and dimethylformamide (DMF) (ACS
reagent, >99.8%) were purchased from Sigma Aldrich, Inc. De-
ionized water was used for solution preparation in all experi-
ments. All materials were used without further purification.
One gram of PVDF and 0.06 g of PEO were dissolved in 9 g
of a mixture of DMF and water (mass ratio 50:3) under gentle
stirring for at least 8 h at 90 C; the solutions were cooled
down to room temperature before electrospinning. The solu-
tion was unstable and formed a gel within 48 h, but could be
electrospun into fibers prior to gelation. The parallel-plate
electrospinning setup described by Shin et al. was used in
the experiments [21]. The flow rate, plate-to-plate distance,
and voltage were 0.05 mL/min, 40 cm, and 22.5 kV, respec-
tively. In each case, randomly oriented nonwoven meshes
were collected on a grounded aluminum foil in a controlled
environment with a temperature of 24 ± 1 C and a relative
humidity of 56 ± 1%. The porous morphology of the as-spun
fibers can be varied by changing the molecular weight and
concentration of PEO relative to PVDF, the amount of water
in the solution and the relative humidity at which the fibers
are formed; details are provided in the Supporting
Information.
2.2. Dehydrofluorination and carbonization
Pretreatment of the PVDF precursor fiber was required to en-
hance thermal stability before the high temperature carbon-
ization. For many carbon fiber precursors such as PAN,
thermal stabilization is carried out at a low temperature in
air. However, thermal stabilization of PVDF occurs mainly at
temperatures above 400 C, which is much higher than its
melting point of around 190 C [22]. For this reason, chemical
dehydrofluorination at lower temperature was used as the
stabilization step, which introduces numerous C–C bonds to
the polymer matrix, as described previously [23]. The electro-
spun PVDF fiber mats were soaked in a mixture of DMF and
methanol with the volume ratio 9:1 at 50 C for several hours,
with different amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU) (Sigma Aldrich, Inc.) added per vinylidene fluoride unit
(DBU/F). After dehydrofluorination, the mats were washed in
methanol for 1 h and dried at room temperature overnight.
The dehydrofluorinated fibers were then heated at a rate of
3 C/min up to 1000 C in nitrogen atmosphere and held for
1 h to complete the carbonization process. During the heat-
treatment, two 5 mm thick molybdenum (Mo) plates were
used to make a Mo-fiber mat-Mo sandwich fixed by Mo wires
 CARBON 4 9 ( 20 1 1 ) 3 3 9 5–34 0 3
in order to keep the mat flat. No additional pressure was ap-
plied to the sample during the heat treatment.
2.3. Characterization
Scanning Electron Microscopy (SEM) (JEOL-6700SEM, JEOL Ltd.,
Japan) was used for morphological characterization of the fibers.
The IMAGEJ image analysis software (National Institutes of
Health) was used to determine the fiber diameter, pore size
and pore number density. Fiber samples were sputter-coated
with a 10 nm layer of gold/palladium using a Desk II cold sput-
ter/etch unit (Denton Vacuum LLC). SEM was used to observe
the surface structure of the fibers at 10 kV acceleration voltage
and 8 mm working distance. The fiber cross sections were pre-
pared by cutting the nonwoven meshes on aluminum foil im-
mersed in a bath of liquid nitrogen. The approximate number
density (i.e. number of pores per unit of surface area) and aver-
age pore diameter on the fiber surface were estimated by inspec-
tion of SEMs of roughly 100 fibers in each sample. Given the
magnification required to image multiple fibers using the
JEOL-6700SEM, the detection limit for pore size was about 20 nm.
Energy Dispersive X-ray Spectroscopy (EDS) was used for
semi-quantitative analysis of the elemental composition of
each mat (typical penetration depth 1–2 lm).
The surface area of the porous fiber mat was measured by
means of the Brunauer Emmett Teller (BET) method
(ASAP2020, Micromeritics) with nitrogen as the adsorbing gas.
