571~576 ()

Journal of the Chinese Society of Mechanical Engineers, Vol.28, No.6, pp.571~576 (2007)
-571
Directly Grown Carbon Nanotubes Applied in
Direct Methanol Fuel Cell
Chen-Hao Wang*, He-Yun Du**, Yu-Tai Tsai***, Hsin-Cheng Hsu***,
Han-Chang Shih***, Li-Chyong Chen* and Kuei-Hsien Chen*
Keywords: carbon nanotube, direct methanol fuel cell,
direct growth, methanol oxidation.
ABSTRACT
Carbon nanotubes (CNTs) were directly grown on
a carbon cloth (DGCNTs), which were employed as the
electrocatalyst support in the direct methanol fuel cell
(DMFC). The CNTs were prepared by an iron-assisted
catalyst grown method using the microwave
plasma-enhanced chemical vapor deposition. From the
morphological analysis, the as-prepared DGCNT is a
multi-walled and bamboo-like structure with a diameter
of 10-20 nm. The Pt-Ru electrocatalysts were deposited
on the DGCNTs using sputtering process
(Pt-Ru/DGCNT), which were acted as an anode in the
DMFC. The diameters of Pt-Ru nanoparticles deposited
on the DGCNTs are ca. 3.54 nm, which are the
high-degree alloy by X-ray diffraction analysis. For
fabricating a membrane electrode assembly (MEA), 0.2
mg/cm
2
Pt-Ru/DGCNT and 4.0 mg/cm
2
Pt black
deposited on carbon cloth were employed as the anode
and cathode, respectively, which the Nafion 117 was
sandwiched in between the electrodes by a hot-pressing
process. The polarization curve shows that the
maximum power density is ca. 1.52 W/Pt-mg feeding 1
M methanol and pure oxygen to the anode and cathode,
respectively, operating at 60
o
C. The low amount of
precious metal loaded on DGCNTs applied in a MEA
shows a high performance, which is suitable for a
DMFC.
INTRODUCTION
A direct methanol fuel cell (DMFC) is an
electrochemical device, which generates energy by
feeding methanol and oxygen/air to the anode and
cathode, respectively (Hampson, N. A. et al., 1979).
The DMFC is different from a proton electrolyte
membrane fuel cell (PEMFC) using hydrogen and
oxygen as fuel and oxidant, respectively, without a
reforming system and a complicated heat-exchange
system, which is suitable for a power supply of portable
device. However, the slow methanol-oxidation kinetics
at the anode decreases the performance. Therefore, to
increase the methanol-oxidation activity, the precious
metal-loading of anode is seldom lower than 1 mg/cm
2
.
The platinum and ruthenium in equal proportions are
now more or less standard electrocatalysts to use at the
anode. However, the cost of precious metal is thought
one of the big challenges for the commercialized
DMFC. In order to achieve a high-performance but
low-cost DMFC, nano-sized and highly dispersed
electrocatalysts deposited on carbon supports with high
conductivity and large specific surface area have been
employed in an electrocatalyst layer (Bessel, Carol A.
et al., 2001; Hyeon, T. et al., 2003; King, W. D. et al.,
2003; Lee, S.-A. et al., 2002; Park, K.-W. et al., 2004;
Steigerwalt, E. S. et al., 2001).
Carbon nanotubes (CNTs) with high conductivity,
large specific surface area and inert electrochemical
characteristic have been employed as the
electrochemical devices, such as supercapacitors, fuel
cells, and biological applications (An, K. H. et al., 2001;
Che, G. et al., 1998; Dillon, A. C. et al., 1997; Wang, G.
X. et al., 2003). The deposition of the electrocatalysts
on the CNTs, which uses the impregnation method or
the ion-exchange method, has been applied in the fuel
cells (Girishkumar, G. et al., 2004; Guo, D.-J. et al.,
2004; He, Z. et al., 2004; Xing, Y. et al., 2004). Then,
the mixtures of the electrocatalysts deposited on CNTs,
Nafion solution and organic solvent were dispersed on
the carbon cloth or carbon paper forming an
Paper Receivedr June, 2007. Revised October, 2007. Accepted
October, 2007. Author for Correspondence: Chen-Hao Wang
* Post Doctoral Fellow, Institute of Atomic and Molecular Sciences,
Academic Sinica, Taipei, Taiwan 10617.
** Research Fellow, Institute of Atomic and Molecular Sciences,
Academic Sinica, Taipei, Taiwan 10617.
*** Institute of Materials Science and Nano Technology, Chinese
Culture University, Taipei, Taiwan
J. CSME Vol.28, No.6 (2007)
-572-
electrocatalyst layer. However, some electrocatalysts
were isolated by Nafion ionomers leading to decrease
the three-phase contact between reactant, electrolyte,
and electrocatalyst in the electrocatalyst layer.
In order to promote the utilization of three-phase
contacts in the electrocatalyst layer, the CNTs were
directly grown on a carbon cloth (DGCNTs). The
electrocatalysts were subsequently dispersed on the
DGCNTs. Therefore, electrons, which were generated
by the methanol oxidation, can directly transfer through
the DGCNTs via the carbon cloth to the outlet circuit.
