Carbon Nanofibers Prepared Via Electrospinning

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Carbon Nanofibers Prepared via Electrospinning

Michio Inagaki,* Ying Yang, and Feiyu Kang
diameters of carbon fibers. CNTs are considered to be an important material for
the development of modern nanotechnology in the 21st century, because carbon
fibers have supported the development of
modern technology since the 1960s.
Electrospinning has been used to produce nanofibers of various polymers with
diameters from a few tens of nanometers
to a few micrometers in different forms
such as nonwoven mats (webs), yarns, etc. It is a relatively
simple and low-cost strategy to produce continuous nanofibers
from polymer solutions or melts. Over the past decade, electrospun nanometer- to sub-micrometer-sized polymer nanofibers
have attracted much attention in both research and commerce.
A few companies started to develop electrospun nanofiber products on the basis of large-scale electrospinning setups. This
technique was reviewed from different viewpoints, focusing on
polymer nanofibers.[817]
In this review, we focuse on carbon nanofibers prepared via
electrospinning and carbonization by summarizing on their
structure and properties in relation to their applications, after
a brief explanation on the setup and conditions for electrospinning, and some polymer nanofibers. Carbon precursors, control
in pore structure, improvement in electrical conductivity, metal
loading of carbon nanofibers are discussed from the viewpoint
of control of structure and texture in the resultant carbon
nanofibers. Although one of the applications of electrospun
carbon nanofibers is the support for catalysts and electrochemically active materials, loading and deposition of these materials
on carbon nanofibers are not included here.
Carbon nanofibers prepared via electrospinning and following carbonization are summarized by focusing on the structure and properties in relation
to their applications, after a brief review of electrospinning of some polymers. Carbon precursors, pore structure control, improvement in electrical
conductivity,and metal loading into carbon nanofibers via electrospinning are
discussed from the viewpoint of structure and texture control of carbon.
1. Introduction
Fibrous carbon materials have attracted the attention of scientists and engineers.[1,2] In the 1960s carbon fibers were developed
as one of the important industrial materials for modern science
and technology, and which have been produced from various
carbon precursors via the melt-spinning process. Polyacrylonitrile (PAN) has been used as the principal precursor associated
with different modifications in processing, such as the use of
additives, oxidative stabilization of as-spun PAN fibers at a low
temperature, and stretching during stabilization and carbonization. Isotropic and anisotropic mesophase pitches and phenolic
resins have also been precursors for carbon fibers. A catalytic
chemical vapor deposition (CVD) process has also produced
carbon fibers with a structure and properties that are different
from those produced via melt-spinning, which is called vaporgrown carbon fiber (VGCF). In the center of VGCFs, thin tubes
consisting of straight carbon layers were found,[3] which were
later reported to be formed via arc-discharging[4] and named
carbon nanotubes (CNTs).[5,6] The process used for the production of VGCFs was successfully applied to synthesize CNTs.[7]
The diameters of CNTs are in the nanometer range, e.g., 7
nm for single-wall CNTs, in contrast to the micrometer-range
2. Electrospinning of Polymers
Prof. M. Inagaki
Professor Emeritus of Hokkaido University
Sapporo 060-8628, Japan
E-mail: im-ii@xj.commufa.jp
Prof. Y. Yang
Department of Electrical Engineering
Tsinghua University
Beijing 100084
China, State Key Laboratory of Control and Simulation
of Power System and Generation Equipments
Tsinghua University
Beijing 100084, China
Prof. F. Kang
Department of Materials Science and Engineering
Tsinghua University
Beijing 100084, China
DOI: 10.1002/adma.201104940
Adv. Mater. 2012, 24, 25472566
2.1. Setup and Conditions for Electrospinning

A fundamental setup for electrospinning of polymers is schematically shown in Figure 1. A viscoelastic solution of polymers
is charged by a DC or AC high voltage due to potential difference between the syringe and grounded target. The repulsion
among the charges on the surface of the drop at the tip of the
syringe (spinneret) competes with the surface tension, which
tends to stabilize the drop. Once a critical condition is reached
at which surface charge repulsion dominates, a jet is drawn
from the spinneret under a constant flow rate. The accelerating
jet decreases in diameter with increasing external applied field
and the surface charge repulsion continually draw on it, until
a point is reached where the axis of the jet bends, and the jet
begins whipping. As the solvent evaporates, the jet solidifies to
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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REVIEW
Michio Inagaki is the professor emeritus of Hokkaido

University and Toyohashi
University of Technology.
He received his PhD from
the Nagoya University,
Japan, in 1963. He worked
in different universities,
Nagoya University, Toyohashi
University of Technology,
Hokkaido University, and
Aichi Institute of Technology.
His research activities are in the fields of science and engineering on carbon materials, and are highlighted by The
SGL Carbon Award from American Carbon Society in 2004.
Ying Yang is the professor

of Tsinghua University.
She received her PhD from
Tsinghua University, Beijing,
China in 2007. She was a
post doctoral associate in
Department of Chemical
Engineering at Massachusetts
Institute of Technology from
2008 to 2009.
Figure 1. Scheme of fundamental setup for electrospinning.
form thin fibers, which are deposited on the grounded target (or
collector). The diameters of polymer fibers are around nanometers (nanofibers), from few tens nanometers to micrometers
an example of polymer nanofibers, although it is still difficult to
electrospin polymer into uniform nanofibers with diameter as
small as several nanometers up to now.
More than 100 kinds of polymers have been used to produce
their nanofibers via electrospinning in the past 20 years. Electrospinning process of various polymers was discussed on the
condition to control fiber diameter in nanometer scale.[8,11,1315]
The electrospun polymer fibers are usually smooth solid fibers.
By using a spinneret consisting of two coaxial capillaries and
different polymer solution in each capillary, nanofibers were
successfully prepared with core-shell structure[1820] or with
hollow structure.[21] The use of volatile solvent resulted in
porous nanofibers.[2224] The mechanical and thermodynamic
properties of electrospun polymer nanofibers were discussed
from the electrospinning conditions.[17]
The electrospun polymer fibers can be collected in the form
of a random nonwoven mat (web) by using flat metallic plate or
mesh as a collector. By using a round collector rotating in a constant speed the continuous fibers can be collected in an aligned
form. By using a spinneret with single nozzle and immiscible
two polymer solutions, side-by-side bicomponent nanofibers
were prepared.[25] The use of multi-needle spinneret can
enhance the production rate of polymer nanofibers.[26] Recent
developments in designs for the collection of spun nanofibers,
in particular, the mass production of nanofibers and the fabrication of various forms, from nonwoven form to yarn, 3D assemblies and patterned structures, were reviewed.[15]
The spinnability of a polymer solution and the morphology
of resulting fibers are known to depend strongly on three factors; properties of polymer solution, processing condition and
2548
Feiyu Kang was born in 1962,

received doctoral degree
from Hong Kong University
of Science and Technology.
He now is a full professor
in Department of Materials
Science and Engineering,
and also a dean in Graduate
School at Shenzhen, Tsinghua
University. His research is
focusing on nanocarbon
materials, graphite, thermal
conductive materials, lithium ion battery, super-capacitors,
electric vehicles, porous carbon and adsorption, indoor air
clearing and water purification.
atmosphere condition. The first factor, solution properties,

includes surface tension, electrical conductivity, dielectric constant, viscosity of the polymer solution, depending strongly on
the polymer (its concentration, molecular weight and architecture), solvent (vapor pressure, diffusivity in air, etc) and additives (surfactants, salts, etc). In electrospinning of poly(ethylene
oxide) PEO, a marked solvent effect was reported; a mixed solvent of ethanol with deionized water in either 1/1 or 3/1 volume
Adv. Mater. 2012, 24, 25472566
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REVIEW
ratio had to be used.[27] The second factor, processing condition,

includes flow rate of the polymer solution controlled by syringe
pump, strength of electric field controlled by power supply,
and distance between the spinneret tip and the collector. The
last factor, atmosphere condition, includes the gas used (such
as air, N2, Ar, vacuum) and its flow rate, and humidity in the
electrospinning hood. Humidity in spinning atmosphere was
reported to affect the morphology and porosity of electrospun
fibers of various polymers, polystyrene PS, poly(vinyl chloride)
PVC and poly(methyl methacrylate) PMMA, poly(vinyl chloride)
PVC.[2830] However, most of the works on electrospinning of
polymer nanofibers focused on the control of the first two factors and ignored the atmosphere effect. Concentration and flow
rate of a combination of precursor polymer and solvent, additives in the solution, power voltage applied for spinning, and
distance between the spinneret tip and the collector are usually
reported as parameters to be controlled. Although a wide variety
of polymers have been studied for electrospinning, there are no
universal ranges for these parameters to synthesize homogeneous thin fibers found until now.
2.2. Polymer Nanofibers
The polymer nanofibers which have been converted to carbon
nanofibers are rather limited, as polyacrylonitrile (PAN), polyimide (PI), poly(vinyl alcohol) (PVA), poly(vinyliden fluoride)
(PVDF) and pitch, although so many kinds of polymers have
been electrospun.
PAN has been commonly electrospun into high-quality
fibers with various diameters[31] and also converted to carbon
nanofibers, as explained in the following sections. Morphology
(i.e., diameter and uniformity) of the electrospun fibers is sensitive to three factors mentioned, but the solution properties are
found to be dominant.[3236] Generally, the diameter of the electrospun fibers decreases dramatically with decreasing polymer
concentration and with increasing electrical conductivity of
solution. Up to now, it is still difficult to electrospin PAN polymer into uniform nanofibers with diameter as small as several nanometers.[37] A special alignment can be also achieved
by manipulating the distribution of electric field.[38] Moreover,
the carbon nanotubes are embedded into the electrospun PAN
fibers in order to improve the mechanical properties, thermal
stability and electrical conductivity, since the pure fibers are not
as strong as desired.[3942]
On a N,N-dimethylformamide (DMF) solution of PAN,
effects of the concentration of the polymer solution and the
applied DC voltage between the electrode immersed into the
solution and the target on the diameter of PAN nanofibers
are studied.[33] Solution concentration governs the diameter of
resultant fibers, as shown in Figure 2a). Effect of PAN concentration in DMF solution on diameter of electrospun nanofibers
was also reported to depend on molecular weight of PAN[43]
and entanglement density of the polymeric solution.[44] Applied
voltage did not appreciably affect on the fiber diameter,[33] as
shown in Figure 2b).
Recently, PI fibers are prepared by many researchers
through electrospinning.[4554] Generally, three-step method is
adopted, which include polymerization of polyamic acid (PAA),
Adv. Mater. 2012, 24, 25472566
Figure 2. Dependences of diameter of polyacrylonitrile fiber on concentration of the precursor solution and applied voltage for spinning.[33]
Reprinted with permission from Elsevier.
electrospinning of PAA solution and then imidization of the

electrospun PAA fibers. Concentration or viscosity of the PAA
solution was found to be one of the most effective variables on
the control of morphology of electrospun PI fibers.[45] Diameter
of the PI fibers synthesized ranges from several tens nanometer to several hundreds nanometer. The applied voltage and
the feeding rate of the precursor solution may have an influence on the diameter, even though the effect is not drastic. By
adding salts to PAA solution and controlling humidity conditions ultrafine uniform nanofibers were prepared with a narrow
range of nanoscale diameters (33 5 nm).[46]
PVDF is a thermoplastic polymer which can be easily processed into various forms. PVDF was electrospun from its
solution of a mixed solvent of acetone and DMAc under several concentrations from 12 to 18 wt%.[55] Webs of electrospun
PVDF fibers were prepared from its mixed solutions of DMF
and acetone,[56] fiber diameter ranging from 50 to 300 nm from
a 15% PVDF solution of 8/2 DMF/acetone. Its porous fibers
were prepared via electrospinning accompanied by phase separation during electrospinning process, which was induced by
poly(ethylene oxide) and water mixed into PVDF solution.[57]
Poly(vinyl alcohol) (PVA) is a water-soluble polyhydroxy
polymer and has been used as a carbon precursor in fundamental researches, even though it is easily decomposed at a
high temperature and gives a low carbon yield. PVA nanofibers
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with various diameters (50250 nm) were easily electrospun