XRD diffraction patterns were recorded using a PANalytical
X’Pert Pro Multipurpose Diffractometer with Cu Ka radiation.
The XRD profiles were recorded at a scanning speed of 3/min
between 5 and 70 in 2h.
A Horiba Jobin Yvon Labram HR800 spectrometer was used
for recording the Raman spectra using different excitation
sources (514.532 nm, 633.0 nm, 784.8 nm) at 3 mW of laser
power. For all samples, three spectra were acquired and aver-
aged, using a 100· objective and a grating with 600 grooves/
mm. The spectral resolution was approximately 4 cm 1,
3 cm 1 and 2 cm 1 using 514.532 nm (Argon-ion laser, Coher-
ent-Innova 90C model), 633.0 nm (He–Ne laser, Melles Griot-
LXH2) and 784.8 nm (diode laser, Sacher-TEC 510) excitation
sources, respectively. The acquisition time for each spectrum
was 120 s, 200 s and 300 s when using the 514.534 nm,
633.0 nm and 784.8 nm excitation lines, respectively. Silicon
was used as a calibration standard.
The XPS measurements were recorded with a Kratos Axis
Ultra instrument equipped with a monochromatic Al Ka
source operated at 150 W. The pressure in the analyzer cham-
ber during acquisition of spectra was 7.0 · 10 9 torr. The ana-
lyzer angle was 90 with respect to the specimen surface.
Wide-scan spectra were recorded over a binding energy range
of 0–1100 eV and pass energy of 160 eV.
The electrical conductivity of the ECP was measured by the
impedance method (Solartron 1260 impedance analyzer) with
a 40 mV amplitude signal over the frequency range from
0.1 Hz to 10 MHz at 25 C and 25% RH. The cross-sectional
area, A, of the ECP was calculated by multiplying the mea-
sured width by the measured thickness of the sample. The
electrical conductivity r was calculated using r = l/AR, where
R is the measured electrical resistance and l is the distance
between the electrodes.
3397
2.4. Electrochemical measurements
Cyclic voltammetry measurements were carried out with a
standard three-electrode cell using a VersaSTAT-3 potentio-
stat with V3Studio software (Princeton Applied Research,
Ametek, Inc., Tennessee, USA). Electrochemical measure-
ments were conducted in a glass cell, thermostated at
25 ± 1 C. The working electrode was the PVDF-based ECP.
Copper tape was used to make the electrical contacts between
the ECP and the copper wires. The counter and reference elec-
trodes were platinum and silver wires, respectively. All poten-
tials are referred to the silver wire. The electrodes were rinsed
with acetone before each experiment. DMF containing 0.1 M
tetra-n-butylammonium hexafluorophosphate (TBAPF6) was
used as an electrolyte. 3.8 ml of DMF/TBAPF6 was carefully
deoxygenated with nitrogen with gentle stirring for 30 min.
A nitrogen atmosphere was maintained over the solutions
during the experiments. The behavior of the electrode was
first studied in a blank solution over a selected potential range
and for a scan rate of 0.1 V/s. After that, 100 lL of 250 mmol
ferrocene in DMF was added to the blanketed solution for fur-
ther testing in the selected potential range and for scan rates
ranging from 0.005 to 0.1 V/s. In each case, the last cycle was
recorded, although reproducible signals were obtained after
the first cycle. After each experiment, the reference electrode
was re-calibrated against a ferrocene solution.
