June 2, 2010 15:13 WSPC/S0218-625X S0218625X10013904

Surface Review and Letters, Vol. 17, No. 1 (2010) 87–91

c World Scientific Publishing Company

DOI: 10.1142/S0218625X10013904

DIRECT GROWTH OF VERTICALLY ALIGNED

CARBON NANOTUBES ON CU FOILS FOR
APPLICATIONS IN LITHIUM ION BATTERIES

BYEONG-JOO LEE, JIN-JU KIM, KANG-HEE CHOI, EUI-CHUL SHIN,

WAN-JUN KIM, SUNG-MAN LEE and GOO-HWAN JEONG∗
Department of Advanced Materials, Science and Engineering,
Kangwon National University, Chuncheon,
Kangwon 200-701, Korea
∗
ghjeong@kangwon.ac.kr

Received 22 January 2009

We report direct growth of vertically aligned carbon nanotubes (VCNTs) on Cu foils using
thermal chemical vapor deposition and present the feasibility of possible applications as anode
materials in lithium ion batteries. The VCNTs were vertically standing on the Cu foils which
were covered with catalytic iron and alumina buffer layers. The growth temperature was 725◦ C
and acetylene under atmospheric pressure was used as a hydrocarbon source. The VCNT grown
had mean diameter of 5.8 nm and showed electrical ohmic contact to Cu foils. Electrochemical
properties of Li ion battery cell using VCNT anode were examined and high capacitance was
observed.

Keywords: Carbon nanotubes; vertical growth; Cu foils; lithium ion battery.

1. Introduction been made as pastes by mixing with organic binder

From a practical viewpoint, carbon nanotubes
(CNTs) have been attracting much attention since
they have been expected to be used in various areas
by virtue of their outstanding physical, electrical,
and chemical properties.1 As a shortcut to rational
applications, controlled growth of designed struc-
tures on any substrate is conceived as basic require-
ment although it still remained to be solved. Among
the various applications, CNTs as an electron emis-
sion source, device interconnects, and electrochem-
ical energy storage applications standing on metal
substrates are definitely beneficial because they can
maintain robust mechanical stability and high con-
ductivity between CNT and metal interfaces.2–4 For
instance, CNTs as electron emission sources have
and printed on metallic cathodes.5 Furthermore,
for electrochemical applications such as superca-
pacitors or secondary batteries, CNTs have also
been employed as mixtures with binding materi-
als to ensure enhanced adhesion on electrodes.6
Also, some researchers have presented a direct
spray deposition of CNT onto current collector in
order to exclude the use of binder in the system.7
However, the rates of ion exchange through the
entangled CNT structures deposited are ques-
tionable and the device reliability in terms of
long term performance would not be enough to
guarantee at present. From the background, the
approach using direct growth of vertically grown
CNTs (VCNTs) on metal electrodes and employing
three-dimensional configurations have recently been

∗
Corresponding author.