from its 715 wt% aqueous solution.[58,59] From a 12 wt% PVA
aqueous solution containing 1.0 wt% MWCNT, the composite
nanofibers were prepared by electrospinning.[60] Effect of pH of
PVA aqueous solution was discussed on the morphology and
diameter of its fibers electrospun from a 7 wt% solution.[61] The
average diameter of PVA nanofibers electrospun at pH 7.2 was
290 nm and it became thinner with increasing pH under basic
conditions. Under acidic conditions, however, the electrospinning of PVA solution was not continuous and PVA with beadson-string structures was obtained due to the protonation of
PVA.
In contrast to PVA, pitch has several advantages as the precursor for carbon nanofibers; high carbon yield and low cost.
For pitches, however, a proper solvent, which dissolves the
pitch to high enough concentration and has a proper vaporization point, has to be selected for its electrospinning. The
DMF-insoluble fraction of a petroleum-derived isotropic pitch
in THF solution and a binary solvent of DMF and THF were
used for the spinning of pitch to convert to carbon nanofibers,
as explained in the next section. Molecular structure of the precursors was shown to have an effect on spinnability of their
THF solution by using two pitches with different weight-averaged molecular weights of 2380 and 556.[62] THF-soluble component of the pitch with the lower molecular weight gave better
spinnability on its 40 wt% THF solution, but the pitch with the
higher molecular weight resulted in more microscopic carbon
nanofibers
3. Carbon Nanofibers Synthesized Via

Electrospinning
In Table 1, the papers reporting on the preparation of carbon
nanofibers via electrospinning process are listed in the order
of published year by summarizing key points on precursor
solution, spinning condition, treatments to convert to carbon
nanofibers and their characteristics.[63141] In Table 1, the main
purpose of the papers is also indicated together with the reference number. As carbon precursors, PAN and pitches were
frequently used, probably because both of them are also used
in the production of commercial carbon fibers. In addition,
poly(vinyl alcohol) (PVA), polyimides (PIs), polybenzimidazol
(PBI) poly(vinylidene fluoride) (PVDF), phenolic resin and
lignin were used.
In order to convert electrospun polymer nanofibers to carbon
nanofibers, carbonization process at around 1000 C has to be
applied. In principle, any polymer with a carbon backbone can
potentially be used as a precursor. For the carbon precursors,
such as PAN and pitches, so-called stabilization process before
carbonization is essential to keep fibrous morphology, of which
the fundamental reaction is oxidation to change resultant carbons difficult to be graphitized at high temperatures as 2500 C.
During stabilization and carbonization of polymer nanofibers,
they showed significant weight loss and shrinkage, resulting in
the decrease of fiber diameter.
Here, the results obtained in these papers are reviewed
by dividing into the sections based on the purposes of the
research works; fundamental structure and properties of the
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carbon nanofibers, their performance in energy storage devices,

lithium-ion rechargeable batteries and electrochemical capacitors, and composite nanofibers with carbon nanotubes.
3.1. Structure and Properties
PAN nanofibers were prepared by electrospinning from DMF
solution, on which structure and electromagnetic properties
were studied.[6365] Structural analysis was performed on carbon
nanofibers, which were prepared from PAN/DMF solution by
carbonization at 750 C followed by 1100 C.[77] The resultant
carbon nanofibers had average diameter of 110 nm, interlayer
spacing d002 of 0.368 nm and Raman band intensity ratio ID/IG
of 0.93. From SEM and TEM observations, the fiber was concluded to have skin-core heterogeneity; in the skin carbon layers
being oriented predominantly parallel to the fiber surface. PANbased carbon nanofiber bundles, which were prepared from 10
wt% PAN/DMF solution added 5 wt% acetone and 0.01 wt%
dodecylethyldimethylammonium bromide, and collected on the
rim of the rotating disc covered with Al foil, were subjected to
the heat treatment at 1400, 1800, and 2200 C for 1 h.[107] The
diameter of nanofibers composing the bundles was approximately 330 nm for as-spun, 250 nm for 1000 C-treated and
220 nm for 1800 C-treated. TEM images are shown in Figure 3
on 1000 C-treated and 2200 C-treated nanofibers, the latter
having d002 of 0.344 nm and ID/IG of larger than 1.0. Aiming
to have better alignment of basic structural units of hexagonal
carbon layers along the fiber axis, multi-walled carbon nanotubes (MWCNTs) were embedded into electrospun PAN-based
carbon nanofibers, although the improvement was observed just
around MWCNTs.[97] TEM observation on MWCNTs-embedded
PAN-based nanofibers by in-situ heating up to 750 C showed
only a local orientation of carbon layers.[142] On PAN-based
nanofibers web after the activation by steam at 800 C, adsorption behavior of benzene vapor was studied at a temperature of
343423 K under a pressure up to 4.0 kPa, confirming a high
adsorption in comparison with activated carbon fiber A-10.[82] By
focusing on PAN, electrospinnability, environmentally benign
nature and commercial viability were recently reviewed.[143]
Core-shell polymeric nanofibers were electrospun through
a doubled capillary, PAN/DMF solution in the outer capillary
and poly(methyl methacrylate) PMMA in the inner capillary,
and converted to hollow carbon nanofibers by carbonization
up to 1100 C.[81] Similar hollow nanofibers were synthesized
by electrospinning of emulsion-like DMF solution of PAN
and PMMA in different ratios through a single capillary of
0.5 mm diameter, followed by carbonization at 1000 C and heat
treatment up to 2800 C,[84] as shown in Figure 4. By changing
PAN/PMMA ratio, mesopore volume could be controlled; mesopore volume Vmeso changed from 0.18 cm3 g1 for 9/1 ratio to
0.47 cm3 g1 for 5/5 ratio, although micropore volume Vmicro
was almost constant of 0.34 cm3 g1.[84]
Mixing of poly(vinylpyrrolidone) (PVP) into PAN was also
employed to control pore structure in the nanofibers.[103] PVP
was dissolved out from as-spun fibers at 100 C under hydrothermal condition and the resultant PAN nanofibers were carbonized at 1000 C after stabilization. The change of PAN/PVP
ratio in the precursor solution from 0.8/0.2 to 0.8/1.0 resulted
Adv. Mater. 2012, 24, 25472566
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Ref. (Purposea))
[6365]
(Structure)
Precursor and additives/

solvent
Spinning conditionsb)
Stabilization, carbonization and activation
Carbon nanofibers synthesized and

functionalities
PAN/DMF
15 kV//15 cm/
no stabilization, carbonized at 600, 800,

1000, 1200 C for 1/2h in vacuum
92.5 164 nm2, = 490 S m1, magnetoresistance (1000 C) of -0.75 at 1.9 K and 9T
[66]
(Composite)
[PAN + SWCNT]/DMF
25 kV//15 cm/0.9 mm
stabilized at 200 C, carbonized at 1100 oC
homogeneous and straight SWCNTs in PAN,

stiffening of PAN
[67]
(EDLCs)
10 wt%PAN/DMF
1025 kv///
stabilized at 280 C, carbonized & activated

at 700-800 C in N2 + steam
200400 nm dia., SBET 1230 m2 g1, Vtotal 0.55cc g1,

173 F g1 at 10 mA g1 in 30vol% KOH
[68]
(Properties)
12 wt%PI/(THF + MeOH)
1315 kV/20 g h1/67

cm/0.41 mm/
imidization at 150250 C, carbonized at

7001000 and 2200 oC
electrical conductivity: from 2.5 and

5.3 S cm1, tensile strength: from 5.0
and 73.9 MPa by 1000 and 2200 oC
[69]
(Properties)
Pitch/THF
carbonization & activation
SBET 20602220 m2 g1, microporous
[70,71]
(EDLCs)
PBI/DMAc
1025 kV///
700850 C for 1/2h in N2+30vol% steam
100-500nm dia., 800 C-treated SBET 1220 m2

g1, Vmicro 0.71mL g1, 175F g1 in 30wt%KOH
[72]
(Properties)
DMF-insoluble pitch/THF
18 kV/3mL h1/10 cm/

0.88 mm
stabilized at 300 C, carbonized at 700,

1000, 1200 C for 1h
dumb-bell like cross-section with (46)

(23)m, electrical conductivity 83S/cm
[73]
(Composite)
[6.7 wt%PAN + 3.3 wt%

Fe-acac]/DMF
30 kV//30 cm/
stabilized at 250 C, Fe reduction at 500

550 C in H2, carbonized at 1100 oC
MWCNTs grown by CVD of hexane at 700 C

on nanofibers
[74]
(EDLCs)
10 wt%PAN/DMF
20 kV////300 rpm

at 800 C for 1/41h in N2 + steam
200350 nm dia., SBET = 1160 m2 g1, Vtotal =

0.64 cc g1, 134 F g1 in 6N KOH with
1 mA cm2
[75]
(EDLCs)
PI/(THF + MeOH)
1315 kV///
imidized at 350 C, carbonized at 1000 C and SBET = 9411450 m2/g, Vmicro = 0.370.56cc g1
activated at 650800 C in N2 + steam
750 C-activated: 175F g1 in 30wt% KOH
[76]
(Composite)
[7 wt%PAN + 235 wt%

MWCNT]/DMF
30 kV//30 cm//10 m/s stabilized at 220 C for 2h in air, carbonized

at 850 C for 1/2h in Ar
[77]
(Properties)
8 wt%PAN/DMF
0.9 kV/cm///0.1 mm/

5 m s1
stabilized at 250 C, carbonized at

1100 C 1h
110 nm dia., 89.4%C, d002 = 0.368 nm, ID/IG =

0.9, weaker than commercially available fibers
[78]
(EDLCs)
20 wt%PBI/DMAc
///0.5 mm/300 rpm
carbonized & activated at 700, 750, 800,

850 C in N2 + 30% steam for 1/2h
800 C-treated: SBET = 1220m2 g1, Vmicro =

0.71 cc g1, 202F g1 in 1M H2SO4 with
1 mA cm2, good rate performance
[79]
(Properties)
[20 wt%PI + Fe-acac

(03.0 wt%)]/DMAc
615 kV/2050 m
min1///
carbonized at 4001200 C for 1h
-Fe and Fe3O4 are formed above 800 C, d002

= 0.34 nm, ID/IG = 1.8 by 3wt% atfter 1200 oC
[80]
(LIBs)
PAN/DMF
25 kV//300 rpm//
0.5 mm
stabilize at 280 C for 1h, carbonized at

7002800 C
1000 C-treated Cdis = 450 mAh g1 but Cirr =

ca. 500 mAh g1 in 1M LiClO4 EC/DEC with
30 mA g1
[81]
(Structure)
PAN/DMF(shell) and
PMMA/Acetone(core)
0.3 kV cm1//18 cm/