3. Results and discussion
3.1. As-spun and dehydrofluorinated PVDF fibers
SEM micrographs showing the typical size and morphology of
the as-spun PVDF fibers are presented in Fig. 1. In combina-
tion with the PEO in solution, a high relative humidity pro-
motes the formation of pores on the PVDF fiber surface,
while water in the solution itself promotes the formation of
connected pores throughout the interior of the fiber; this
behavior is described in more detail in the Supporting Infor-
mation. A similar effect for PEO and non-solvent concentra-
tion on porosity and pore size in thin films has been
reported by Xi et al. [24]. The average diameter of the fibers
was 2.5 ± 1.8 lm, the average pore diameter on the surface
was 350 ± 200 nm and the average number density of pores
on the fiber surface was 9 ± 3 pores/lm2. The BET surface area
for the as-spun PVDF fibers, which includes both superficial
and internal pore surfaces, was 20.6 ± 0.3 m2/g; this is about
15 times the nominal specific surface area that would be esti-
mated from the diameters of the fibers alone.
Upon dehydrofluorination using DBU/F ratios from 0.1 to
10, for periods of either 5 h or 10 h, the color of the PVDF mats
turned progressively from white to dark brown. The mass loss
relative to the mass of the starting PVDF mat (DMchem./MPVDF)
and the elemental composition obtained from EDS were used
to monitor the degree of dehydrofluorination. The results
showed that under mild dehydrofluorination (DBU/F = 0.1
for 5 h) the mass-loss was 1.5% and the C/F mole ratio was
1.1; under dehydrofluorination at DBU/F = 1 for 5 h, the mass
lost was 4.6% and the C/F mole ratio was 1.27; under dehydro-
fluorination at DBU/F = 10 for 5 h, the mass lost was 15% and
3398 CARBON 4 9 ( 2 0 1 1 ) 3 3 9 5 –3 4 0 3
Fig. 1 – SEM images of as-spun porous PVDF fibers (a) at low
magnification; (b) fiber surface at high magnification; (c)
cross-section of one fiber.
the C/F mole ratio was 1.35; under dehydrofluorination at
DBU/F = 10 for 10 h, the mass lost was 20% and the C/F mole
ratio was 1.61. There is a good correlation between DMchem./
MPVDF and the C/F mole ratios (Fig. 2) as the dehydrofluorina-
tion treatment progressed. All the fibers retained their porous
morphology after the dehydrofluorination treatment, as
shown by Fig. 3(a.1), (a.2), (b.1) and (b.2). The average fiber
diameter was substantially unchanged after the dehydrofluo-
rination process (2.3 ± 2 lm).
3.2. PVDF-based carbon fibers
Different fiber morphologies were obtained upon carboniza-
tion, depending on the dehydrofluorination pretreatment, as
illustrated in Fig. 3. PVDF fibers with no pretreatment melted
Fig. 2 – C/F mole ratios and mass loss (DMchem./MPVDF) from
EDS as functions of DBU/F (all data at 5 h, with exception of
highest datum at DBU/F = 10, at 10 h).
upon heating to elevated temperature, and only carbon char
was obtained. Under mild dehydrofluorination at DBU/
F = 0.1 for 5 h, the fiber morphology was partially retained.
Nevertheless, some of the fibers melted during the process,
as is evident in Fig. 3(a.3) and (a.4), and the microporous
structure of the fiber was totally lost. Under dehydrofluorina-
tion at DBU/F = 1 for 5 h, however, the fiber morphology, as re-
flected in the local curvature and roughness of the carbon
fiber surface, was retained, as shown in Fig. 3(b.3). However,
the cross-sectional SEM in Fig. 3(b.4) shows that the interior
porosity of the fibers was lost under these conditions. Under
dehydrofluorination at DBU/F = 10 for 5 h, the porous fiber
morphology was again partially retained, as shown in
Fig. 3(c.3) and (c.4). The pore diameter and the pore density
on the surface of the fibers were 100 ± 30 nm and
4.3 ± 3 pores/lm2, respectively. These pores were much smal-
ler than the pores on the as-spun PVDF fiber, and the pore
number density was low compared to the number density
in the as-spun fibers. Part of the porous surface melted and
finally formed highly rough fibers. Finally, under dehydrofluo-
rination at DBU/F = 10 for 10 h, the porous fiber morphology
was almost completely retained, as shown in Fig. 3(d.3) and
(d.4). The pore diameter and the number density of pores on
the surface of the fiber were 200 ± 60 nm and 8 ± 5 pores/
lm2, respectively.
