10.1098/rsta.2004.

1437

Applications of carbon nanotubes in

the twenty-first century
By M o r i n o b u E n d o1 , Takuaya Hayashi1 , Y o o n g A h m K i m1 ,
Mauricio Terrones2 a n d M i l r e d S. Dresselhaus3
1
Faculty of Engineering, Shinshu University, 4-17-1 Wakasato,
Nagano-shi 380-8553, Japan (endo@endomoribu.shinshu-u.ac.jp)
2
Advanced Materials Department, IPICyT Camino a la Presa,
San José 2055, Lomas 4a sección 78216,
San Luis Potosı́, SLP, Mexico
3
Massachusetts Institute of Technology, 77 Massachusetts Avenue,
Cambridge, MA 02139-4307, USA

Published online 13 August 2004

Carbon nanotubes, which consist of rolled graphene sheets built from sp2 hybridized
carbon atoms, are now attracting scientists from various disciplines due to their
fascinating physico-chemical properties. In this account, we will review the recent
progress on the synthetic techniques for the large-scale production of carbon nano-
tubes, especially focusing on the floating-catalyst method used in the chemical vapour
deposition (CVD) process. We will also describe effective purification methods avoid-
ing structural damage, and discuss the electrochemical applications of these systems
including the fabrication of: (i) lithium-ion secondary batteries; (ii) lead-acid batter-
ies; (iii) electric double-layer capacitors; (iv) fuel cells; and (v) multifunctional fillers
in polymer composites. We foresee that carbon nanotubes will find numerous appli-
cations and take an important place in the development of emerging technologies in
the near future.
Keywords: carbon nanotubes; chemical vapour deposition; growth; size-effects

1. Introduction
We will define nanocarbons as materials built at a nanometre scale from sp2
hybridized carbon atoms. These include various forms ranging from fullerenes (Kroto
et al . 1985) and carbon nanotubes (Oberlin et al . 1976; Iijima 1991) to nanoporous
materials (Tanaka et al . 1999). Among them, one-dimensional carbon nanotubes have
attracted particular interest due to their unique morphology, nanosized scale, novel
physico-chemical properties and, furthermore, their versatile applications (Dressel-
haus et al . 1996; Saito et al . 1998; Harris 1999; Ajayan & Zhou 2001; Baughman et
al . 2002; Yasuda et al . 2003). Carbon nanotubes could be visualized as rolled sheets
of graphene (sp2 carbon arranged in a honeycomb lattice), which are sometimes
capped (by a fullerene-like hemisphere) at each end (see figure 1). They could be
either single walled with diameters as small as 0.4 nm, or multi-walled consisting of

One contribution of 12 to a Theme ‘Nanotechnology of carbon and related materials’.

Phil. Trans. R. Soc. Lond. A (2004) 362, 2223–2238

c 2004 The Royal Society
2223
2224 M. Endo and others

Figure 1. Schematic of an individual layer of honeycomb-like carbon called graphene,

and how this could be rolled in order to form a carbon nanotube.

1.5

1.0
band gap (eV)

0.5

0 0.5 1.0 1.5

nanotube radius (nm)
Figure 2. Band gap as a function of nanotube radius calculated using
an empirical tight-binding Hamiltonian.

nested tubes (e.g. 2–30 concentric tubes positioned one inside the other) with outer
diameters ranging from 5 to 100 nm. The constituent cylinders within multi-walled
carbon nanotubes (MWNTs) may possess different chiral structures. In particular, it
has been predicted that the electronic properties of single-walled carbon nanotubes
(SWNTs) may vary from semiconductors to metals, depending upon the chiral angle
(the way the hexagons are positioned with respect to the tube axis) (Dresselhaus et
al . 1996; Saito et al . 1998). Figure 2 shows the band gap, estimated by a tight-binding
approach, as a function of the nanotube radius. The plot indicates that as the nano-
tube’s diameter becomes larger (the curvature of a graphene cylinder becomes less

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2225

(a) (b) (c)

200 nm 5 nm 5 nm

Figure 3. (a) SEM image exhibiting web-like SWNT structures on the surface of zeolite template.
(b), (c) TEM images of CVD derived SWNTs in an isolated and a bundle state, respectively.

pronounced), the value of the band gap is closer to that of a planar graphene sheet
(Mintmire & White 1995). In particular, three typical chiral structures of SWNTs
have been proposed (armchair, zigzag and helical), and their structures have been
confirmed using scanning tunnelling microscopy (STM) and electron diffraction stud-
ies (Ge & Sattler 1993; Dresselhaus et al . 1996; Wilder et al . 1998). For example, if
the C60 molecule is bisected normally to the fivefold axis, the cap for an ‘armchair’
nanotube is formed, and if the C60 molecule is bisected normally to the threefold
axis, the cap for a ‘zigzag’ nanotube is generated. In addition to the armchair and
zigzag nanotubes, a large number of chiral or helical carbon nanotubes could be
obtained, exhibiting a screw-like hexagonal pattern along the nanotube axis, which
is terminated by a large variety of ‘hemispherical’ but asymmetric caps. It is impor-
tant to emphasize that three-dimensional stacking does not exist in MWNTs, even
though each individual shell consists of a perfect rolled hexagonal graphene sheet.
In MWNTs, the curvature of the graphene sheets is responsible for weaker van der
Waals interactions, thus resulting in a larger inter-layer spacing (0.34 nm) when com-
pared with three-dimensional crystalline graphite (0.335 nm). In this paper, we will
review large-scale synthetic methods for producing carbon nanotubes, their purifica-
tion technique, and finally we will discuss some applications of these nanomaterials
in electrochemical systems and as multifunctional fillers in the fabrication of polymer
composites.