87
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88 B.-J. Lee et al.
proposed8–10 especially in the electrochemical appli-
cations of CNTs. Here, we demonstrate the direct
growth of VCNTs on commercial Cu foils and present
electrochemical properties using the VCNT-grown
Cu anode system.
2. Experimental
To directly apply as an active anode electrode, a
commercial Cu foil having 1 µm thick was used as
substrate for VCNT growth. Fe or Ni layers as
CNT growth catalysts were deposited by electron
beam evaporation. The effect of supporting layer
between catalyst film and Cu foils was investigated
using alumina layer (Al2 O3 ). The CNT growth was
carried out in thermal chemical vapor deposition
(CVD) unit. After the film deposition, the Cu foils
were inserted into the quartz tube and heated to
optimized growth temperature of 725◦ C. Air oxi-
dation of the catalyst was performed at 725◦ C for
10 min under atmospheric pressure, then the cham-
ber quickly evacuated to 10−3 Torr and filled with
Ar (500 sccm) and H2 (500 sccm) gases to reduce the
oxidized catalyst surface.11 After 10 min hold under
the reduction environment, C2 H2 gas of 50 sccm was
additionally introduced for 15 min to grow VCNT.
The CVD furnace was air cooled to ambient temper-
ature after the growth process. The growth proce-
dure was schematically shown in Fig. 1.
Surface morphologies of Cu foils were investi-
gated using atomic force microscope (AFM, Park
Systems XE-70). For structure observation and
height estimation of the VCNT, scanning electron
microscope (SEM, COXEM CX-100) was employed.
Fig. 1. Schematic flow of CNT growth process.
A transmission electron microscopy (TEM, JEOL
JEM2100 F) was used to analyze the precise tube
diameter and wall number. A micro-Raman spec-
troscopy (HORIBA ARAMIS) using 532 nm exci-
tation wavelength was used to analyze the grown
VCNT. Two-point proven I–V characteristics were
measured to verify the electrical connection between
VCNT and Cu foils at room temperature.
Electrochemical tests were performed using coin
cell structures with lithium foil as a counter elec-
trode. The electrolyte was 1 M LiPF6 solution in a
mixture of ethylene carbonate (50 vol.%) and diethyl
carbonate (50 vol.%). The charge–discharge tests
were carried out in a constant current mode with
cutoff voltages of 0.005 and 2.0 V until 30th cycle
and changed to 0.005 and 3.0 V for subsequent tests
(vs Li/Li+ ).
3. Results and Discussion
We tried to directly grow CNT on Cu foils which
might act as the most effective electron path from the
CNT and representative results are shown in Fig. 2.
(a)
(b)
(c)
Fig. 2. SEM images showing CNT growth features with-
out supporting layer. (a) 1 nm Fe/Cu foil, (b) 10 nm
Fe/Cu foil, and (c) 10 nm Ni/Cu foil.
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Direct Growth of Vertically Aligned Carbon Nanotubes on Cu Foils 89

We varied Fe film thickness from 1 to 10 nm and also
used 10 nm Ni layer as shown in Figs. 2(a)–2(c),
respectively. It was found that CNT growth was pos-
sible but it neither produced uniform CNT layer nor
VCNT on the Cu foils.
We thereafter utilized Al2 O3 supporting layer
between Fe catalyst layer and Cu foils using the
e-beam evaporation. The thickness of Al2 O3 was var-
ied and optimized at 10 nm for VCNT growth. Actu-
ally, Al2 O3 layer was known to act as a buffer layer
of Fe diffusion into substrates to prevent formation
of inactive compounds or alloys.12 In addition, a
specific chemical interaction between Al2 O3 and Fe
has recently reported that Al2 O3 restricts Fe surface
mobility resulting in narrow catalyst particle size dis-
tribution and the rational nucleation of VCNT.13
Figures 3(a)–3(c) are SEM images showing the evolu-
tion of surface morphologies of the bare Cu foils, after
1 nm Fe/10 nm Al2 O3 deposition, and after annealing
of 1 nm Fe/10 nm Al2 O3 /Cu foils, respectively. Cor-
responding and more magnified surface morphologies
were given as AFM topographic images in Figs. 3(d)–
3(f). It was found that the surface morphologies of
the Cu foils look similar before anneal treatment but
the morphology was changed after 10 min annealing
at 725◦ C [Figs. 3(c) and 3(f)]. It was expected that
the nanoparticles observed might be iron oxides and
formed from the 1 nm Fe layer. The mean diameter
of the particles was estimated to be 5.8 nm from the
size analysis as presented in Fig. 3(g).
Figure 4(a) shows a tilted SEM image of VCNT
grown using the optimized growth condition with
Fe 1 nm/Al2 O3 10 nm/Cu foil substrate. The VCNT
length on Cu reached 260 µm which is similar to
that of SiO2 substrate case (not shown). It was
found that the effect of substrate materials can be
ignored if we utilize buffer layer. Inset in Fig. 4(a)
is a representative TEM image showing the VCNTs
were consisted of mostly triple-walled and partially
double-walled CNTs. The diameters of the tubes
were quite uniform with values around 5–6 nm, which
is almost the same as catalytic nanoparticle mean
size in Fig. 3(f). Figure 4(b) shows a representative
result of Raman spectroscopy, which is a powerful
and convenient tool for estimating structural com-
pleteness of CNTs by comparing the peak intensities
of structure disorder induced peak (at ∼1300 cm−1 ,
ID ) and tangential stretching vibration mode of
graphite (at ∼1590 cm−1 , IG ). Here, the ID /IG val-
ues of the grown VCNT were similar to those of usual
thin-walled CNT, which range from 0.8 to 1.2.
According to the above described optimization
process, we could grow VCNTs on Cu foils. Here, the
important concern for application is electrical con-
tact between VCNT and Cu foils. We utilized two-
point probe to obtain I–V character from the sample.
One probe was directly contacted on Cu foils and the
other is placed on the top surface of site selectively
grown VCNTs. The height of VCNTs used for mea-
surements was over 600 µm with prolonged growth