Elemental composition (by mass) of the electrospun
PVDF-based carbon fibers was obtained by EDS to analyze
the elements present on the fiber surface. The EDS results
show distinct carbon and oxygen peaks, representing the
major constituents of the carbon fibers investigated. The per-
centage of carbon increased with increasing DBU/F, as shown
in Table 1. The EDS results also show that the fluorine content
was substantially eliminated during carbonization.
The crystalline morphologies of the PVDF-based carbon fi-
bers obtained after different dehydrofluorination treatments
were investigated by XRD and compared with those of a com-
mercial carbon paper (Toray, EC TP1 060) (CCP), as shown in
Fig. 4(a). Two broad diffraction peaks are observed, in the
vicinity of 2h = 22–24 and 43. The first peak is assigned to
the (0 0 2) reflection of graphitic carbon [25,26], and is notice-
ably shifted towards lower 2h in the ECPs compared to the
 CARBON 4 9 ( 20 1 1 ) 3 3 9 5–34 0 3 3399

Fig. 3 – SEM images of porous fibers after various dehydrofluorination treatments and carbonization. (a) DBU/F = 0.1 for 5 h; (b)
DBU/F = 1 for 5 h; (c) DBU/F = 10 for 5 h; (d) DBU/F = 10 for 10 h. (x.1) PVDF fibers after the dehydrofluorination treatment; (x.2)
cross-sectional view of PVDF fibers after the dehydrofluorination treatment; (x.3) PVDF-based carbon fibers; (x.4) cross-
sectional view of PVDF-based carbon fibers.

Table 1 – Elemental mass composition of the carbon paper

the 2-dimensional lattice of turbostratic carbon; this peak is
by EDS.
absent in the CCP. Both peaks are quite broad in the ECPs,
DBU/F C (%) O (%) F (%) but apparently shift towards larger 2h with more intensive
0.1 (5 h) 93.24 6.76 0.00 dehydrofluorination treatment. The full width at half maxi-
1 (5 h) 95.61 4.39 0.00 mum also decreases with increasing dehydrofluorination for
10 (5 h) 96.32 3.68 0.00 both peaks. These observations indicate that the ECPs are
10 (10 h) 96.37 3.63 0.00 far more turbostratic in content than the CCP, but that the
structure becomes more compact and regular with more in-
tense dehydrofluorination pretreatment.
CCP, indicative of larger inter-layer spacing. The second peak By comparison, the XRD data for the PVDF fibers before
is significantly asymmetric, typical of the (1 0) reflection in and after dehydrofluorination (but before carbonization) are

Fig. 4 – XRD patterns of the electrospun fibers. (a) (i) Commercial carbon paper (CCP); (ii) PVDF-based ECP (DBU/F = 0.1, 5 h); (iii)
PVDF-based ECP (DBU/F = 1, 5 h); (iv) PVDF-based ECP (DBU/F = 10, 5 h); (v) PVDF-based ECP (DBU/F = 10, 10 h). (b) PVDF fibers
before and after dehydrofluorination. (i) As-spun PVDF; (ii) dehydrofluorinated PVDF (DBU/F = 0.1, 5 h); (iii)
dehydrofluorinated PVDF (DBU/F = 1, 5 h); (iv) dehydrofluorinated PVDF (DBU/F = 10, 10 h).
3400 CARBON 4 9 ( 2 0 1 1 ) 3 3 9 5 –3 4 0 3
shown in Fig. 4(b). The peak observed around 2h = 21 in all of
these samples is typical of the (1 1 0) and (2 0 0) reflections of
the b crystal phase of PVDF. This is as expected, since it is well
known that crystallization from solution as well as the appli-
cation of extensional force such as that present during elec-
trospinning favor the formation of the b-phase [27]. Smaller
peaks at 28 and 40 indicate only a small amount of the a
crystal modification of PVDF. There is no evidence of the crys-
tallographic peaks of PVDF after carbonization (Fig 4(a)).