2. Large-scale production of carbon nanotubes

In order to use carbon nanotubes in novel devices, it is necessary to produce these
materials with a high crystallinity on a large scale economically. In this context, the
catalytic chemical vapour deposition (CVD) method is considered to be the opti-
mum for producing large amounts of carbon nanotubes, particularly with the use of
a floating-catalyst method (Endo 1988; Tibbetts et al . 1994; Lake 2001). This tech-
nique is more controllable and cost efficient when compared with arc-discharge and
laser ablation methods (Ebbesen & Ajayan 1992; Thess et al . 1996; Journet et al .
1997; Liu et al . 1998). Various groups have been able to produce SWNTs for labo-
ratory experiments (Cheng et al . 1999; Colomer et al . 2000). Recently, experimental
groups have decided to use SWNTs produced using the high-pressure carbon monox-
ide (HIPCO) process developed by Smalley and his Rice University colleagues—this

Phil. Trans. R. Soc. Lond. A (2004)

2226 M. Endo and others

unit: nanometre

1.222
intensity (arb. units)

1.389
arc-discharge

1.223
1.667 1.389 0.989 0.845
CVD

100 200 300 1200 1400 1600 1800

Raman frequency (cm−1) Raman frequency (cm−1)
Figure 4. Raman spectra of arc-discharge and CVD derived SWNTs. The values inserted in
this figure are calculated through the correlation between diameter and RBM Raman frequency
(Bandow et al . 1998).

Figure 5. A graphical description of the tip-growth and root-growth nanotube models, in which
the catalytic particles are located at the tip and at the root, respectively. Carbon species are
illustrated as benzene molecules, and the base is the simplified model of the zeolite (Hayashi et
al . 2003).

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2227

(a) (b)

3 nm 2 nm

Figure 6. TEM images of the tubes with the catalytic particles (dark contrast) at (a) the root
of the tubes, and (b) the tip of the tube. This demonstrates that the tube growth in the zeolite
floating-substrate method occurs both at the root and at the tip of the tube (Hayashi et al .
2003).

have enabled the production of large amounts of high-purity SWNTs (Nikolaev et

al . 1999).
More recently, we reported an alternative route for the large-scale synthesis of
SWNTs by combining the use of catalytic substrates and floating methods (Hayashi
et al . 2003). The template (substrate) prevents metal particle aggregation, thus
resulting in the formation of high-purity SWNTs. The method is able to pro-
duce either individual nanotubes or nanotube bundles, exhibiting a wide range of
diameters (0.4–4 nm). In particular, nanosized zeolites were impregnated with Fe-
containing compounds (seeding method) and placed inside a furnace (ca. 1000 ◦ C)
together with benzene vapour, and H2 as the carrier gas. The resulting material was
purified via immersion in hydrofluoric acid (HF).
Scanning electron microscope (SEM) images (figure 3a) show web-like structures
attached to the surface of the zeolite template. Transmission electron microscopy
(TEM) studies confirm the presence of isolated SWNTs and bundles of nanotubes
of various diameters (figure 3b). We could attribute the diameter variations of the
tubes to the size of the catalytic particles embedded in the zeolite. For the case
of bundle formation, the diameter distribution of SWNTs within a bundle is small
(figure 3c), which may be due to the presence of homogeneous surfaces containing
catalyst particles of very similar size; growth conditions, such as carbon density,
reaction temperature and flow rate, should also be similar.
Raman spectroscopy is a useful technique for characterizing SWNTs because it
reveals information related to tube diameter and the degree of structural perfection of
the graphene sheets (Dresselhaus & Eklund 2000; Saito et al . 2000). Figure 4 displays
Raman spectra of arc-discharge and CVD-produced SWNTs. The radial breathing
modes (RBMs) are observed between 100 and 300 cm−1 , whereas the G-bands, with
a zone-folding spread, are observed at ca. 1590 cm−1 for both spectra. From the
spectra it is clear that CVD SWNTs exhibit a wide diameter distribution (0.845–

Phil. Trans. R. Soc. Lond. A (2004)