0.31.65 mm
stabilized at 250 C carbonized at 1100 C

for 1h
hollow carbon nanofibers
[82]
(Properties)
10 wt% PAN/DMF
20 kV//18 cm//
stabilized at 280 oC, carbonized at 80 C,

activated at 800 C in 30% steam for 1h
SBET = 1193m2 g1, Vmicro = 0.455 cc g1 high

adsorptivity for benzene vapor
[83]
(EDLCs)
[PAN + Ru-acac]/DMF
20 kV//18 cm/
0.5 mm/300 rpm

at 800 C in N2 + 30 vol% steam
200-900nm dia., Ru metal (215 nm)embedded, 7.31wt% Ru: 391F g1 (261F g1

pseudocapactitance)
[84]
(Properties)
[PAN + PMMA(5/5, 7/3,

9/1)]/DMF
20 kV///0.5 mm/
300 rpm
stabilized at 280 C for 1h, carbonized at

1000 & 2800 oC
PAN/PMMA = 5/5 and 1000 C-carbonized:

SBET = 940 m2 g1, Vmeso = 0.47 & Vmicro =
0.35 cc g1
[85]
(EDLCs)
[10wt%PAN + 155 wt%

ZnCl2]/DMF
25 kV////300 rpm
stabilized at 280 C, carbonized at 800 C

for 1h in Ar, repeatedly wash by HCl
SBET = 310550 m2 g1, Vtotal = 0.170.34cc g1,

140 F g1 in 6M KOH
[86]
(Properties)
[PI + 1, 3, 5wt%TEA]/DMF
1923 kV//15 cm/
stabilized by oxidation, carbonized

at 1000 C for 1 h in Ar
80 nm dia. from 18wt%PAA solution, conductivity of the mat under 22,000Pa pressure was
16S/cm
[87]
(Properties)
[9.1wt%PAN + SiO2]/
18 kV/1.0 mL h1//1.27
mm/300 rpm

1050 C for 1h in N2, washed out Si by HF
fiber diameter increases, bead, bead-on-string

and fiber structures, SBET = 340 m2 g1, Vtotal =
0.472 cc g1
[88]
(Properties)
[PAN + PI (10/0, 7/3, 5/5,

3/7, 0/10)]/DMF
20 kV////ca. 300 rpm
stabilized at 280 C for 1 h, carbonized at

1000 C in Ar
carbon yield increases, decreases and ID/IG

increases with increasing PI content
Adv. Mater. 2012, 24, 25472566
REVIEW
Table 1. Preparation of carbon nanofibers via electrospinning.
100300nm dia., 5% MWCNT composite

shows max. strength 80MPa
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2552
Table 1. Continued.
Ref. (Purposea))

solvent

functionalities
[89]
(Properties)
[Ph + PVB]/MeOH
15 kV/0.010.20 mL
min1/10-20cm/1.0 mm
cured by adding formaldehyde, carbonized at flexible carbon nanofiber fabric by adding PVB,
900 C for 2 h in N2
SBET = 495 m2 g1
[90]
(LIBs)
[PAN + Co(OAc)2]/DMF
1011 kV/2.5 L m1/

12 cm/0.6 mm

600 C for 10h
[91]
(LIBs)
[PAN + Fe-acac]/DMF
1214 kV/4L min1/

12 cm/
stabilize at 240 C, carbonized at 500700 C Fe3O4-included, interesting cycle performance

for 10h
[92]
(Properties)
[8 wt%PAN + 4.8 wt%

Pd(OAc)2]/DMF
30 kV//30 cm/
stabilized at 230 C for 3 h, reduced Pd2+ at

300 C, carbonized at 1100 C in Ar
200500 nm dia., Pd (37nm size) dispersed,

high sensitivity for H2O2 and NADH
[93]
(Fuel cells)
PAN/DMF
13.7 kV//12 cm/
stabilized at 280 C in air, carbonized at

1200 C for 1h in Ar
150 nm dia., = 50S/cm, electrochemical

deposition of Pt(50-200 nm), high electrocatalytic activity and stability
[94]
(EDLCs)
[10 wt%PAN+
3 wt%MWCNT]/DMF
20 kV/1 mL h1/ 15 cm/

0.5 mm/300 rpm
stabilized at 280 C, carbonized and

activated at 800 C, coated by polypyrole
PAN-based: SBET = 742m2 g1, 141 F g1, PAN/

CNT: SBET = 1170m2 g1, 180 F g1, PPy/PAN/
CNT: 333 F g1
[95]
(EDLCs)
[10 wt%PAN + 10 wt%

V2O5]/DMF
20 kV/1 mL h1/
stabilized at 250 C for 8h, carbonized and
130 rpm/17 cm/1.27 mm activated with KOH at 800 C in Ar
V(5wt%)-embedded, SBET = 2800 m2 g1,

107F g1 in 1M (C2H5)4NBF4/PC with 20 A g1
[96]
(Properties)
[10 wt%PAN + V2O5]/DMF
15 kV/1 mL h1/
17 cm/1.27 mm/130 rpm 1050 C for 1h, activated by KOH at 750 C
V(25wt%, 80nm)-embedded, SBET =

2780 m2 g1, H2 adsorption = 2.41wt% at
303K &10 MPa
[97]
(Structure)
[PAN + 2.5, 5, 25 wt%

MWCNTs]/DMF
12 kV//15 cm/
0.5 mm/1000 rpm
stabilized at 250 C 1h in air, carbonized at

750, 1200 C for 1h in N2
little improvement in carbon layer alignment

around MWCNTs
[98]
(Properties)
[10 wt%PAN + 0.5

1.5 wt%Mn(OAc)]/DMF
20 kV/1 mL h1/ 18 cm/

0.5 mm/300 rpm

1000 C, activated at 800 C in N2 +
30 vol%H2O
Mn(0.23wt%)-embedded: SBET =
1230 m2 g1, Vmicro = 0.42 cc g1, toluene
adsorption = 68g/100g
[99]
(LIBs)
[8 wt%PAN + Mn(OAc)2]/
DMF
14 kV/0.75 mL h1/
15 cm/
stabilized at 280 C in air, 700 C for 1h
MnO+Mn3O4-loaded porous nanofibers:

800450mAh g1
100300 nm dia., 40wt%Co loaded, high discharge capacity >750 mAh/g & good cyclability
[100]
(LIBs)
[PAN + (poly-L-lactic acid) + 21 kV/0.75 mL h1/

Si(17:3:6)]/DMF
15 cm/
stabilize at 280 C for 8h in air, 700 C for 1h Si nanoparticle-loaded, Cdis = 1100 and Cirr =
in Ar
240 mAh g1
[101]
(Properties)
[PAN + pitch]/(DMF + THF) 25 kV///
Carbonization at 1000 C, steam activation at Improvement in spinnability by PAN, SBET =

700-1000 C for 1h
732-1877 m2 g1, Vtotal = 0.3-1.1 cc g1
[102]
(EDLCs)
[PAN + CA]/DMF
[103]
(Structure)
[PAN + PVP]/DMF
[104]
(LIBs)
[105]
800 C for 0h
without CA: SBET = 742 m2 g1, pore 2.0 nm,

141F g1 with 15wt%CA: SBET = 1160 m2 g1,
pore 2.8 nm, 245F g1
dissolved PVP by hot water, stabilized at

270 C and carbonized at 1000 oC
SBET 330-570 m2 g1,
PAN/DMF, TBT/mineral oil, 20 kV/15 & 5 L min1/

(PAN/TBT = 1/1)
15 cm/1.2 & 0.5 mm
dissolved out mineral oil in n-octane,

carbonized at 1000 C for 5 h
Sn@carbon nanotube, 200 nm dia. with ca.

100 nm Sn, reversible capacity 737 mAh g1
(EDLCs)
[7.2 wt% PAN+0.8 wt%

MWCNT]/DMF

700 C, activated at 650 C with H2O2 vapor
PAN: SBET = 930 m2 g1, = 0.86S cm1,

170F g1 in H2SO4 PAN/MWCNT: SBET =
810 m2 g1, = 5.32S cm1, 310F g1
[106]
(LIBs)
[PAN + PMMA + tin octoate]/

DMF
stabilized at 250 C,
multichannel tubular with 2m dia. & 150 nm

channels, reversible capacity 648 mAh g1
[107]
(Properties)
10 wt%PAN/(DMF +
acetone + bromide)
[108]
(EDLCs)
[PAN + 0, 35, 100, 135 wt% 35 kV/0.5 mL h1/

Ni(OAc)]/DMF
20 cm/0.6 mm
[109]
(EDLCs)
[10 wt%PAN + 1, 3,
5 wt%Ni(NO3)2]/DMF
25 kV//20 cm//350 rpm stabilized at 280 C in air, carbonized at

1000 C, leached excess Ni in 4M NaOH
SBET = 480682 m2 g1, Vmeso =

0.210.32cc 1, Vmicro = 0.190.23 cc g1
for 15 wt%Ni-salt added,
[110]
(LIBs)
[7 wt%PAN + 5, 10,
15 wt%ZnCl2]/DMF
14 kV/0.5 mL h1/ 15 cm/ stabilized at 280 C for 2.5 h, carbonized at

700 C for 1h in N2, washed out Zn by HCl
15 wt% ZnCl2-mixed gives SBET = 438 m2 g1,

Vtotal = 0.29 and Vmicro = 0.24 cc g1, Cdis =
400 mAh g1 at 10th cycle
10 kV///1015 cm/
800m
30 kV//30 cm/
20 kV/1.5 mL/h1/ 22 cm/ stabilized at 280 C, carbonized at

0.55 mm/ 1500 rpm
1000 C in vacuo, heated to 14002200 C
for 1h
1000 C for 1h
bundles, 2200 C-treated: d002 = 0.344 nm, ID/

IG>1, // = 840, strength = 542 MPa, Youngs
modulus = 58GPa
22.4 wt%Ni: 164 F/g in 6 M KOH at 2 mV s1
scan
Adv. Mater. 2012, 24, 25472566
www.advmat.de
Ref. (Purposea))

solvent

functionalities
[111]
(LIBs)
[10 wt%PAN + (030 wt%)

Si]/DMF
17 kV/0.75 mL h1/
15 cm/
stabilized at 280 C in air for 5.5 h,

carbonized at 700 C for 1h in Ar
Cdis = 855 and Cirr = 321 mAh g1 with

100 mA g1 in 1M LiPF6/(EC + EMC)
[112]
(LIBs)
[PVA + Si[/(H2O + Na
alkyl- benzenesulfonate)
20 kV/1 mL h1/ 11cm/
dried on copper current collector and then

heated at 500 C for 2 h in Ar
Si nanoparticles (40 nm) embedded in

irregular pores, Cdis increase with cycles, Cdis =
892 mAh g1 after 50 cycles
[113]
(LIBs)
8 wt%PAN + (15, 30,

50 wt%) Si(>70 nm)]/DMF
21 kV/0.75 mL h1/
15 cm//
stabilized at 280 C in air for 5 h, carbonized 30 wt%Si precursor: Cdis = 1281mAh g1, Cirr =
at 700 C for 1 h in N2
260 mAh g1, for 1st cycle, but Cdis =
318 mAh g1 for 50th.
[114]
(Properties)
[10 wt%PAN + 1, 2, 3 wt%

(FeSO4 + FeCl3)]/DMF
25 kV//20 cm//
stabilized at 280 C in air for1h, immersed

into 4M NaOH, carbonized at 1000 C
containing 3wt% iron oxide: SBET = 550 m2 g1
[115]
(Properties)
[10 wt%PAN + 15 wt%

SiWA or SiMoA]/DMF
25 kV//20 cm//

1000 C, sashed in 4 M NaOH
A3-sized webs consisting of 100-300 nm fibers,

for SiMoA-contained fiber: 1.7 103 S cm1
[116]
(LIBs)
[7 wt%PAN + 0, 5, 10,
20 wt% fumed SiO2]/DMF
21 kV/0.8 mL h1/
15 cm/
stabilized at 280 C for 2.5 h, carbonized at