Raman spectroscopy is widely used as a structural probe of
carbonaceous materials [28–31]. The G band around 1580 cm 1
is characteristic of highly ordered graphite, while the D band
around 1350 cm 1 is indicative of defects and edges in the gra-
phitic domains [32]. In the Raman spectra of carbonaceous
materials, the frequency of the D peak [33] and the ID/IG area
ratio [32] depend strongly on the laser excitation energy. Given
a collection of graphitic domains of various sizes (i.e. with dif-
ferent band gaps), the Raman spectrum is dominated by the
domains whose band gap matches the excitation energy.
Thus, Raman spectroscopy with lower excitation energy is
more sensitive to larger domains, whose band gap is relatively
small, whereas higher excitation energy is more sensitive to
smaller domains. Thus, multiple spectra using different exci-
tation energies can reveal important information about the
population of domain sizes in the mixture [29,30,33].
The results of the Raman analysis are presented in Table 2;
the original Raman spectra can be found in the Supporting
Information. Because the D band shifts as a function of the
excitation line for all the samples, we can conclude that these
materials comprise a collection of graphitic domains of vari-
ous sizes. The increase in the D band frequency for spectra
acquired with 514 nm and 633 nm excitation lines indicates
that, qualitatively, the average dimensions of small and med-
ium size graphitic domains increase as a function of DBU/F.
The average dimension of the large size graphitic domains
appears to be relatively insensitive to, or to slightly decrease
with, DBU/F (i.e., the D band frequency decreases with DBU/
F for spectra acquired with a 785 nm excitation line). For all
excitation lines, the D band full width at half maximum
(FWHM) decreases as a function of DBU/F, indicating that
the domains become more nearly monodisperse as the treat-
ment progresses. Qualitatively, the relative number of defects
in the graphitic domains can be estimated by the ID/IG ratio.
The number of defects in the smaller and larger graphitic do-
mains is reduced with the stronger dehydrofluorination treat-
ment (ID/IG decreases with increasing DBU/F), whereas the
medium domains are relatively unchanged [32].
Table 2 – D band frequency (mD), D band full width at half maximum (DFWHM) and ID/IG ratio as a function dehydrofluorination
treatment and exciting lines.
514 nm 2.41 eV (small domains) 633 nm 1.96 eV (medium domains)
1 FWHM 1 1
DBU/F mD (cm ) D (cm ) ID/IG mD (cm )
0.1 (5 h) 1349.0 214.3 4.69 1322.5
1 (5 h) 1353.4 188.2 4.53 1327.6
10 (5 h) 1353.7 175.7 4.51 1328.1
10(10 h) 1357.0 158.9 3.48 1330.0
3.3. Electrochemical electrode performance
The PVDF-based ECP produced under the 10 h dehydrofluori-
nation treatment with DBU/F = 10 was characterized electro-
chemically by cyclic voltammetry to test its performance as
an electrode in driving a redox reaction. The surface area of
this material was 382.3 ± 7.7 m2/g based on the BET result,
and the carbonized fiber diameter was 1.6 ± 1.2 lm. If no
new pores were formed and the pore shrinkage in the carbon-
ization process was commensurate with the reduction in fiber
diameter, the calculated surface area of the electrospun car-
bon paper should be less than 100 m2/g, as the BET surface
area for as-spun PVDF fibers was 20.6 ± 0.3 m2/g with an aver-
age fiber diameter of 2.5 ± 1.8 lm. We attribute the unexpect-
edly large BET surface area measured for these carbon fibers
to either, or both, the decomposition of PEO in the fibers dur-
ing the carbonization, which may generate additional fine
pores, or the dehydrofluorination treatment. It has been re-
ported that 1–2 nm diameter nanopores are produced in PVDF
fibers when the weight loss by dehydrofluorination is about
18% under appropriate treatment conditions [22]. In our case,
the weight loss was about 18–20%, and thus is consistent with
these observations. The electrical conductivity of the PVDF-
based ECP was 11.4 ± 1.5 S/cm, while the electrical conductiv-
ity of the Toray CCP was 80 ± 0.3 S/cm. The wettability of the
electrode in DMF was assessed by placing drops of DMF on
the surfaces of both ECP and CCP. The DMF with TBAPF6 elec-
trolyte spread very quickly, resulting in contact angles of 0
for both cases, indicating very good wettability of the ECP
and CCP in DMF/TBAPF6.