2228 M. Endo and others

1.667 nm) compared with those produced by the arc-discharge method. In addition,
the intensity of the D-band (ca. 1350 cm−1 ), in the case of CVD-derived SWNTs, is
higher than that of arc-discharge SWNTs (see Dresselhaus & Eklund (2000) and Saito
et al . (2000) for details on Raman spectroscopy). This result indicates a larger defect
concentration, including point defects due to a lower tube-formation temperature. It
is important to emphasize that each Raman spectrum exhibits different RBMs, thus
confirming the diversity of SWNTs produced, due to the different growth conditions
of the metal particles embedded in the zeolite template.
There are two major mechanisms for the catalytic growth of carbon nanotubes
depending on the position of the catalyst with respect to the substrate. Figure 5
shows both the tip-growth mechanism, whereby the catalyst particle is always located
at the tip of a growing tube, and the root-growth mechanism, in which the catalytic
particle is placed at the root (bottom) of the tube (Oberlin et al . 1976; Tibbetts
1984; Tibbetts et al . 1987; Baker 1989). For the SWNTs, catalytic particles can be
found at both: the roots and the tips of the tubes (figure 6). This indicates that
SWNTs are able to grow within these two frameworks. Moreover, we believe that
both growth mechanisms occur simultaneously and depend on the position of the
catalytic particle, which acts as a carbon ‘extruder’.
Regarding the bulk production of nanotubes (concentric graphene tubules) and
nanofibres (irregular carbon nanofilaments) for industrial applications, it is impor-
tant to mention that in the early 1990s, Hyperion Catalysis International, Inc. (Cam-
bridge, MA) started the large-scale production of MWNTs. This company has a wide
range of patents on synthesis and applications of nanotubes and nanofibres of carbon,
which expire in 2004. The Carbon Nanotech Research Institute (CNRI), a subsidiary
of Mitsui & Co., Ltd., plans to engage in developing technologies for the large-scale
production of 120 t of MWNTs annually. Others companies such as Applied Sci-
ences, Inc. (API) and Showa Denko (SDK) already have a large-scale production
capacity for MWNTs, which exhibit a wide distribution of diameters in the range
from 70 to 200 nm. The most interesting point is that all companies selected a cat-
alytic CVD method, and furthermore three companies (not Hyperion) adopted the
floating-reactant technique for the large-scale production of MWNTs. The devel-
opment of the floating-reactant/catalyst techniques allows a three-dimensional dis-
persion of the hydrocarbon together with the catalytic particles derived from the
pyrolysis of organometallic compounds. This results in a semi-continuous production
of MWNTs (Endo 1988; Tibbetts et al . 1994; Lake 2001; Collins et al . 2002).
Therefore, it is clear that a great deal of progress has been achieved related to
the bulk synthesis of carbon nanotubes. However, at present the most important
challenge is to tailor the chirality of SWNTs and MWNTs.

3. Purification of carbon nanotubes

Even though synthetic techniques have been improved to obtain high-purity carbon
nanotubes, the formation of byproducts containing impurities such as metal-encapsu-
lated nanoparticles, metal particles in the tip of a carbon nanotube, and amorphous
carbon has been an unavoidable phenomenon, because the metal nanoparticles are
essential for the nanotube growth. Thus, extensive research has been dedicated to
the purification of carbon nanotubes in order to remove foreign nanoparticles that
modify the physico-chemical properties of carbon nanotubes.

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2229

(a) (b) (c)

0.34 nm

10 nm 10 nm

Figure 7. (a) HR-TEM image of highly disordered carbon nanotubes. (b) HR-TEM image of an
annealed carbon nanotube at 2800 ◦ C showing linear, stiff graphene layers along the tube axis.
(c) Enlarged HR-TEM image of (b). Note that the distance between adjacent graphene layers
is 0.34 nm.

Chemical methods have been applied for purifying SWNTs. A generalized method
for SWNT purification developed by Smalley and co-workers (Liu et al . 1998) consists
of refluxing as-grown SWNTs in nitric acid solutions. Subsequently, more-effective
purification techniques have been developed with minor physical damage of the tubes
(Bandow et al . 1997; Rinzler et al . 1998; Dillon et al . 1999). Chattopadhyay et al .
(2002) reported the complete removal of metallic impurities through a sonication-
mediated treatment of as-grown SWNTs in a mixture of hydrofluoric and nitric acids.
Also, Martinez et al . (2002) reported a combined technique of high-temperature
air oxidation in conjunction with microwave acid treatments, thus removing a high
portion of metal particles in relatively short periods of time.
For MWNTs, high-temperature treatments in an inert atmosphere (graphitiza-
tion or annealing) are the most effective methods for removing structural defects
(heptagons and heptagon–pentagon pairs) or impurities such as metallic compounds
(Andrews et al . 2001; Grimes et al . 2001; Endo et al . 2001a).
In this context, figure 7 shows the structural transformation of a disordered
MWNT into a highly ordered multi-wall carbon nanotube. This crystallization is
a stepwise process:
(i) straightening and rearrangement of distorted graphene layers,
(ii) fusion between graphene layers, and
(iii) growth to larger graphene layers along the tube axis and removal of stacking
faults between graphene layers (Kim et al . 2003).