The DGCNTs were synthesized by microwave
plasma-enhanced chemical vapor deposition, and then
the electrocatalysts, platinum and ruthenium, were
sputtered on the CNTs. The electrochemical property
was measured by cyclic voltammogram and the fuel
cell was preformed by polarization curves, which
shows the unique feature of DGCNT as the
electrocatalyst support.
EXPERIMENTAL
The DGCNTs were synthesized by the microwave
plasma enhanced vapor chemical deposition (MPECVD)
using the iron-assisted catalytic grown method. Iron
particles were deposited on the carbon cloth by the ion
beam sputtering deposition (IBSD). The ion beam was
generated by a Kaufman type ion gun using the voltage
and current of 1250 V and 20 mA, respectively, under
argon atmosphere of 510
-4
Torr. The deposition time of
iron particles was 10 min. Following deposition, the
carbon cloth coated with the iron particles was
introduced into the MPECVD reactor. Before the
growth, the iron particles were treated by the hydrogen
plasma of 1 kW at 28 Torr in order to clean and etch the
particle surfaces. The DGCNTs were synthesized in a
gas mixture of CH
4
/H
2
/N
2
at 20/80/80 sccm,
respectively. The microwave power and the chamber
pressure were 2.5 kW and 45 Torr, respectively. The
growth time was 10 min.
The platinum and ruthenium were simultaneously
dispersed on the DGCNT (Pt-Ru/DGCNT) using the
dual-gun sputtering system. The platinum and
ruthenium targets were separately placed into the radio
frequency planar magnetron sputtering guns. In order to
get a uniform deposition, the DGCNT was situated on
the holder with rotation of 20 rpm. The deposition was
carried out at argon atmosphere of 510
-2
Torr, and the
deposition time was 10, 20 or 40 min dependent on the
requirement.
High resolution scanning electron microscopy,
(HRSEM, JEOL-6700) and transmission electron
microscopy, (TEM, JEM-4000EX) were employed to
view morphological structures of the DGCNT and
Pt-Ru/DGCNT. The crystal structure and particle size
of Pt-Ru deposited on DGCNTs were determined by
X-ray diffraction (XRD, PANalytical X' Pert PRO
diffractometer system with Cu K radiation at 1.54056
). The weight loading and atomic ratio of Pt and Ru
were examined by inductively coupled plasma-optical
emission spectroscopy (ICP-OES, PerkinElmer
ICP-OES Optima 3000). The cyclic voltammogram
(CV) was measured by the three-electrode
electrochemical instrument (Solatron 1280B). The
reference electrode and the counter electrode were used
3 M Ag/AgCl (0.207 vs. SHE) and platinum foil,
respectively. The sample was acted as a working
electrode located in a specific holder, which a golden
wire connected the working electrode with the
instrument. All solutions were degassed using high
purity nitrogen and the CV data were recorded until the
CV scans remained constant.
The membrane electrode assembly (MEA), a
sandwiched structure of a Nafion membrane between
an anode and a cathode, was fabricated by a
hot-pressing process. For the anode, the Pt-Ru/DGCNT
was immersed in 5 wt.% Nafion solution about 10 min.
Besides, the commercial 20 wt.% Pt-Ru/C was
prepared on the carbon cloth for the comparison. The
standard cathode, 3.0 mg/cm
2
Pt black, was purchased
from E-TEK Inc. Nafion 117 (H
+
, Dupont) was
employed as the proton-exchange membrane. The
hot-pressing process was operated at pressure of 130
kg/cm
2
and temperature of 135
o
C for 2 min. The MEA
test was operated at 60
o
C as well as purity oxygen and
1 M methanol feeding to the cathode and anode,
respectively. The polarization curve was performed by
the DMFC test station (DMFCTS-01, Asia Pacific Fuel
Cell Technologies, Ltd.).
RESULTS AND DISCUSSION
From Figure 1a, the CNTs are directly grown on
the carbon cloth, and the lengths of DGCNTs are
around 5 to 10 m. The diameters of DGCNTs are 10
to 20 nm, as shown in Figure 1b. From the TEM image
as shown in Figure 2, the DGCNT is a multi-walled and
bamboo-like structure, which is associated with the
incorporation of nitrogen atoms resulting in distortion
sites by forming pentagon and hexagon structure (Cui,
H. et al., 2000; Chen, L.-C. et al., 2002; Chan, L. H. et
al., 2004). It is believed that these distortion sites may
be the active sites, which are beneficial for the
electrocatalysts stably located and highly dispersed on
the wall of CNT (Sun, C.-L. et al., 2005; Wang, C.-H.
et al., 2006).
C.H. Wang et al.: Directly Grown Carbon Nanotubes Applied in Direct Methanol Fuel Cell
-573-
Figure 1. The HRSEM images of CNTs directly
grown on a carbon cloth.
Figure 2. The TEM image showing the multi-walled
and bamboo-like CNTs.