700 or 1000 C, washed out SiO2 by HF
Cirr = 593 mAh g1 for 20wt% SiO2, large

irreversible capacity
[117]
(LIBs)
[10 wt%PAN + 30 wt%

Ni(OAc)2]/DMF
12.5 kV/0.5 mL h1/

15 cm/
stabilized 280 C for 6 h in air, carbonized at dispersed Ni with 20nm size, Cdis =
600 C for 8h in Ar
795 mAh g1 and Cirr = 225 mAh g1 in LiPF6
electrolyte
[118]
(LIBs)
[8 wt%PAN +15, 30, 50 wt% 21 kV///

Mn(OAc)2]/DMF
stabilized at 280 C for 5 h, carbonized at

700 C for 1 h in Ar
MnOx(10 nm)-embeddedwith, Cdis =

785 mAh g1 in 1M LiPF6 (EC/EMC = 1/1)
with 50 mA g1
[119]
(Properties)
[15 wt%PAN-itaco acid

copolymer]/DMF
25kV//40cm/ 0.4 mm/

200 rpm
stretched in hot water, stabilized under

tension, carbonized at 10001500 oC
aligned carbon nanofiber bundles, expecting

high mechanical strength
[120]
(LIBs)
[8 wt%PAN + poly-L-lactic
acid]/DMF
17 kV/0.5 mL h1/ 15 cm/ stabilized at 280 C for 5.5 h in air,

carbonized at 800 C for 1 h
SBET = 235 m2 g1, Vtotal = 0.114 cc g1, Vmicro =

0.086 cc g1, Cdis = 435 mAh g1 after 50 cycles
[121]
(Properties)
[Ph + PVB, piridine and/or

Na2CO3]/MeOH
15 kV/0.01 mL min1/
15 cm/0.5 mm
addition of PVB improves spinnability, addition

of electrolyte (pyridine and Na2CO3 allows
thinner fibers
[122]
(LIBs)
[PVA + SnCl2]/H2O
25 kV/1.0 mL h1/ 15 cm/ carbonized at 500 C for 3 h in Ar/H2

1 mm
including ca. 1nm Sn, Cdis = 382 mAh g1 at

20th cycle
[123]
(LIBs)
[PVA + SnCl2]/H2O
35 kV/1.0 mL h1/ 20 cm/ carbonized at 550 C for 3 h in Ar/H2

1 mm
Sn/SnOx containing fibers, 735 and

510 mA h1 in 1st and 40th cycle.
[124]
(LIBs)
[8 wt%PAN + 50 wt%
Cu(OAc)2]/DMF
10.5 kV/0.5 mL h1/

15 cm/
stabilized at 280 C 5.5 h, carbonized at

600 C for 8 h in Ar
fcc-Cu particles embedded in fibers, Cdis = 617

and Cirr = 253 mAh g1 in LiPF6 (EC/EMC =
1/1) with 50 mA g1
[125]
(Properties)
50 wt%Polycarbosilane/THF 10 kv/4 mL h1/10 cm/

0.8 mm
carbonized in Ar + Cl2 at 800 or 90 C for 2

or 3 h,
SBET = 3116 m2 g1, high storage capacity of H2

as 3.86% at 17bar and 77K
[126]
(Properties)
[10 wt%PAN+7wt%
CoFe2O4]/DMF
20 kV/5 mL h1/15 cm/

0.8 mm/800 rpm
stabilized at 25 C for 2 h in air, carbonized

at 100 C for 4 h in Ar
Superparamagnetic, saturation magnetization

of 63emu/g
[127]
(Properties)
[Lignin + Pt-(acac)]/ethanol 12 kV//2025 cm/
stabilized at 20 C for 36 h in air flow,

carbonized at 6001000 C
400 nm 1 m, 0.6wt%Pt-loaded: SBET =

1200 m2 g1, Vmicro = 0.52 cc g1,
[128]
(EDLCs)
10 wt%PAN/DMF
25 kV///
Stabilized at 28 C, 1h, carbonized & activated ca. 900 nm dia., microporous, SBET =
by steam at 800 C
550 m2 g1, Vmicro = 0.35cc g1, Na-ion
capture = 3.2 mg g1
[129]
(LIBs)
[PAN + Si]/DMF
15 kV/1 mL/h/25 cm/
carbonized at 800, 1000, 120 C for 1 h in Ar
[130]
(Properties)
9 wt%PAN/DMF
1525 kV//1525 cm/
stabilized at 30 C, carbonized at 800140 C, 380-530nm, tensile strength = 3.5 GPa,

Youngs modulus = 172 GPa after 140 C,
[131]
(EDLCs)
[PAN + PVP]/DMF PAN/

DMF and PVP/DMF
20 kV//15 cm/
stabilized at 30 C, carbonized to 97 C, acti- blend & side-by-side fibers of PAN/PVP,

interconnected membranes, the latter
vated by CO2 at 850 C
ca. 220F g1 in 1M H2SO4
[132]
(Properties)
30 wt% Ph (novolac-type)/
MeOH
25 kV//20 cm/
cured in formaldehyde + HCl, carbonized at

80 C for 2 h
Adv. Mater. 2012, 24, 25472566
cured by adding formaldehyde, carbonized

at 900 C for 2 h in N2
REVIEW
Table 1. Continued.
Si(5080 nm)-embedded, 120 C-treated: Cdis =

500 mAh g1 and better capacity retention of
78% after 50th cycle.
100450 nm dia., narrow pore size in

0.40.7 nm, Vtotal = 0.91cc g1, ID/IG = 0.88
2553
www.advmat.de
REVIEW
Table 1. Continued.
Ref. (Purposea))
[57]
(Properties)

solvent
[PVDF + PEO]/(DMF+water) 22.5 kV//40 cm/

stabilized and defluorized with DBU at 5 C,
carbonized at 1000 C for 1h

functionalities
2.3 m dia., pores with ca. 100 nm in
4.3 pores m2, high electrode performance
for redox reaction
[133]
(LIBs)
[4 wt%PAN+8 wt% LiFePO4 15 kV//15 cm/ 0.012 inch stabilized 28 C for 5h in air, carbonized at70 LiFePO4/C composite nanofibers + beads,
C 18h in Ar
precursor]/DMF
160 mAh g1 in 1M LiPF6 EC/EMC
[134]
(Properties)
PAN/DMF
[62]
(Propeties)
17 kV///1.27 mm
40 & 45 wt% pitches (Mw = 25 kV/3 mL h1/10cm/

2380 & 556)/THF
0.88 mm
30 kV/1.5 mL h1/
35 cm/
stabilized at 26 C, carbonized at 105 C for

1h, activated by H3PO4 at 75 C for 3h
activated by using 80 wt% H3PO4: SBET =

621 m2 g1, Vtotal = 0.501cc g1, Vmicro =
0.071cc g1, NO gas sensitive
carbonized at 100 C for 1h, activated by

steam/N2 at 700, 800, 90 C for 1h
Mw had a strong effect on spinnability, SBET =

2053 m2 g1 after 90 C activation of pitch A
with Mw = 2380
[135]
(Properties)
10 wt% PAN/DMF
[136]
(EDLC)
10 wt%[PAN + TEOS (7/3)]/ 20 kV//25 cm//

DMF
stabilized at 28 C in air, carbonized at 800,

900, 1000 C
[137]
(EDLC)
10 wt%[PAN+-CD]+ 3 wt% 25 kV////

AgNO3/DMF
stabilized at 28 C for 1h, activated at 80 C in PAN/30%-CD: 350 nm diameter, SBET =

steam/N2,
1096 m2 g1, microporous, 150F g1 in 6 M
KOH, <20 nm Ag dispersed
[138]
(EDLC)
[2050 wt%Pitch/THF ]+
PAN/DMF (7/3)
20 kV//25 cm//
sabilized and carbonization at 1000 C
SBET = 966 m2 g1, Vpore = 0.38cc g1, wmicro =

1.6 nm, 130 F g1, 100 kW kg1, 15 Wh kg1
[139]
(Properties)
[10wt%PAN+(1, 5,
10 wt %Fe3O4 + X100]/
DMF
1112kV/2mL
h1/17cm//
stabilized at 25 C for 20 min, carbonized at

700, 90 C for 1 h
290270 nm diameter, Fe3O4 nanoparticles

dispersed, = 9.2 S cm1 and Ms = 16 emn g1
(10 wt%, 90 C)
[140]
(Properties)
10 wt%PAN/DMF
20kV/1mL h1/
15cm/0.5 mm/
stabilized at 28 C, carbonized & activated in SBET = 710 m2 g1, Vmicro = 0.345 cc g1, >60%
30 vol% steam at 80 C
removal of NO, no (NO + NO2) detected
(Properties)
30 wt%Ph+0.9 wt%PVB +
0.1 wt%Na2CO3/MeOH
25kV/1mL h1/20 cm//
[141]
immersed into formaldehyde and HCl

solution, carbonized at 80 C for 2 h
hot-pressed at 20 C under 400kPa, stabilized the mats consisting of carbon nanofibers with
at 27 C, carbonized at 1000 C
380 nm diameter and having the bulk density
of 1.211.23 g cc1
80 C-treated: 150nm diameter, microporous
with SBET = 1200 m2 g1, wmicro = 0.6 nm,
160130F/g in 6M KOH
100-450nm diameter, SBET = 812 m2/g1,

Vmicro = 0.91cc g1, wmicro = 0.4-0.7 nm, H2O &
EtOH vapor adsorption
a) Classified into structure, properties, electrochemical capacitors (EDLCs), lithium-ion rechargeable batteries (LIBs), fuel cells and composites with carbon nanotubes.b)
Voltage/flow rate/distance between nozzle and collector/needle diameter, and collector rotation if any. PAN: poly(acrylonitrile, PI: polyimide. PBI: poly(benzimidazole),
PMMA: poly(methyl methacrylate), PVB: poly(vinyl butyral), PVP: poly(vinyl pyrrolidone), CA: cellulose acetate, Ph: phenolic resin, SWCNT: single-wall carbon nanotube,
MWCNT: multiwalled carbon nanotube, DMF: N,N-dimethylformamide, THF: tetrahydrofurane, DMAc: dimethylacetamide, EtOH: ethanol, MeOH: methanol, TEA: triethylamide, TBT: tributyltin, acac: acetylacetonate, OAc: acetate. SiWA: silicotungstic acid, SiMoA: silicomolybdic acid, TEOS: tetraethoxy orthosilicate, -CD: -cyclodextrin,
X-100: surfactant Triton X-100, : electrical conductivity, SBET: BET surface area, Vtotal: total pore volume, Vmicro: micropore volume, Vmeso: mesopore volume, wmicro: micropore size, d002: interlayer spacing, ID/IG: intensity ratio of D-band to G-band in Raman spectrum, Cdis: reversible discharge capacity, Cirr: irreversible capacity, NADH: nicotinamide adenine dinucleotide, Mw: weight-averaged molecular weight, Ms: saturation magnetization
in the carbon nanofibers with SBET from 237 to 571 m2 g1

and total pore volume Vtotal from 0.10 to 0.19 cm3 g1. PVP/
PAN solutions were separately fed into the spinneret to form
side-by-side bicomponent nanofibers and compared with PAN/
PVP blend nanofibers after carbonization up to 970 C and
their activation at 850 C in CO2.[131] Side-by-side bicomponent
nanofibers changed the cross-section morphology from round
to cocoon-like shape by PVP extraction.
The DMF-insoluble fraction of a petroleum-derived isotropic
pitch in THF solution (40 wt% pitch) was successfully electrospun to form the web of carbon fibers with 2-6 m diameter.[69,72] The difficulty to prepare thinner fiber was pointed
out to be resulted from the low boiling point (6567 C) of
the solvent THF, the viscosity of the jet increasing due to the
volatilization of THF during electrospinning. After activation,
2554
the webs were microporous, showing very high SBET as