4. Electrochemical system
(a) Lithium-ion battery
The outstanding mechanical properties and the high surface-to-volume ratio (due
to their small diameter) make carbon nanotubes potentially useful as anode materi-
als (Endo et al . 1995; Tatsumi et al . 1999; Frackowiak et al . 1999; Wu et al . 1999;
Gao et al . 1999; Frackowiak & Beguin 2002) or as additives (Endo et al . 2001b) in
lithium-ion battery systems. An SEM image of an electrode containing 10 wt % of

Phil. Trans. R. Soc. Lond. A (2004)

2230 M. Endo and others

(a) (b)
100

95

cyclic efficiency (%)

90

85
added weight percents of nanotube
0 1 5 10
3 µm
80
0 10 20 30 40 50 60 70
cycle number
Figure 8. (a) SEM micrographs of the anode sheet containing carbon nanotubes in a commercial
lithium-ion battery. (b) The cyclic efficiency of synthetic graphite, heat treated at 2900 ◦ C, as a
function of weight percent, in the range 0–1.5 V, with a current density of 0.2 mA cm−2 .

carbon nanotubes as the additive displays a homogeneous distribution of nanotubes

in synthetic graphite (figure 8a). Figure 8b reveals the cyclic efficiency of a syn-
thetic graphite anode as a function of the weight percent of carbon nanotube. With
increasing weight percent of carbon nanotubes, the cyclic efficiency of the synthetic
graphite battery anode increases continuously, and, in particular, when 10 wt % of
the nanotubes was added, the cyclic efficiency was maintained at almost 100% up
to 50 cycles. At higher concentrations, the nanotubes interconnect graphite powder
particles together to form a continuous conductive network. The characteristics of a
carbon nanotube when used as a filler in the electrodes of lithium-ion batteries can
be summarized as follows.
(i) The small diameter of the nanotube makes it possible to distribute the nano-
tubes homogeneously in the thin electrode material and to introduce a larger
surface area to react with the electrolyte.
(ii) The improved electrical conductivity of the electrode is related to the high
electrical conductivity of the tubes, and the function of the electrical bridge
between graphite particles.
(iii) The relatively high intercalation ability of nanotubes did not in itself lower the
capacity of anode materials upon cycling.
(iv) A high flexibility of the electrode is also achieved due to the network formation
of the nanotube in a tube-mat structure.
(v) The electrode has high endurance due to the presence of nanotubes, which
absorb the stress caused by intercalation of lithium ions.
(vi) Improved penetration of the electrolyte due to the homogeneous distribution
of the tubes surrounding the anode material.

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2231

100
addition of CNTs
to negative plate

discharge capacity (%)

80

60

no addition
40

0 200 400 600 800 1000

cycle number
Figure 9. The effects of carbon nanotubes embedded in a conductive filler in polyvinylidene-
derived carbon electrode and compared with a carbon black/polyvinylidene composite.

(vii) The cyclic efficiency of the lithium-ion battery was improved for a relatively
long cycle when compared with that of carbon black.

(b) Additives to the electrodes of lead-acid batteries

In order to increase the conductivity of electrodes in lead-acid batteries, differ-
ent weight percents of carbon nanotubes are added to the active anode material
(with average diameters of ca. 2–5 mm) of the positive electrode. The resistivity of
the electrode is lowered for the case of 1.5% nanotube addition. When this sam-
ple (0.5–1 wt %) is incorporated in the negative electrode, the cycle characteristics
are greatly improved compared with those of an electrode without additive (fig-
ure 9) (Endo et al . 2001b). This is probably due to the ability of carbon nanotubes
to act as a physical binder, resulting in electrodes that undergo less mechanical
disintegration and shedding of their active material. Therefore, it is expected that
the use of carbon nanotubes as an electrode’s filler should produce an enhanced
cyclic behaviour for electrodes in lead-acid batteries compared with electrodes using
conventional graphite powder, because the unusual morphology of the carbon nano-
tube, such as the concentric orientation of their graphite crystallites along the fibre
cross-section, induces a high resistance towards oxidation, and furthermore the nano-
tube network embedded in the polymer would enhance the reactivity of the elec-
trode.

(c) The electric double-layer capacitor

The merit of the electric double-layer capacitor (EDLC) is considered to be a
high discharge rate (Conway 1999), which makes them applicable as a hybrid energy
source for electric vehicles and portable electric devices (Miyadera 2002). EDLCs
containing carbon nanotubes in the electrode exhibit relatively high capacitances
resulting from the high surface area accessible to the electrolyte (Niu et al . 1997;
An et al . 2001; Frackowiak & Beguin 2002). On the other hand, the most important
factor in commercial EDLCs is considered to be the overall resistance. In this context,
carbon nanotubes with strong electrical and mechanical properties can be used as an
electrical conductive additive in the electrode of EDLC. It has been demonstrated

Phil. Trans. R. Soc. Lond. A (2004)

2232 M. Endo and others

10 nm

Figure 10. An HR-TEM image of highly dispersed Pt nanoparticles deposited on both

outer and inner surfaces of shortened stacked-cone nanotubes/nanotubes.

that the addition of carbon nanotubes results in an enhanced capacity at higher

current densities, when compared with electrodes containing carbon black (Takeda
et al . 2001).