Cyclic voltammetry (CV) is the experimental technique
most commonly used in the electrochemical characterization
of redox-active compounds and electrodes. While most redox
reactions are very sensitive to the surface chemistry, this is
not the case for the relatively insensitive ferrocene/ferroce-
nium redox reaction used here. Nevertheless, the surface
chemistry for this electrode is reported in the Supporting
Information for future reference with other redox reactions.
Fig. 5(a) shows the potential windows for the CCP and ECP
electrodes tested in DMF/TBAPF6 under a typical scan rate
of 0.1 V/s. In this study, the working potential window is de-
fined as the difference between the potentials at which the
anodic and cathodic current densities reach 1 mA/g. The
ECP electrode has a larger background current, around 0.4 A/
g, which is attributed to the double layer capacitance associ-
ated with the larger effective surface area, and a wide poten-
tial window ranging from 2.7 V to 1.9 V. The CCP electrode
785 nm 1.58 eV (large domains)
FWHM 1
D (cm ) ID/IG mD (cm 1) DFWHM (cm 1) ID/IG
271.0 9.48 1310.4 225.10 19.20
225.5 8.29 1309.8 231.47 17.12
207.0 10.25 1307.8 208.83 14.06
205.2 9.34 1307.7 193.50 13.00
 CARBON 4 9 ( 20 1 1 ) 3 3 9 5–34 0 3 3401

Fig. 5 – (a) Cyclic voltamograms (CV) obtained for CCP and ECP electrodes in DMF (scan rate: 0.1 V/ s); (b) CVs of CCP and ECP
electrodes in 100 lL of 250 mmol ferrocene in DMF containing 0.1 M TBAPF6 3.8 ml at a scan rate of 0.1 V/s; (c) CVs of ECP
electrode at different scan rates in 100 lL of 250 mmol ferrocene in DMF containing 0.1 M TBAPF6 3.8 ml (scan rates increase
from innermost curve to outermost curve) at a scan rate of 0.1 V/s; (d) linear relationship of the peak potential separation to
the square root of scan rate; (e) working curve showing variation of peak potential separation with w [31]; (f) linear
relationship of peak current to the square root of scan rate.

has a much smaller background current, less than 0.01 A/g,
and a narrow potential window ranging from 1.7 V to 1.5 V.
The ECP electrode thus has the capability to serve as an elec-
trode for redox reactions in the range of 1.7 V to 2.7 V that
cannot be accommodated by the CCP.
To further understand the performances of the electrodes,
cyclic voltamograms obtained with ECP and CCP at a series of
scan rates ranging from 0.005 to 0.1 V/s were measured, as
shown in Fig. 5(b) and (c). Ferrocene was used here to demon-
strate the working properties of the electrode, as ferrocene is
easily oxidized to the ferrocenium cation, producing a single
electron; both ferrocene and ferrocenium are chemically in-
ert. The cyclic voltamograms obtained were normalized by
the weight of the electrode. If the redox process is reversible,
the peak potential separation DEp (=Epc Epa) should be 59 mV
at 25 oC for single electron transfer redox systems. Fig. 5(d)
shows that DEp increases progressively with increasing scan
rate, and lies in the range from 146 mV to 383 mV for the
ECP and from 77 mV to 187 mV for the CCP. DEp is linearly pro-
portional to the square root of the scan rate. This is attributed
to ‘‘slow’’ electrode kinetics, in which electrochemical
‘‘Nernst’’ equilibrium could not be attained on the electrode
surface at these scan rates. The processes for both the ECP
and the CCP are quasi-reversible.