2200 m2 g1. By mixing PAN with a pitch, spinnability using a
binary solvent DMF+THF (1/1) was improved, resulting in the
fibers with the diameter of 750 nm.[101] After activation by using
steam at 900 C, SBET of 1877 m2 g1 and Vtotal of 1.11 cm3 g1,
consisting of both micro- and meso-pores, were obtained. THFsoluble component of the pitch with a low molecular weight of
556 gave better spinnability on its 40 wt% THF solution, but
the carbon nanofibers prepared from a high molecular weight
pitch as 2380 showed higher development of micropores,
giving SBET of 2053 m2 g1, after carbonization at 1000 C and
activated at 900 C in steam/N2 flow.[62] Highly porous carbon
nanofibers were obtained by electrospinning of THF solution of
polycarbosilane, followed by pyrolysis at different temperatures
and chlorination to extract Si.[125] The nanofibers pyrolyzed at
Adv. Mater. 2012, 24, 25472566
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Adv. Mater. 2012, 24, 25472566
REVIEW
liquid-liquid phase separation and the micropores were due to the decomposition of PEO
during carbonization. Dehydrofluorination
process was found to be the key to retain the
pore morphology in as-spun fibers during
carbonization.
For electrospinning of phenolic resin
(novolac type), its concentration had to be
selected, the solution with more than 65 wt%
was difficult to be spun and that with less
than 50 wt% gave fibers having beads.[89]
Spinnability of phenolic resin solution was
improved by the addition of a small amount
of poly(vinyl butyral) (PVB) with a molecular
weight (Mw) of 110,000, 1 to 3 wt%. The
resultant carbon nanofiber fabrics prepared
at 900 C were flexible and had SBET of ca.
500 m2/g. Addition of a high molecular weight
PVB (Mw of 340,000) markedly improved the
spinnability of phenolic resin solution due to
decreasing solution viscosity and the addition of an electrolyte (pyridine or Na2CO3)
allowed to give thinner fibers because of
increasing electrical conductivity of the precursor solution; 0.1 wt% Na2CO3 resulting in
the carbon nanofibers with an average diameter of 110 nm and SBET of 790 m2 g1.[121]
Microporous carbon nanofibers having Vmicro
of 0.9 cm3 g1 were prepared from novolacFigure 3. TEM images of PAN-based carbon nanofibers after heat treatment at 1000 C (a) and type phenol-formaldehyde by adding PVB and
Na2CO3, followed by carbonization at 800 C
2200 C (b).[107] Reprinted with permission from Elsevier.
without activation.[141] Electrical conductivity
of these carbon nanofiber fabrics was 5.29 S cm1. Carbon
900 C and chlorinated at 850 C had very high SBET as 3116
nanofibers with a narrow pore size distribution of 0.40.7 nm
m2 g1 and Vtotal of 1.66 cm3 g1, which were reported to have
were prepared from novolac-type phenolic resin via electrosa high storage capacity for hydrogen as 3.86 wt% at 17 bar and
pinning of its methanol solution, curing in formaldehyde/HCl
77 K.
and carbonization at 800 C.[132] Even though no activation was
Polyimide (PI) was also spun to prepare carbon
applied, the nanofibers had SBET of 812 m2 g1, Vtotal of 0.91 cm3
nanofibers.[68,75,79,86,88] Carbon nanofibers prepared from a PI
g1 and relatively low ID/IG of 0.88.
of PMDA/ODA with the diameter less than 2-3 m could give
Electrical conductivity was measured to be 4.9 S cm1 on
relatively high tensile strength as 74 MPa and electrical con800 C-carbonized PAN-based carbon nanofibers[63] and the
ductivity of 5.3 S cm1 after the heat treatment at 2200 C.[68]
1000 C-treated nanofibers showed a large negative magneA thermotropic PI (Matimid 5218) dissolved into dimethytoresistance, -0.75 at a temperature of 1.9 K under a magnetic
lacetamide (DMAc) together with 0.33.0 wt% iron(III) acetyfield of 9 T.[65] Although the papers have said that fibrous morlacetnate (AAI) was spun to nanofibers in the atmosphere
phology was survived under the heat treatment, it has to take
with 24% humidity and then carbonized at 4001200 C.[79] It
into account that these nanofibers are not stabilized before carwas declared that AAI worked as a catalyst after decomposing
bonization when these properties were compared with those of
to a-Fe and Fe3O4 during carbonization, although the struccommercial PAN-based carbon fibers. The PAN-based carbon
ture parameters changed a little, d002 decreasing from 0.37 to
nanofiber bundles prepared by carbonization at 2200 C showed
0.34 nm, Lc(002) increasing from 1.0 to 4.2 nm. The addition
the conductivity of 840 S cm1 in parallel with fiber axis, but
of PAN in PI solution improved spinnability and decreased the
[
88
]
61 S cm1 in perpendicular to the fiber axis.[107] Electrospun
diameter of resultant carbon fibers.
PAN-based carbon nanofibers showed electrical conductivity
Poly(vinylidene fluoride) (PVDF) nanofibers were spun from
changes sensitive to NO gas after activation through immersion
the solution of DMF with poly(ethylene oxide) (PEO) and water,
into 80 wt% H3PO4 aqueous solution for 12 h and then heatof which the webs were dehydrofluorized by using 1,8-diazabitreatment at 750 C in Ar.[134]
cyelo[5,4,0]undec-7-ene at 90 C, followed by carbonization at
Mechanical property measurements on single fibers were
1000 C for 1 h in N2 to convert to carbon nanofiber webs.[57]
carried out on PAN-based carbon nanofibers.[77] Averaged
They contained three kinds of pores; the largest pores were
bending modulus was measured to be 63 GPa by mechanical
the interstices among nanofibers, intermediate-sized pores
resonance method and Weibull fracture stress was 640 MPa
with 100-300 nm size were formed on the fiber surface due to
2555
www.advmat.de
REVIEW
Figure 4. SEM images as-spun (a), 1000 C-carbonized (b) and 2800 C-treated (c) fibers and TEM image of 2800 C-treated fiber (d) prepared from
the mixture of PAN/PMMA = 5/5.[84] Reprinted with permission from Elsevier.
with a failure probability of 63%. Tensile strength and Youngs

modulus measured on the bundles of electrospun PAN-based
carbon nanofibers were 542 MPa and 58 GPa, respectively.[107]
These mechanical properties reported on electrospun carbon
nanofibers are much inferior to commercially available PANbased carbon fibers. Since oxidative stabilization of PAN fibers
has been known to be the most important unit-process for
PAN-based carbon fibers, optimization of stabilization condition for electrospun PAN nanofibers has to be studied in
detail. Relatively high tensile strength and Youngs modulus
were reported on electrospun single nanofibers prepared from
9 wt% PAN/DMF solution, followed by stabilization at 300 C
for 1 h in air and carbonized at 800, 1100, 1400 and 1700 C
in N2.[130] Tensile strength depended strongly on heat treatment
temperature, showing the maximum of 2.30 GPa at 1400 C,
2556
and Youngs modulus increased with increasing temperature,

giving 181 GPa at 1700 C, as shown in Figure 5. These changes
in mechanical properties with heat treatment were explained
by the growth of crystallite in nanofibers. However, it has to
be pointed out that orientation of crystallites in the nanofibers
is randomly oriented, not axial. Stretching on as-spun PAN
nanofiber bundles was applied before and during their stabilization, expecting well-developed nanotexture and high mechanical properties,[119,143] although no detailed experimental data
were presented regrettably.
Loading of nanoparticles of various metals and metal oxides
were performed via electrospinning process. Various transition
metal nanoparticles were loaded to carbon nanofibers in order to
improve the performance of electrochemical capacitors and lithium-ion rechargeable batteries, and also loading of platinum to
Adv. Mater. 2012, 24, 25472566
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Adv. Mater. 2012, 24, 25472566
REVIEW
capacitors was studied either by controlling pore structure in the nanofibers as the
electrode for electric double-layer capacitors
(EDLCs) or by loading fine metal particles to
the nanofibers via electrospinning in order to
add some pseudocapacitance. Advantage of
electrospinning is that it can produce webs,
which make their activation and formation of
electrode for capacitors easy.
Webs of PAN-based carbon nanofibers,
which were prepared by electrospinning, stabilization, carbonization and activation at 700,
750 and 800 C in a flow of N2 containing
Figure 5. Dependences of tensile strength and Youngs modulus of carbon nanofibers on car- 30 vol% steam, were used as electrodes of
bonization temperature.[130] Reprinted with permission from Elsevier.
EDLC using 30 wt% KOH aqueous solution.[5]
The 700 C-activated webs gave a high capacicarbon nanofiber webs was carried out for fuel cell applications,
tance as 173 F g1 at low discharge current density as 10 mA
as described separately in the following sections. By electrosg1, but at high current density as 1000 mA g1 the 800 C-actipinning of lignin/ethanol solution containing 0.2 and 0.4 wt%
vated webs gave a high capacitance as 120 F g1: the former
Pt acetylacetonate, followed by stabilization at 200 C in air and
had SBET of 1230 m2 g1 consisting of micropores but the latter
carbonization at 6001000 C, microporous Pt-loaded carbon
had SBET of 850 m2 g1 consisting of mesopores. Similar results
nanofibers were obtained.[127] Pd-loaded carbon nanofibers were
were obtained in other papers.[74] The importance of the presprepared from 8 wt% PAN/DMF solution containing 4.8 wt%
ence of mesopores was reported in many papers using different
Pd acetate Pd(OAc)2 by electrospinning, accompanying by the
carbon materials.[145] PAN-based carbon nanofibers prepared by
stabilization in steps from 230 to 300 C and carbonization at
mixing PAN with 15 wt% cellulose acetate (CA) gave Smicro of
1100 C.[92] The resultant nanofibers showed high electrocata919 m2 g1 and Smeso of 241 m2 g1, and consequently showed
lytic activity toward the reduction of H2O2. Magnetic CoFe2O4
the capacitance of 245 F g1 in 6M KOH aqueous solution with
nanoparticles were embedded in PAN-based carbon nanofibers
a current density of 1 mA cm2.[102] Electrospun PAN-based
via electrospinning of PAN/DMF solution with dispersed oleic
carbon nanofibers prepared from PAN/DMF solution conacid-modified CoFe2O4 nanoparticles with 5 nm size, followed
taining PVP by carbonization at 970 C in N2 and activation at
by stabilization and carbonization.[126] CoFe2O4-embedded
800 C in CO2 were tested in 1 M H2SO4 aqueous solution.[131]
nanofibers were superparamagnetic because of nanosized magSide-by-side bicomponent carbon nanofibers prepared by using
netic particles and saturation magnetization increased from
8 wt% PVP gave the capacitance of 221 F g1, higher than that
45 to 63 emu g1 by carbonization. SiO2-embedded carbon
measured on carbon nanofibers prepared from PAN solution
nanofibers were prepared by electrospinning of PAN/DMF
blended with PVP.
solutions containing different amounts of SiO2, followed by
PAN/DMF solution dispersed multiwalled carbon nanotubes
stabilization and carbonization.[87] SiO2 particles embedded in
(MWCNTs) was successfully spun and carbonized to get webs
carbon nanofibers were washed out by HF, but SBET and Vtotal
consisting of carbon nanofibers which gave improved EDLC perincreased only to 340 m2 g1 and 0.472 cm3 g1. Vanadiumformance in aqueous electrolytes.[94,105] The addition of 3 wt%
embedded carbon nanofibers were prepared by electrospinMWCNTs in precursor PAN increased SBET to 1170 m2 g1 and
ning of PAN/DMF solutions containing different amounts of
electrical conductivity to 0.98 S cm1, consequently increased
V2O5.[96] After activation by using KOH at 750 C, nanoporous
EDLC capacitance to 180 F g1 in 6M KOH.[94] Coating of
nanofiber were obtained, SBET reaching to 2780 m2 g1, Vtotal to
polypyrole (PPy) on these MWCNT-embedded nanofibers led
2.67 cm3 g1 and Vmicro to 1.52 cm3 g1, which gave a hydrogen
to further increase in capacitance to 333 F g1. For MWCNTstorage capacity of 2.41 wt% at 303 K and 10 MPa. Mn-loaded
embedded carbon nanofibers, electrical conductivity and capacicarbon nanofibers, which were activated by steam at 850 C
tance in 1 M H2SO4 increased to 5.32 S cm1 and 310 F g1,
3
1
and had Vmicro of 0.42 cm g , gave relatively high adsorption
respectively, from 0.86 S cm1 and 170 F g1 for the nanofibers
capacity for toluene at 289 K.[98]
without MWCNTs.[105] Polybenzimidazol (PBI) was also
selected as carbon precursor for electrospinning.[70,71,78] Carbon
nanofiber webs were prepared by electrospinning of dimethyl
3.2. Electrode Materials for Electrochemical Capacitors
acetamide (DMAc) solution of PBI (20 wt%), carbonization and
activation at 700850 C in a flow of N2 containing 30 vol%
Porous carbon materials are essential for the electrodes of elecsteam. Dependences of EDLC capacitance in 1 M H2SO4
trochemical capacitors, including electric double-layer capaciaqueous electrolyte on discharge current density are shown on
tors. In commercially available capacitors, activated carbons are
the webs activated at different temperatures in Figure 6. The
commonly used. For the improvement of capacitor performcapacitance of about 202 F g1 was measured on the webs actiance, various carbon materials have been proposed, activated
vated at 800 C with discharge current density of 1 mA cm2,
carbon fibers, templated carbons, carbon nanotubes etc.[144]
which had SBET of 1220 m2 g1, Vmicro of 0.71 cm3 g1 and Vmeso
Application of electrospun carbon nanofibers to electrochemical
of 0.20 cm3 g1.
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REVIEW
Figure 7. Electrochemical adsorption capacity of Na ion in NaCl