(d ) Fuel cells
Fuel cells have been considered as the next generation of energy devices because
this type of system transforms the chemical reaction energy from hydrogen and oxy-
gen into electric energy (Williams 2001). Carbon nanotubes decorated with metal
nanoparticles as the electrode have doubled the performance of the fuel cell, owing
to the increased catalytic activity of nanotube-based electrodes (Britto et al . 1999;
Che et al . 1999; Yoshitake et al . 2002). In this context, we have reported the efficient
impregnation of Pt nanoparticles (outer diameter less than 3 nm) on cup-stacked-
type carbon nanotubes (Endo et al . 2003). The method involves dispersion of the
fibres in H2 PtCl6 , followed by low-temperature annealing. The Pt particle deposition
is always homogeneous, and can be controlled selectively on the outer or inner core
using the hydrophobic nature of the material (see figure 10). Since the Pt particle
activity on the fibres is high, this material could find application as an efficient cata-
lyst or biological device. It may be that carbon nanotube technology will contribute
to the development of fuel cells as a catalyst support and also as a main component
of bipolar systems. However, additional basic and applied research is necessary.

5. Multifunctional fillers in polymer composite

It has been shown that carbon nanotubes could behave as the ultimate one-dimen-
sional material with remarkable mechanical properties (Lu 1997; Li et al . 2000). The
density-based modulus and strength of highly crystalline SWNTs are 19 and −56
times that of steel. Based on a continuum shell model, the armchair tube exhibits
larger stress–strain response than the zigzag tube under tensile loading (figure 11).

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2233
150

D = 1.37 nm

armchair (10,10)
tensile stress (GPa)

100

zigzag (17,0)

50 CNT
σ b = 11–63 GPa
ε b ~ 12%
E = 0.94 TPa
D = 1.35 nm

0 5 10 15 20
strain, ε (%)
Figure 11. Stress–strain response of a carbon nanotube under tensile loading.

human hair
nanogear

0.2 mm

0.1 mm

2 µm

Figure 12. SEM image of the smallest working gear (carbon nanotube/nylon composite);
the inset shows the fractured surface.

Strong mechanical properties of carbon nanotubes due to a strong carbon–carbon

covalent bond are highly dependent upon the atomic structure of nanotubes and the
number of shells. Moreover, carbon nanotubes exhibit strong electrical and thermal
conducting properties. Therefore, carbon nanotubes (single and multi-walled) have
been studied intensively as fillers in various matrices, especially polymers (Ajayan
et al . 1994; Lau & Hui 2002; Calvert 1999; Mamedov et al . 2002; Zhan et al . 2003).

Phil. Trans. R. Soc. Lond. A (2004)

2234 M. Endo and others

The best use of the intrinsic properties of these fibrous nanocarbons in polymers
can be achieved by optimizing the interface interaction of the nanotube surface and
the polymer. Therefore, surface treatments via oxidation could be used in order to
improve adhesion properties between the filler and the matrix. This results in a good
stress transfer from the polymer to the nanotube. There are various surface oxida-
tive processes, such as electrochemical, chemical and plasma techniques. From the
industrial point of view, ozone treatment is a very attractive technique. In addition,
the dispersion of the nanotubes/nanofibres in the polymer should be uniform within
the matrix.
The smallest working composite gear has been prepared by mixing nanotubes into
molten nylon and then injecting into the tiny mould. As shown in figure 12, this gear
is as small as the diameter of a human hair. This piece exhibits a high mechanical
strength, high abrasion resistance and also good electrical and thermal conductivity.
When cup-stacked-type carbon nanotubes are incorporated in polypropylene, the
improvement of the tensile strength is very noticeable (up to 40%). This remarkable
result can be explained by the particular morphology of cup-stacked-type carbon
nanotubes. In other words, a large portion of edge sites on the outer surface of the
nanotubes might act as nucleation sites, resulting in good adhesion between nano-
tubes and polymers (good stress transfer). Recently, various studies on the nucle-
ation effect of nanotubes on the crystallization of semi-crystalline polymers have
been reported (Valentini et al . 2003; Bhattacharyya et al . 2003; Cadek et al . 2003).

6. Conclusion
This account has mainly described the possible routes to large-scale synthesis of
carbon nanotubes (single and multi-walled), with emphasis on their applications in
electrochemical systems and polymer nanocomposites. The unique electronic prop-
erties of nanotubes also make them good candidates in the electronics industry for
replacing silicon-based technologies with those based on nanocarbons (Collins &
Avouris 2002). At present, researchers are working on the following areas in order to
apply carbon nanotubes in emerging technologies.
(i) Production of defect-free and high-purity carbon nanotubes.
(ii) Establishment of useful techniques for quantifying the number of defects (their
types, where they are, etc.) in the nanotube structure.
(iii) Development of effective purification techniques (below the parts per million
level) for the metal particles within carbon nanotubes, especially for biological
and electronic applications.
(iv) Achieving homogeneous carbon nanotube dispersions in polymer composites.
The possible applications of carbon nanotubes range from electronics to field-
emission displays, energy-storage devices and functional fillers in composites. These
have attracted both industrial and academic interest. Therefore, it is important that
some of the basic knowledge is transferred to industry very shortly so that real and
novel technologies appear commercially.
We are thankful for financial support from the CLUSTER of Ministry of Education, Culture,
Sports, Science and Technology. We also thank CONACYT-México, grants W-8001-Millennium
Initiative (H.T., M.T.), 37589-U (M.T.) and 41464-Inter American Collaboration (M.T.).