3402 CARBON 4 9 ( 2 0 1 1 ) 3 3 9 5 –3 4 0 3
Based on the Nicholson model, the standard rate constant
at the standard potential, ks, is used to characterize the pro-
pensity for electron transfer [34]. According to the Nicholson
model, w = caks(paD0) 1/2, where w is a dimensionless charge
transfer parameter, a = nFv/RT, a = 0.5, c = (D0/DR)1/2 and D0
and DR are the diffusion coefficients of the oxidized and re-
duced species, D0 = DR = 1.1 · 10 5 cm2/s in this case [35]. v is
the scan rate, n is the stoichiometric number of electrons con-
sumed in the electrode reaction (one, in this case), and F is the
Faraday constant. Fig. 5(e) shows the dependence of the peak
potential separation on w, based on the data reported in Ta-
ble 1 of Nicholson [34]. The value of w can be inferred from
the observed peak potential separation in Fig. 5(d). In this
way, we obtain a value of ks = 0.84 · 10 3 cm/s for the ECP
electrode, and ks = 5.5 · 10 3 cm/s for the CCP electrode, at a
scan rate of v = 0.01 V/s. According to Ferro and Battisti, ks
for the Pt electrode is on the order of magnitude of 10 3 cm/
s, while ks for the diamond electrode is on the order of mag-
nitude of 10 5 cm/s [36]. The ks results for the ECP and CCP
electrodes are thus intermediate between those for the metal
and sp3 electrodes.
The peak current, ip, depends on analyte concentration
and the stability of the electro-generated species. The anodic
current and the cathodic peak current ratios were unity for all
scan rates. As shown in Fig. 5(f), the average current was pro-
portional to the square root of the scan rate, v. The larger val-
ues of ip/v1/2 correspond to larger production rates of the
oxidized or reduced species. The current per unit mass of
the ECP electrode was approximately four times larger than
that of the CCP electrode.
4. Conclusions
Phase separation and electrospinning were employed to pro-
duce porous PVDF-based carbon fibers using PEO as an addi-
tive and water as non-solvent. The morphology of the
carbon fibers was varied by changing DBU/F. After dehydroflu-
orination with DBU/F = 10 for 10 h and subsequent carboniza-
tion, the fibers were smaller in diameter and retained pores
with diameter of 200 ± 60 nm and surface pore density of
8 ± 5 pores/lm2. XRD and Raman data show that the PVDF-
based carbon fibers, derived at 1000 C, were turbostratic
and disordered in nature; this structure, combined with the
high surface area of the fibers, could be beneficial for subse-
quent functionalization in some applications, such as catalyst
supports, sensors, or redox flow battery electrodes. The elec-
trochemical test indicates that a porous PVDF-based ECP with
high specific surface area performs well in driving redox reac-
tions. Further efforts to graphitize these porous PVDF-based
ECPs are expected to improve the performance of these mate-
rials as electrodes.
Acknowledgment
This work was supported by the MIT-Dupont Alliance. We
would like to acknowledge Prof. Michael Strano of MIT for
use of the furnace, and Dr. Richa Sharma and Dr. Jae-Hee
Han of MIT, for helpful discussions on the carbonization pro-
cess. This work made use of the Shared Experimental Facili-
ties supported by the MRSEC Program of the National
Science Foundation under award number DMR-0819762. Sup-
porting Information is available online from Wiley Inter-
Science or from the author.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.carbon.2011.04.015.
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