solution.[128]
Figure 6. Dependences of electric double-layer capacitance on discharge

current density for polybenzimidazol-derived carbon nanofiber webs heattreated at different temperatures.[78] (a) 700 oC, (b) 750 oC, (c) 800 oC and
(d) 850 C. Reprinted with permission from Elsevier.
Polyimide (PI)-derived carbon nanofiber webs were also

tested as electrode materials of EDLC using 30 wt% KOH
aqueous solution and showed a relatively high capacitance of
175 F g1 with a high current density of 1000 mA cm2.[75] The
precursor for spinning was pyromellitic dianhydride (PMDA)
and 4,4-oxydianiline (ODA) dissolved in a mixed solution of
THF and methanol. The PI webs obtained after spinning were
thermally imidized by heating up to 350 C and carbonized
at 1000 C. All webs activated in air flow containing 40 vol%
steam at a temperature of 650800 C gave a peculiar behavior:
capacitance increased with increasing current density up to 10
mA cm2 and then decreased.
Addition of inorganic salts into PAN influenced on the pore
structure of the resultant carbon nanofibers.[85,108110] Electrospinning from PAN/DMF solutions containing 1-15 wt% ZnCl2
resulted in microporous carbon nanofibers without any activation process after removing Zn compounds by HCl.[85,110] Addition of 5 wt% Ni(NO3)24H2O into PNA/DMF solution resulted
in the increase in SBET, mainly due to the increase in mesopores, without any activation process after carbonization.[109]
Pore structure control in microporous carbon nanofibers was
tried by mixing of tetraethoxy orthosilicate and AgNO3 into
PAN[136,137] and by changing concentration of carbon precursor
pitch/PAN.[138]
The principle of electrochemical capacitors, i.e., physical
adsorption/desorption of electrolyte ions in solution, was
applied for water purification (capacitive de-ionization) by using
different carbon materials.[146] Electrochemical adsorption
capacity of Na+ of electrospin PAN-based carbon fiber webs,
which was measured in NaCl aqueous solution, was compared
for various carbon materials in Figure 7. They showed the
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capacity of 3.2 mg g1, which was comparable with those for

carbon nanotube film and carbon aerogel.
In order to add pseudo-capacitance to electric double-layer
capacitance, loading of Ru on electrospun carbon nanofibers
was carried out.[83] By the addition of Ru acetylacetonate into the
10 wt% PAN/DMF solution, metallic Ru particles with 215 nm
size were embedded in the nanofibers. Nanofibers loaded by
7.31 wt% Ru showed the capacitance of 391 F g1 in 6M KOH
aqueous solution, although the nanofibers without Ru loading
gave 140 F g1. Carbon nanofibers containing nanoparticles of
metallic Ni were prepared through electrospinning of PAN/
DMF solution added 35, 100 or 135 wt% nickel acetate.[117] The
fibers obtained had a diameter of about 150 nm and fine Ni
particles were deposited on their surfaces. The nanofiber webs
with 22.4 wt% Ni loading showed the capacitance of 164 F g1
in 6M KOH with a current density of 250 mA g1, which was
much larger than about 50 F g1 for the nanofiber webs without
Ni loading. Imbedding of metallic V into PAN-based carbon
nanofibers were performed through electrospinning of PAN/
DMF solution containing V2O5.[95] After activation using KOH
at 800 C, SBET reached 2800 m2 g1, due to micropores with
0.71.2 nm and mesopores with 24 nm.
3.3. Anode Materials for Lithium-Ion Rechargeable Batteries
Carbon nanofiber webs prepared through electrospinning and
following carbonization have an advantage for anode of lithium-ion rechargeable batteries (LIBs), because of no necessity
to use an electric conductive additive, such as acetylene black,
and an organic binder, such as PTFE. However, they can not
be expected to give low irreversible capacity, as natural graphite
which is currently used in commercially available batteries,
because most of carbon nanofibers have low graphitization
degree. Few papers reported the results of their application
to anode of LIBs, but a high irreversible capacity could not
be avoided. On 1000 C-treated PAN-based carbon nanofiber
webs, reversible discharge capacity Cdis of 450 mAh g1
was obtained with a current density of 30 mA g1, a little higher
than natural graphite, but irreversible capacity Cirr was as high
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Adv. Mater. 2012, 24, 25472566
REVIEW
as 500 mAh g1.[80] High temperature treatment of the webs

could not improve LIB performance. Pores were introduced
into carbon nanofibers by adding poly-L-lactic acid (PLLA) in
PAN/DMF solution.[100,120] Addition of PLLA created micropores without activation process, Vmicro being 0.086 cm3 g1,
and increased Cdis to 435 mAh g1 after 50th cycle with a current density of 50 mA g1.[120] Addition of fumed SiO2 with
minute particles in PAN/DMF solution was carried out in order
to create pores after leaching out of SiO2, but it showed a low
SBET as 92 m2 g1 and very high Cirr, more than 1000 mAh g1,
at the first cycle.[116]
Many works applying electrospinning are aiming to load
some electrochemically active metallic particles to carbon
nanofibers in order to improve LIB performance. Si-loaded
carbon nanofibers were prepared from PAN/DMF solution
with Si nanoparticles (ca. 70 nm)[100,111,113,129] and also from
PVA/H2O solution dispersed Si nanoparticles (ca. 40 nm) with
a surfactant.[112] Galvanostatic charge-discharge curves and
cyclic performance with a current density of 100 mA g1 in 1 M
LiPF6/EC+EMC solution are shown on the webs prepared from
15 wt% Si mixed PAN/DMF solution by carbonization at 700 C
in Figure 8. Cdis for the 1st cycle is very high as 855 mAh g1
with a relatively large Cirr of 312 mAh g1. Cdis decreases slowly
with cycling, 781 mAh g1 after 10th cycle and 773 mAh g1
after the 20th cycle, which is much higher than the theoretical
capacity for graphite and also than carbon nanofiber webs prepared without Si addition.
Sn-loading via electrospinning was performed by adding
a Sn compound into the precursor solution.[104,106,122,123] Sncontained carbon nanofiber webs were prepared from PVA/
H2O solution dissolved SnCl2 by electrospinning and following
carbonization in Ar/H2 (95/5 v/v).[122,123] The diameter of the
resultant nanofibers was about 4 m and contained Sn/SnOx
particles of about 20-40 nm size, most of which were located
in pores of carbon nanofibers, as shown in Figure 9a). The
webs show relatively high Cdis as 735 mAh g1 but relatively
large Cirr for the 1st cycle (457 mAh g1), although Cirr becomes
smaller after the 2nd cycle (Figure 9b). Sn-encapsulated carbon
nanofibers were prepared through electrospinning of PAN
nanofibers containing tributyltin (TBT) dissolved into a mineral
oil, followed by extracting the mineral oil, most of which located
at the core of the fiber, in n-octane and by heating at 1000 C
in Ar/H2 atmosphere to carbonize the outer PAN sheath and
to decompose the TBT core to metallic Sn.[104] The resultant
nanofibers showed high Cdis as 737 mAh g1 (91% of the theoretical capacity), even after 200 cycles. Sn-encapsulated carbon
nanofibers were also prepared from PAN/DMF containing
PMMA and tin octoate.[106] The nanofibers had the diameter
of about 2 m and consisted of hollow channels with about
100 nm diameter containing metallic Sn nanoparticles. Sn
content in these nanofibers was 66 wt% and its particles were
covered by carbon layer with a thickness of about 5 nm. The
nanofibers showed a high Cdis as 648 mAh g1 with a current
density of 100 mA g1 even after 140 cycles.
Loading of Co, Fe, Mn, Ni and Cu was carried out
mostly by adding their acetates into PAN/DMF solution.[90,91,99,114,115,117,118,124] Carbon nanofibers containing either
metallic Co, Ni or Cu nanoparticles delivered relatively high Cdis
in 1 M LiPF6/EC+DEC electrolyte.[90,117,124] When Mn acetate
Figure 8. Charge-discharge curves and cyclic performance of the carbon

nanofiber webs prepared from 15 wt% Si-dispersed PAN/DMF solution.[111] Reprinted with permission from Royal Society of Chemistry.
(Mn(OAc)2) was used, carbon nanofibers containing crystalline

MnO and Mn3O4 nanoparticles were obtained after carbonization at 700 C, which had steady cyclic performance.[99,118] The
resultant carbon nanofibers include MnOx nanoparticles in
their matrix with pores, as shown in Figure 10a), and give high
capacity with good cyclic performance, the nanofibers prepared
by adding 50 wt% Mn(OAc)2 giving a steady capacity value of
about 600 mAh g1, much higher than the nanofibers prepared
without Mn(OAc)2, as shown in Figure 10b). When ferric acetylacetonate was added into PAN/DMF solution, Fe3O4-loaded
carbon nanofibers were obtained.[91] After the carbonization at
600 C, the resultant carbon fibers included crystalline Fe3O4
particles with about 20 nm size, of which content was calculated as 31 wt%. Cdis of the nanofibers decreases rapidly during
first few cycles and then tends to increase with increasing cycle,
giving higher discharge capacity than that without Fe3O4.
Nanofibers of LiFePO4/C composite were obtained
as nanofibers via electrospinning of PAN/DMF solution
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REVIEW
Figure 9. TEM image of Sn/SnOx-containing carbon nanofibers (a) and

cyclic performance in 1 M LiPF6/EC+DMC electrolyte solution with a current density of 30 mA g1.[123] Reprinted with permission from Elsevier.
containing phosphate precursor (LiCO2CH3, Fe(CO2CH3)2 and