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2235

References
Ajayan, P. M. & Zhou, O. Z. 2001 Application of carbon nanotubes. In Carbon nanotubes.
Topics in applied physics (ed. M. S. Dresselhaus, G. Dresselhaus & Ph. Avouris), vol. 80,
pp. 381–425. Springer.
Ajayan, P. M., Stephan, O., Colliex, C. & Trauth, D. 1994 Aligned carbon nanotube arrays
formed by cutting a polymer resin–nanotube composite. Science 265, 1212–1214.
An, K. H., Kim, W. S., Park, Y. S., Moon, J. M., Lim, S. C., Lee, Y. S. & Lee, Y. H. 2001
Electrochemical properties of high power supercapacitors using singlewalled carbon nanotubes
electrodes. Adv. Mater. 11, 387–392.
Andrews, R., Jacques, D., Qian, D. & Dickey, E. C. 2001 Purification and structural annealing
of multiwalled carbon nanotubes at graphitization temperatures. Carbon 39, 1681–1687.
Baker, R. T. K. 1989 Catalytic growth of carbon filaments. Carbon 27, 315–323.
Bandow, S., Rao, A. M., Thess, A. & Smalley, R. E. 1997 Purification of single wall carbon
nanotubes by microfiltration. J. Phys. Chem. B 101, 8839–8842.
Bandow, S., Asaka, S., Saito, Y., Rao, A. M., Grigorian, L., Richter, E. & Eklund, P. C. 1998
Effect of the growth temperature on the diameter distribution and chirality of single-wall
carbon nanotubes. Phys. Rev. Lett. 80, 3779–3782.
Baughman, R. H., Zakhidov, A. A. & De Heer, W. A. 2002 Carbon nanotubes—the route toward
applications. Science 297, 787–792.
Bhattacharyya, A. R., Sreekumar, T. V., Liu, T., Kumar, S., Ericson, L. M., Hauge, R. H.
& Smalley, R. E. 2003 Crystallization and orientation studies in polypropylene/single wall
carbon nanotube composite. Polymer 44, 2373–2377.
Britto, P. J., Santhanam, K. S. V., Rubio, A., Alonso, A. & Ajayan, P. M. 1999 Improved charge
transfer at carbon nanotube electrodes. Adv. Mater. 11, 154–157.
Cadek, M., Coleman, J. N., Barron, V., Hedicke, K. & Blau, W. J. 2003 Morphological and
mechanical properties of carbon-nanotube-reinforced semicrystalline and amorphous polymer
composites. Appl. Phys. Lett. 81, 5123–5125.
Calvert, P. 1999 Nanotube composites: a recipe for strength. Nature 399, 210–211.
Chattopadhyay, D., Galeska, I. & Papadimitrakopoulos, F. 2002 Complete elimination of metal
catalysts from single wall carbon nanotubes. Carbon 40, 985–988.
Che, G., Lakshmi, B. B., Fisher, E. R. & Martin, C. R. 1999 Carbon nanotubule membranes
for electrochemical energy storage and production. Nature 393, 346–349.
Cheng, H., Li, F., Su, G., Pan, H. & Dresselhaus, M. S. 1999 Large-scale and low-cost synthesis
of single-walled carbon nanotubes by the catalytic pyrolysis of hydrocarbons. Appl. Phys.
Lett. 72, 3282–3284.
Collins, P. G. & Avouris, P. 2002 Nanotubes for electronics. Scientific American, December,
pp. 62–69.
Collins, S., Brydson, R. & Rand, B. 2002 Structural analysis of carbon nanofibres grown by the
floating catalyst method. Carbon 40, 1089–1100.
Colomer, J. F., Stephan, C., Lefrant, S., Van Tendeloo, G., Willems, I., Konya, Z., Fonseca, A.,
Laurent, Ch. & Nagy, J. B. 2000 Large-scale synthesis of single-wall carbon nanotubes by
catalytic chemical vapor deposition (CCVD) method. Chem. Phys. Lett. 317, 83–89.
Conway, B. E. 1999 Electrochemical supercapacitors—scientific fundamentals and technological
applications. Dordrecht: Kluwer Academic.
Dillon, A. C., Gennett, T., Jones, K. M., Alleman, J. L., Parilla, P. A. & Heben, M. J. 1999
A simple and complete purification of single-walled carbon nanotube materials. Adv. Mater.
11, 1354–1358.
Dresselhaus, M. S. & Eklund, P. C. 2000 Phonons in carbon nanotubes. Adv. Phys. 49, 705–814.
Dresselhaus, M. S., Dresselhaus, G. & Eklund, P. C. 1996 Science and fullerenes and carbon
nanotubes, 1st edn, pp. 1–505. Academic.