(a) (b) (c)

(g)
(d) (e) (f)

Fig. 3. SEM and corresponding AFM images showing surface morphologies. (a, d) Bare Cu foil, (b, e) Cu foil covered
with 1 nm Fe/10 nm Al2 O3 , (c, f) annealed 1 nm Fe/10 nm Al2 O3 /Cu foil, and (g) a histogram showing diameter
distribution of catalyst particles obtained from the annealed substrates.
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90 B.-J. Lee et al.

(a)

Fig. 5. A representative current–voltage (I–V) curve of

VCNT grown on Cu foils.

(b)

Fig. 4. (a) SEM image showing VCNT directly grown

on Cu foils. Inset shows TEM image of the tubes.
(b) Raman profile recorded from the same sample of
Fig. 4(a).

time. The repeated measurements were conducted to

ensure the consistency of the data. The typical result
measured was shown in Fig. 5. It was found that elec-
trical contact between the VCNT and Cu substrate
was ohmic with small resistance of 10 Ω m which is
still larger than pure Cu (∼10−8 Ω m) or individual
CNT (∼10−4 Ω m). Actually the values of the resis-
tance were changed by different loading pressures of
the probe on the tubes. However, the ohmic contact
was consistently observed in all the measurements,
which means we can utilize this Fe/Al2 O3 system as
an active electrode for electrochemical applications
such as supercapacitors or lithium ion secondary bat-
teries. To sum up briefly, we succeeded in the direct
growth of VCNT on commercial Cu foils with the Fig. 6. Charge–discharge characteristics for (a) the 1st
and 2nd cycles, (b) 25th, (c) 30th, and (d) 37th cycles.
help of alumina buffer layer and also confirmed that
The cutoff voltages were changed at the 30th cycle. Color
the structures were electrically conductive. online.
 April 13, 2010 11:29 WSPC/S0218-625X
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Direct Growth of Vertically Aligned Carbon Nanotubes on Cu Foils
Finally, we examined electrochemical properties
using Cu anode with vertically standing VCNT and
representative charge–discharge curves were shown
in Fig. 6. As we can see in other reports using CNT
deposited anodes, discharge plateau was observed
about 0.8 V cell voltages which is known to the for-
mation of solid electrolyte interface film on the tube
surfaces.14,15 In the subsequent cycles, the volt-
age plateau disappeared and a reversible capac-
ity ∼280 mAh/g is obtained [Fig. 6(a)]. It was
found that the irreversibility of the system grad-
ually decreased [Fig. 6(b)]. Interestingly, when we
changed cutoff voltage to 0.005 and 3.0 V, the capac-
ity of the system significantly increased [Figs. 6(c)
and 6(d)]. This means that insertion site, interac-
tion between Li ion and CNT, and electrical con-
tact between tube and Cu foils might be responsible
for observed capacity change. To understand exact
insertion–extraction mechanism and also to enhance
electrochemical performances of the system, further
investigation is underway.
4. Conclusions
We have demonstrated growth of VCNTs on com-
mercial Cu foils for direct use in lithium ion batteries
as an effective anode. The growth temperature and
time yielding VCNT with 260 µm height were opti-
mized at 725◦ C and 15 min, respectively. The VCNTs
had good electrical contact although 10 nm alumina
buffer layer was inserted between 1 nm Fe film and
Cu foils. Electrochemical properties of Li ion battery
with VCNT anode were examined and it was found
that high capacity of 3000 mAh/g was obtained in
the first discharge. A large amount of irreversible loss
91
was observed in the first discharge and was removed
from the subsequent charge–discharge cycles. Fur-
ther study to enhance electrochemical properties are
undergoing by modification of VCNT structures such
as tube length or density.
Acknowledgments
We thank Mr. J. H. Cho and S. J. Park of Seoul
National University for technical support of TEM
and electrical measurements, respectively. G. H.
Jeong thanks Prof. Eleanor E. B. Campbell of Edin-
burgh University for consistent support. This study
was supported by 2008 Research Grant from Kang-
won National University.
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