H3PO4 in equal mole ratio) with a wide range of diameters of
10200 nm, together with beads.[133] The nanofibers carbonized
at 700 C gave the highest Cdis of 160 mAh g1 in 1 M LiPF6/
EC+EMC solution as cathode. Nanofibers of Li2ZnTi3O8/C
composites were synthesized via electrospinning of an ethanol
solution of tetrabutyl titanate, zinc acetate and lithium acetate
with PVP, followed by calcination at 750 C in air.[147]
3.4. Composite With Carbon Nanotubes
Various carbon nanotubes (CNTs) were included in carbon
nanofibers via electrospinning for the reinforcement of their
mechanical properties.[66,76,107] Carbon nanofibers were prepared by electrospinning of PAN/DMF solution, in which
14 wt% single-wall carbon nanotubes (SWCNTs) were dispersed, stabilizing in air and carbonizing at 1100 C.[66]
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Figure 10. TEM image of MnOx-loaded carbon nanofiber (a) and cyclic
performance in 1 M LiPF6 EC/DEC electrolyte (b) for carbon nanofibers
prepared by adding 0. 10, 30 and 50 wt% Mn(OAc)2 into PAN/DMF solution.[118] Reprinted with permission from Elsevier.
SWCNTs were distributed in parallel to the fiber axis, maintaining their straight shape, in PAN nanofibers with the diameter of 50200 nm. Elastic modulus of SWCNT/PAN nanofibers,
which was evaluated using AFM, increased with increasing
SWCNT content, from 60 GPa for PAN fiber to 140 GPa for
that containing 4 wt% SWCNT. Multi-walled carbon nanotubes (MWCNTs) were also successfully included into electrospun carbon nanofibers prepared from PAN/DMF solution, in
which the content of MWCNTs were 2-35 wt%.[76] In as-spun
nanofibers, most MWCNTs are aligned well along the fiber
axis, but slightly-curved MWCNTs resulted in curved nanofibers
and winding or helical MWCNTs could not be embedded
within the nanofibers. The PAN nanofibers containing 5 wt%
MWCNTs showed tensile strength of 80 MPa and tensile modulus of 3.1 GPa. The fibrous morphology was maintained after
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4. Discussions
4.1. Carbon Precursors
For the production of carbon materials, the selection of precursor is the most crucial, because it determines the nanotexture of the resultant carbon under ordinary carbonization
conditions, such as the heat treatment under atmospheric pressure. The nanotexture formed during carbonization process,
which is classified into random, planar, axial and point orientations on the basis of the scheme of preferred orientation of the
basic structural units of carbon layers, is known to govern the
structural development by further treatment at high temperatures and, as a consequence, to influence on various properties,
such as electrical, mechanical and chemical properties.[1,148]
Also, carbon materials prepared from various precursors have
been classified into two groups, based on whether the structural change to graphite (three-dimensionally ordered structure) is easy or not at high temperatures above 2500 C, calling
graphitizing and non-graphitizing carbons,[1] even though some
of them are known to show different behaviors.
The diameter of electrospun carbon nanofibers is 100 to
1000 nm, which might give some influence on the formation
of nanotexture during their carbonization process and also on
structural modification at high temperatures. Size of carbon
layers evaluated as La by X-ray diffraction was experimentally
shown to depend strongly on the particle size of spherical
carbon materials.[148] PAN-derived carbon fibers prepared via
melt-spinning, stabilization and carbonization have a random
nanotexture and are non-graphitizing (called general-purpose
grade). In order to improve nanotexture to axial orientation,
stretching of the as-spun fibers is known to be necessary during
further heat treatments, and the resultant PAN-based carbon
fibers give higher strength and Youngs modulus (high-performance grade).[2] The carbon prepared in the gallery of layer-structured montmorillonite (template carbonization) is easily converted to graphite at a high temperature as 2800 C, because the
pyrolysis of PAN is performed in monolayer of carbon atoms
between template layers.[149] Therefore, the formation of nanotexture in nano-sized fibrous carbons (carbon nanofibers) and
their change in structure and properties with high temperature
treatment might be a little different from our knowledge based
on large-sized particles of carbons with different nanotextures.
PAN-based continuous nanofibers were prepared under tension
Adv. Mater. 2012, 24, 25472566
during stabilization and carbonization by expecting superior

mechanical properties.[119] However, no structural studies had
been reported yet and the heat treatment had been done only
up to 1500 C.
Stabilization of PAN fibers with micrometer-sized diameters
is known to be the most important process on the production
of carbon fibers.[2] In most literatures working on PAN-based
carbon nanofibers, however, as-electrospun PAN fibers were
stabilized at 280 C in air and carbonized at a temperature of
6001100 C in inert atmosphere. It might be needed to explore
the optimum condition for stabilization and carbonization
from structural view points, such as the size of basis structural
units of carbon layers and their orientation in nanofibers, carbonization yield, content of foreign atoms, hydrogen, nitrogen
and oxygen, which remain even after carbonization, and also
changes in diameter and its distribution.
Aromatic polyimides (PIs) are interesting carbon precursors
because they give a wide range of structure, from well-crystallized
graphite film to amorphous carbon with random nanotexture,
by selecting a combination of the starting dianhydride and the
diamine.[150] However, one kind of polyimide (a combination of
pyromellitic anhydride and 4,4-oxydianiline, PMDA/ODA) was
mostly used for electrospinning.[75,86] Even when starting from
PMDA/ODA, the thickness of its film is known to govern the
graphitizability: thin films with less than 25 m thickness can
be converted to highly crystalline graphite by high temperature
treatment, but thicker films can not, which is explained by the
orientation of precursor molecules in the film.[150] Studies on
different PIs by coupling with heat treatment at high temperatures and detailed structural analyses may give a more wide
range of nanotextures in the resultant carbon nanofibers and,
consequently, may open more wide applications, because of the
possibility to have a controlled structure from graphite to amorphous. For applications requiring high electrical conductivity,
some of PIs are worthwhile to be tested as a precursor.
Pitch is less costly than other carbon precursors, such as PAN
and PI, but not many reports discuss its use for electrospinning. Since pitch is a mixture of various hydrocarbons, certain
components might be needed to be selected for electrospinning
in relation to the solvent selected, as the DMF-insoluble part of
the pitch with THF.[72] Mesophase pitch, which is used as a precursor for commercial mesophase-pitch-based carbon fibers, is
worthwhile to be used for electrospinning, even though a stabilization process is needed to get pitch-based carbon nanofibers,
which is expected to lower its graphitizability.
Although poly(vinyl alcohol) PVA has a very low carbonization yield (few wt%), it might be an interesting precursor
because water can be used as a solvent.[112,122,123]
Phenolic resins are often used as carbon precursor, which
gives non-graphitizing carbon in a conventional carbonization
process with the advantage of a relatively high carbonization
yield. However, it is rarely used in studies on carbon nanofibers
via electrospinning.[89,121,132]
REVIEW
carbonization at 850 C, even though PAN shrunk largely but

MWCNTs did not.
Carbon nanotubes were grown on the surface of electrospun
carbon nanofibers.[73] Fe-loaded carbon nanofibers were prepared from PAN/DMF solutions containing 3.3 and 6.7 wt%
Fe acetyleacetonate Fe(acac)3 by electrospinning, stabilization,
reduction of Fe3+ to metallic Fe at 500550 C in H2 and carbonization at 1100 C in Ar. Metallic Fe particles with 1020 nm
size dispersed in the nanofibers. On the surface of the carbon
nanofibers thus prepared, MWCNTs were grown by catalytic
CVD of hexane, of which the length depended on the period of
catalytic CVD.
4.2. Pore Structure Control

In most cases, electrospun carbon nanofibers were prepared
in the form of webs (mats), which is an advantage for various
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2562
applications, such as electrodes for EDLCs and LIBs as mentioned above. In these webs consisting of carbon nanofibers,
different kinds of pores are formed; large pores (maybe better
to call them spaces), macropores (>50 nm size), mesopores
(250 nm size) and micropores (<2 nm size).
Large spaces are formed due to entangling of different
nanofibers and disperse widely in their size and morphology.
These pores are very difficult to control and characterize mainly
because they are flexible (flexible interparticle pores).[1] The
bulk density or porosity of the webs is the parameter that is
easy to determine and effective for characterizing these large
spaces. However, information on the bulk density or porosity
has not been presented in most literature reporting on electrospun carbon nanofiber webs. It has to be emphasized that their
presence in the webs is very important for applications: they are
pathways for electrolytes in energy storage devices to diffuse
into smaller pores to be adsorbed, but a too large amount of
pores makes the volumetric storage capacity small. When electrospinning conditions are not appropriate, bead-like particles
are formed together with fibrous particles and rigidly bound
interconnections between nanofibers are formed after carbonization, which may result in a rigid macropore system.
Macro-, meso- and micropores are formed in each nanofiber
and are rigid (rigid intraparticle pores). Most micropores and
some mesopores are intrinsically formed in fibrous carbon particles during the carbonization process due to the evolution of
different gaseous species, such as hydrocarbons of various sizes,
CO, CO2, etc., and thus strongly depends on the carbon precursor used and carbonization conditions. To increase and control the amount of micropores, a conventional activation process
has been applied in many works by using either steam, KOH,
or H3PO4 as an activation reagent on electrospun nanofibers
after their carbonization (Table 1). The addition of ZnCl2, which
was one of reagents for conventional activation, into a PAN/
DMF solution before electrospinning was also adopted, but no
pronounced improvement of SBET was obtained.[85] For application to the electrode of electrochemical capacitors, the activation process was applied on electrospun carbon nanofibers
derived from PAN,[67,74,128] PBI,[70,71,78] and PI.[75] By the activation of PAN-based carbon nanofibers in a flow of N2 containing
30 wt% steam at 800 C, SBET increased to 1160 m2 g1, Vtotal to
0.64 cm3 g1 and capacitance to 134 F g1 in 6M KOH aqueous
electrolyte with a current density of 1 mA cm2.[75] By the activation of PBI-derived carbon nanofibers at 800 C, capacitance of
202 F g1 in 1 M H2SO4 aqueous electrolyte was obtained with
good rate performance.[78] Also the addition of cellulose acetate
into PAN was tried to control pore structure without activation
process, giving certain increases in SBET from 740 to 1160 m2 g1
and in capacitance from 141 to 245 F g1 in 6M KOH with a
current density of 1 mA cm2.[102] By the activation of carbon
nanofibers, micropores are supposed to be formed on their
surface, which is expected to be advantageous for adsorption/
desorption. For commercially available activated carbon fibers
(ACFs) their advantages for adsorption/desorption of gases due
to the presence of micropores on their surface are now well
known.[1] Good rate performance in electrochemical capacitors
was reported on electrospun carbon nanofiber webs,[74,78] probably due to the formation of micropores on the nanofiber surface, but its experimental evidence is not reported yet.
Mesopores can be increased by applying a conventional activation process on the electrospun carbon nanofibers, but it is
possible only by sacrificing micropores. It might be interesting
to add a template, either surfactants or MgO precursors into
electrospinning precursor solution, which can leave mesopores
after carbonization.[151]
Most of the macropores and some of the mesopores have to
be introduced into fibrous particles intentionally, by using either
an additional carbon precursor, which gives pores after carbonization because of its low carbonization yield, such as PMMA in
PAN to introduce tubular macropores,[84] or an additional solvent for electrospinning solution, such as water in DMF.[57]
Not only micro- and mesopores of the electrodes in EDLCs are
important for adsorption of electrolyte ions, but also the diffusion of ions to micro- and/or meso-pore surfaces to be adsorbed
is known to give a strong influence on capacitor performance,
particularly charge/discharge process with high rates. The presence of mesopores, in addition to micropores, has been pointed
out to be important for getting good rate performance, in other
words, high retention in capacitance with high rate charge/discharging. Obtaining webs consisting of carbon nanofibers may
be one of the merits of the process via electrospinning, because
any binder and electroconductive additives (commonly carbon
blacks) are not needed to form electrode sheets and the presence
of large spaces between nanofibers may be advantageous for
the diffusion of electrolyte ions to the micro- and meso-pores in
nanofibers. However, it has to be mentioned that the webs usually have a low bulk density, which may lead to low volumetric
capacitance.
The optimum conditions for electrode carbon, including its
pore structure, is not yet clearly understood and they might be
different for charge/discharge conditions and also for electrolyte ions. It also has to be pointed out that direct comparison
among the capacitance values reported is very difficult because
their determination procedure is not standardized.[144] In order
to show the merits of using carbon nanofibers prepared via electrospinning clearly under the present situation, more detailed
studies are strongly demanded on pore structure control, not
only the control of meso- and micropores in nanofibers, but also
proper characterization and the control of large spaces in the
webs. In addition, wettability of the resultant carbon nanofiber
webs with electrolyte solutions, either aqueous or non-aqueous,
has to be studied, which might depend on precursor and carbonization temperature.
4.3. Improvement in Electrical Conductivity
High electrical conductivity of electrospun carbon nanofibers
is required in various applications, electrode materials for
energy storage devices, EDLCs and LIBs, and also catalyst
supports.
As the anode of LIBs, carbon nanofiber webs are required
to have both high electrical conductivity and well-developed
graphite structure. High temperature treatment is known to
be preferred to improve these two factors. However, graphitizability of a carbon depends strongly on carbon precursor used,
for examples, PAN-based carbon fibers can not get high degree
of graphitization but mesophase-pitch-based carbon fibers can
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4.4. Loading of Metallic Species