Phil. Trans. R. Soc. Lond. A (2004)

2236 M. Endo and others

Ebbesen, T. W. & Ajayan, P. M. 1992 Large-scale synthesis of carbon nanotubes. Nature 358,
220–222.
Endo, M. 1988 Grow carbon fibers in the vapor phase. CHEMTECH 18, 568–576.
Endo, M., Nakamura, J., Sasabe, Y., Takahashi, T. & Inagaki, M. 1995 Lithium secondary
battery using vapor grown carbon fibers as a negative electrode and analysis of the electrode
mechanism by TEM observation. Trans. IEE Jpn A 115, 349–356.
Endo, M., Kim, Y. A., Fukai, Y., Hayashi, T., Terrones, M., Terrones, H. & Dresselhaus, M. S.
2001a Comparison study of semi-crystalline and highly crystalline multiwalled carbon nano-
tubes. Appl. Phys. Lett. 79, 1531–1533.
Endo, M., Kim, Y. A., Hayashi, T., Nishimura, K., Matushita, T., Miyashita, K. & Dressel-
haus, M. S. 2001b Vapor-grown carbon fibers (VGCFs): basic properties and their battery
applications. Carbon 39, 1287–1297.
Endo, M., Kim, Y. A., Ezaka, M., Osada, K., Yanagisawa, T., Hayashi, T., Terrones, M. &
Dresselhaus, M. S. 2003 Selective and efficient impregnation of metal nanoparticles on cup-
stacked-type nanofibers. Nano Lett. 3, 723–726.
Frackowiak, E. & Beguin, F. 2002 Electrochemical storage of energy in carbon nanotubes and
nanostructured carbons. Carbon 40, 1775–1787.
Frackowiak, E., Gautier, S., Gaucher, H., Bonnamy, S. & Beguin, F. 1999 Electrochemical storage
of lithium in multiwalled carbon nanotubes. Carbon 37, 61–69.
Gao, B., Kelinhammes, A., Tang, X. P., Bower, C., Wu, Y. & Zhou, O. 1999 Electrochemical
intercalation of single-walled carbon nanotubes with lithium. Chem. Phys. Lett. 307, 153–157.
Ge, M. & Sattler, K. 1993 Vapor-condensation generation and STM analysis of fullerene tubes.
Science 260, 515–518.
Grimes, C. A., Dickey, E. C., Mungle, C., Ong, K. G. & Qian, D. 2001 Effect of purification of
the electrical conductivity and complex permittivity of multiwall carbon nanotubes. J. Appl.
Phys. 90, 4134–4137.
Harris, P. J. F. 1999 Carbon nanotubes and related structures: new materials for the twenty-first
century, 1st edn, pp. 1–293. Cambridge University Press.
Hayashi, T., Kim, Y. A., Matoba, T., Ezaka, M., Nishimura, K., Tsukada, T., Endo, M. &
Dresselhaus, M. S. 2003 The smallest freestanding single-wall carbon nanotube. Nano Lett.
3, 887–889.
Iijima, S. 1991 Helical microtubules of graphic carbon. Nature 354, 56–58.
Journet, C., Maser, W. K., Bernier, P., Loiseau, A., Delachapelle, M. L., Lefrant, S., Deniard,
P., Lee, R. & Fisher, J. E. 1997 Large-scale production of single-walled carbon nanotubes by
the electric-arc technique. Nature 388, 756–758.
Kim, Y. A., Osada, K., Hayashi, T., Endo, M. & Dresselhaus, M. S. 2003 Annealing effect on
disordered multi-wall carbon nanotubes. Chem. Phys. Lett. 380, 319–324.
Kroto, H. W., Heath, J. R., O’Brien, S. C., Curl, R. F. & Smalley, R. E. 1985 C60: Buckmin-
sterfullerene. Nature 318, 162–163.
Lake, M. L. 2001 Large scale production of VGCF. In Carbon filaments and nanotubes: common
origins, differing applications? Applied Science, Series E, vol. 372, pp. 187–196. Dordrecht:
Kluwer Academic.
Lau, K. T. & Hui, D. 2002 The revolutionary creation of new advanced materials–carbon nano-
tube composites. Composites B 33, 263–277.
Li, F., Cheng, B. S., Su, G. & Dresselhaus, M. S. 2000 Tensile strength of single-walled carbon
nanotubes directly measured from their macroscopic ropes. Appl. Phys. Lett. 77, 3161–3163.
Liu, J. (and 14 others) 1998 Fullerene pipes. Science 280, 1253–1256.
Lu, J. P. 1997 Elastic properties of single and multilayered nanotubes. J. Phys. Chem. Solids
58, 1649–1652.

Phil. Trans. R. Soc. Lond. A (2004)

 Applications of carbon nanotubes in the twenty-first century 2237

Mamedov, A. A., Kotov, N. A., Prato, M., Guldi, D. M., Wicksted, J. P. & Hirsch, A. 2002
Molecular design of strong single-wall carbon nanotube/polyelectrolyte multilayer composites.
Nature Mater. 1, 190–194.
Martinez, M. T., Callejas, M. A., Benito, A. M., Maser, W. K., Cochet, M., Andres, J. M.,
Schreiber, J., Chauvet, O. & Fierro, J. L. 2002 Microwave single walled carbon nanotubes
purification. Chem. Commun., pp. 1000–1001.
Mintmire, J. W. & White, C. T. 1995 Electronic and structural properties of carbon nanotubes.
Carbon 33, 893–902.
Miyadera, K. 2002 Development of ES3 small sized low-fuel consumption vehicle. Toyota Tech.
Rev. 52, 22–27.
Nikolaev, P., Bronikowski, M. J., Bradley, R. K., Rohmund, F., Colbert, D. T., Smith, K. A.
& Smalley, R. E. 1999 Gas-phase catalytic growth of single-walled carbon nanotubes from
carbon monoxide. Chem. Phys. Lett. 313, 91–97.
Niu, C., Sickel, E. K., Hoch, R., Moy, D. & Tennent, H. 1997 High power electrochemical
capacitors based on carbon nanotube electrodes. Appl. Phys. Lett. 70, 1480–1482.
Oberlin, A., Endo, M. & Koyama, T. 1976 Filamentous growth of carbon through benzene
decomposition. J. Cryst. Growth 32, 335–349.
Rinzler, A. G., Liu, J., Dai, H., Nikolaev, P., Huffman, C. B. & Rodriguez-Marcias, F. J. 1998
Large-scale purification of single-wall carbon nanotubes: process, product, and characteriza-
tion. Appl. Phys. A 67, 29–37.
Saito, R., Dresselhaus, G. & Dresselhaus, M. S. 1998 Physical properties of carbon nanotubes,
1st edn, pp. 1–259. London: Imperial College Press.
Saito, R., Dresselhaus, G. & Dresselhaus, M. S. 2000 Trigonal warping effect of carbon nano-
tubes. Phys. Rev. B 61, 2981–2990.
Takeda, T., Takahashi, R., Kim, Y. J., Koshiba, K., Ishi, K., Kasahi, T. & Endo, M. 2001 Effect of
VGCF addition into the carbon electrode for electric double layer capacitor (EDLC). TANSO
196, 14–18.
Tanaka, K., Yamabe, T. & Fukui, K. 1999 The science and technology of carbon nanotubes, 1st
edn, pp. 1–190. Elsevier.
Tatsumi, K., Zaghib, K., Abe, H., Higuchi, S., Ohsaki, T. & Sawada, Y. 1999 A modification in
the preparation process of a carbon whisker for the anode performance of lithium rechargeable
batteries. J. Power Sources 54, 425–427.
Thess, A. (and 14 others) 1996 Crystalline ropes of metallic carbon nanotubes. Science 273,
483–487.
Tibbetts, G. G. 1984 Why are carbon filaments tubular? J. Cryst. Growth 66, 632–638.
Tibbetts, G. G., Devour, M. G. & Rodda, E. J. 1987 An adsorption–diffusion isotherm and its
application to the growth of carbon filaments on iron catalyst particles. Carbon 25, 367–375.
Tibbetts, G. G., Bernnardo, C. A., Gorkiewicz, D. W. & Alig, R. L. 1994 Role of sulfur in the
production of carbon fibers in the vapor phase. Carbon 32, 569–576.
Valentini, L., Biagiotti, J., Kenny, J. M. & Santucci, S. 2003 Effects of single-walled carbon
nanotubes on the crystallization behavior of polypropylene. J. Appl. Polym. Sci. 87, 708–
713.
Wilder, J. W. G., Venema, L. C., Rinzler, A. G., Smalley, R. E. & Dekker, C. 1998 Electronic
structure of atomically resolved carbon nanotubes. Nature 391, 59–62.
Williams, M. C. 2001 Status and promise of fuel cell technology. Fuel Cells 2, 87–91.
Wu, G. T., Wang, C. S., Zhang, X. B., Yang, H. S., Qi, Z. F., He, P. M. & Li, W. Z. 1999
Structure and lithium insertion properties of carbon nanotubes. J. Electrochem. Soc. 146,
1696–1701.
Yasuda, E., Inagaki, M., Kaneko, K., Endo, M., Oya, A. & Tanabe, Y. 2003 Carbon alloys: novel
concept to develop carbon science and technology, 1st edn, pp. 1–569. Elsevier.

Phil. Trans. R. Soc. Lond. A (2004)

2238 M. Endo and others

Yoshitake, T., Shimakawa, Y., Kuroshima, S., Kimura, H., Ichihashi, T., Kubo, Y., Kasuya,
D., Takahashi, K., Kohai, F., Yudasaka, M. & Iijima, S. 2002 Preparation of fine platinum
catalyst supported on single-wall carbon nanohorns for fuel cell application. Physica B 323,
124–126.
Zhan, G. D., Kuntz, J. D., Wan, J. & Mukherjee, A. K. 2003 Single-wall carbon nanotubes as
attractive toughening agents in alumina-based nanocomposites. Nature Mater. 2, 38–42.

Phil. Trans. R. Soc. Lond. A (2004)