One of the requirements for electrospun nanofibers to be
applied to energy storage devices is uniform loading of metallic
nanoparticles. There have been proposed different techniques,
as some of them were described in the previous section and
also reviewed in a reference.[16] The process for loading via electrospinning may be divided into two, mixing either metallic
nanoparticles or metal precursors into carbon precursor before
electrospinning and loading of metal particles on electrospun
fibers either before or after carbonization. By the former process,
metallic nanoparticles are embedded and immobilized into the
resultant carbon nanofibers, but they have to survive as active
species under the temperature for carbonization and some of
nanoparticles might not be active because they are placed in
the center of the fibers. By the latter process, however, they are
preferentially deposited on the surface of the nanofibers and so
the substrate nanofibers can be treated under different conditions, such as high temperature treatment for their graphitization to improve electrical conductivity, but immobilization and
grain growth inhibition of the deposited metallic nanoparticles
has to be taken into consideration.
Adv. Mater. 2012, 24, 25472566
For LIB applications, the loading of nanoparticles of various

metallic species, which are electrochemically active for lithium
storage, is carried out by mixing their precursors with or without
organic additives into a carbon precursor solution before electrospinning, as described in the previous section. Most Sn/SnOx
nanoparticles formed in carbon nanofibers electrospun from
PVA/H2O solution containing SnCl2 are located in the pores,
as shown in Figure 9a, which is the reason why the nanofiber
webs show a stable cycle performance (Figure 9b) because the
space neighbored to Sn/SnOx particles in the pore may absorb
a large volume expansion due to lithium alloying.[123] Carbon
nanofibers encapsulated Sn nanoparticles (ca. 100 nm size) via
electrospinning using coaxial spinneret showed a steady cyclic
performance at high Cdis of 737 mAh g1 (91% of theoretical
capacity).[104] It has to be mentioned that electrospinning of
carbon precursor with Sn precursor can be done easily and
effectively more than the deposition of Sn after carbonization,
because Sn and/or SnOx nanoparticles included into carbon
matrix can be active in LIBs, in other words, lithium ions in
LIBs can penetrate into carbon nanofibers to react with metals.
Cathode material for LIBs, LiFePO4, was loaded into carbon
nanofibers via electrospinning,[133] but it did not show an advantage for the electrospinning process because the appropriate
spinning conditions were not selected.
In order to add pseudo-capacitance due to redox reaction to
the EDLC of the substrate carbon nanofiber webs, loading of the
metallic species onto carbon nanofibers via electrospinning was
carried out by using Ru acetylacetonate Ru(acac)3[83] and V2O5.[95]
By addition of 20 wt% Ru(acac)3 into a PAN/DMF solution,
nanometer-sized Ru particles (215 nm) were embedded and, as
a consequence, the capacitance in 6M KOH electrolyte increased
from 140 to 391 F g1 by embedding 7.31 wt% Ru, about
250 F g1 being added as pseudo-capacitance.[83] In contrast to
LIBs, metallic species have to be located on the surface by exposition to an electrolyte solution and the species included into the
carbon matrix is difficult to work with because most electrolyte
ions in capacitors cannot penetrate into the carbon matrix, which
may reduce the utilization efficiency of loaded metal.
REVIEW
be graphitized.[1] Since the stabilization process for the preparation of carbon nanofibers from PAN and pitch is essential to
keep fibrous morphology after carbonization, the possibility
to have highly graphitized nanofibers is supposed to be lowered, although detailed study is needed. PAN-derived carbon
nanofibers could not be graphitized even by the heat treatment
at 2800 C, giving d002 of 0.341 nm and electrical conductivity of
20 S cm1, of which Cdis became low as about 120 mAh g1 in
1 M LiClO4/EC+DEC electrolyte.[80] Since the nanofibers have
low graphitization degree, a large Cirr could not be avoided;
1000 C-treated nanofibers showed Cdis of ca. 450 mAh g1 and
Cirr of ca. 500 mAh g1 for the 1st charge/discharge cycle. On
the other hand, some of polyimides (PIs) is known to have very
high graphitizability after high temperature treatment in very
thin films without stabilization and to get thin graphite film.[150]
Carbon nanofibers prepared from one of PIs, PMDA/ODA, and
heat-treated at a high temperature as 3000 C are worthwhile to
be tested as the anode of LIBs.
High temperature treatment is known to improve conductivity not only due to the development of graphitic structure
but also due to exclusion of foreign atoms in carbon materials.
However, it is also known to reduce meso- and micropores
easily,[151,152] which is not desirable for EDLC applications. In
order to increase electrical conductivity of electrospun carbon
nanofibers, embedding of MWCNTs was performed in the
relation to EDLC application.[94,105] Embedding of 0.8 wt%
MWCNTs led to the increase in electrical conductivity of the
webs from 0.86 to 5.32 S cm1, accompanied by the increase in
EDLC capacitance from 170 to 310 F g1 in 1 M H2SO4 aqueous
electrolyte.[105]
In order to control the electrical conductivity of carbon
nanofibers prepared via electrospinning, therefore, fundamental studies on changes in structure and nanotexture with
heat treatment in a wide range of temperature are needed on
various carbon precursors, including PAN, pitch and PI.
5. Conclusions
Carbon nanofibers prepared via electrospinning and following
carbonization are summarized by focusing on the structure and
properties in relation to their applications. The precursor, pore
structure, electrical conductivity, and metal loading of carbon
nanofibers were discussed from the viewpoint of structure and
nanotexture of carbons.
Electrospinning is an interesting and promising technique
to prepare carbon nanofibers, having intermediate diameters
between carbon nanotubes and carbon fibers. There have
been many reports on the preparation of carbon nanofibers
via electrospinning, as summarized in Table 1. However, more
detailed studies still remain to be carried out, such as the selection of carbon precursors from the viewpoint of structure and
nanotexture control in nanofibers, optimization of electrospinning conditions and further treatment, including stabilization, carbonization, activation and further heat treatment at
high temperatures. Important factors to be controlled through
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REVIEW
electrospinning are pore structure, degree of graphitization,

electrical conductivity and metallic species loading of carbon
nanofibers, which depend strongly on the selection of precursors, including carbon precursor, metal precursor and additives,
and preparation conditions of carbon nanofibers, including
electrospinning and carbonization.
Acknowledgements
The authors acknowledge the financial supports from National Natural
Science Foundation of China (No. 51102143), New Teachers Fund for
Doctor Stations (20100002120006, Ministry of Education) (Y.Y.) and also
from Guangdong Province Innovation R&D Team Plan.
Received: December 27, 2011
Revised: January 31, 2012
Published online: April 17, 2012
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2.1. Setup and Conditions for Electrospinning

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Michio Inagaki is the professor emeritus of Hokkaido

Ying Yang is the professor

Figure 1. Scheme of fundamental setup for electrospinning.

Feiyu Kang was born in 1962,

atmosphere condition. The first factor, solution properties,

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2012, 24, 25472566

ratio had to be used.[27] The second factor, processing condition,

Adv. Mater. 2012, 24, 25472566

electrospinning of PAA solution and then imidization of the

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

with various diameters (50250 nm) were easily electrospun

3. Carbon Nanofibers Synthesized Via

carbon nanofibers, their performance in energy storage devices,

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2012, 24, 25472566

Precursor and additives/

Stabilization, carbonization and activation

Carbon nanofibers synthesized and

no stabilization, carbonized at 600, 800,

stabilized at 200 C, carbonized at 1100 oC

homogeneous and straight SWCNTs in PAN,

stabilized at 280 C, carbonized & activated

200400 nm dia., SBET 1230 m2 g1, Vtotal 0.55cc g1,

1315 kV/20 g h1/67

imidization at 150250 C, carbonized at

electrical conductivity: from 2.5 and

carbonization & activation

SBET 20602220 m2 g1, microporous

700850 C for 1/2h in N2+30vol% steam

100-500nm dia., 800 C-treated SBET 1220 m2

18 kV/3mL h1/10 cm/

stabilized at 300 C, carbonized at 700,

dumb-bell like cross-section with (46)

[6.7 wt%PAN + 3.3 wt%

stabilized at 250 C, Fe reduction at 500

MWCNTs grown by CVD of hexane at 700 C

stabilized at 280 C, carbonized & activated

200350 nm dia., SBET = 1160 m2 g1, Vtotal =

[7 wt%PAN + 235 wt%

30 kV//30 cm//10 m/s stabilized at 220 C for 2h in air, carbonized

0.9 kV/cm///0.1 mm/

stabilized at 250 C, carbonized at

110 nm dia., 89.4%C, d002 = 0.368 nm, ID/IG =

///0.5 mm/300 rpm

carbonized & activated at 700, 750, 800,

800 C-treated: SBET = 1220m2 g1, Vmicro =

[20 wt%PI + Fe-acac

carbonized at 4001200 C for 1h

-Fe and Fe3O4 are formed above 800 C, d002

stabilize at 280 C for 1h, carbonized at

1000 C-treated Cdis = 450 mAh g1 but Cirr =

0.3 kV cm1//18 cm/

stabilized at 250 C carbonized at 1100 C

hollow carbon nanofibers

stabilized at 280 oC, carbonized at 80 C,

SBET = 1193m2 g1, Vmicro = 0.455 cc g1 high

stabilized at 280 C, carbonized & activated