Platinum has been thought of a good choice for
methanol oxidation. However, platinum is strongly
bonded with carbon monoxide forming Pt-CO during
methanol oxidation, which is called Pt-poisoning,
resulting in the decrease of methanol-oxidation activity.
Therefore, ruthenium, which can dissociate water
forming Ru-OH at low potential, is mixed in the
electrocatalyst layer to detoxify the Pt-poisoning, as
shown in below:
Pt-CO + Ru-OH Pt-Ru + CO
2
+ H
+
+ e (1)
The HRSEM and TEM images of Pt-Ru/DGCNT
are shown in Figure 3a and 3b, respectively. From Fig.
3a, the Pt-Ru electrocatalysts are successively
deposited on the DGCNTs. It is clear that the
electrocatalysts are highly dispersed on the DGCNT, as
shown in Fig. 3b. The diameter of electrocatalyst is
around 3.5 nm. The rings in the corresponding selected
area diffraction (SAD) reveals that the electrocatalysts
are polycrystalline and randomly oriented, as shown in
the inset of Fig. 3b. The XRD pattern shows that the
Pt-Ru/DGCNT has the diffraction peaks at 40, 47, 67
and 83 degree, which are corresponding to the
reflection planes of Pt fcc-structure at (111), (200), (220)
and (311), respectively, as shown in Figure 4. The
diffraction peak of Pt (220) is employed to calculate the
alloy-degree and particle size of Pt-Ru due to it is
independent of the diffraction peaks of DGCNT. The
alloy degree of Pt-Ru is about 45 % according to
Vegards law (Antolini, E. et al., 2000). The particle
size of Pt-Ru is about 3.54 nm using Scherrer equation
(equation (2)), which is closed to the observation from
TEM image.
max 2
1
cos
9 . 0

B
L
k

(2)
Figure 3. (a) The HRSEM image of Pt-Ru/DGCNT;
(b) the TEM image of Pt-Ru/DGCNT and
the corresponding SAD pattern showing in
the inset.
Figure 4. The XRD patterns of the Pt-Ru/DGCNT
and DGCNT.
Figure 5 shows that the CV scans of
Pt-Ru/DGCNT and Pt/C perform in the 1 M methanol
and 1 M sulfuric acid at the scan rate of 10 mV/s. Both
of CV results show two oxidation peaks, which occur
from the forward and backward sweep scans. The
forward peak is associated with the methanol-oxidation
activity of electrocatalysts, and the backward peak is
contributed by the Pt-poisoning. Therefore, it is
believed that the high methanol-oxidation activity of
electrocatalysts performs the high forward but low
backward peaks in a CV scan. The forward peak of
Pt-Ru/DGCNT shows the potential and current density
of 0.56 V and 17.5 mA/cm
2
, respectively. Because of
the ruthenium incorporation, the backward peak at 0.45
V is about one-third of the forward peak, indicating that
the Pt-poisoning is effectively suppressed. For the
comparison of Pt-Ru/DGCNT and Pt-Ru/C, the forward
peak of Pt-Ru/DGCNT is higher than that of Pt-Ru/C,
indicating that the methanol-oxidation activity of the
former is higher than that of the latter. Besides, the
J. CSME Vol.28, No.6 (2007)
-574-
methanol-oxidation onset potential of the forward
sweep scan shows that the Pt-Ru/DGCNT is earlier
than the Pt-Ru/C, revealing that methanol is easily
oxidized by the Pt-Ru/DGCNT.
Figure 5. The CV scans of the Pt-Ru/DGCNT and
Pt-Ru/C in 1 M methanol and 1 M sulfuric
acid at the scan rate of 10 mV/s.
Figure 6 shows the polarization curves of MEAs
using the Pt-Ru/DGCNT and the Pt-Ru/C as the anodes.
The maximum power densities of Pt-Ru/DGCNT and
Pt-Ru/C are 1.52 W/Pt-mg and 0.82 W/Pt-mg,
respectively, which the former is about twice of the
latter. From the CV scans and polarization curves, the
Pt-Ru/DGCNT shows the high methanol-oxidation
activity, which is contributed by the prerogative of
DGCNT. The electrons, which are generated by
methanol oxidation, transfer via the DGCNT and then
directly deliver to the outlet circuit. Therefore, the
internal resistance of electrocatalyst layer can be
reduced. Besides, the electrocatalysts are deposited on
the DGCNT, so the utilization of electrocatalysts can be
increased. Using the conventional Pt-Ru/C, some
electrocatalysts are isolated by Nafion solution not only
resulting in the increase of internal resistance but also
leading to the decrease of utilization. The
Pt-Ru/DGCNT not only reduces the internal resistance
but also promote the three-phase contact, and therefore
the activity of methanol oxidation can be enhanced.
CONCLUSION
In this study, the CNTs were successfully directly
grown on a carbon cloth, and the Pt-Ru electrocatalysts
were subsequently deposited on the DGCNT, which
were employed as the anode in the DMFC. Comparing
of the Pt-Ru/DGCNT and the conventional Pt/C,
Pt-Ru/DGCNT shows a higher methanol-oxidation
activity. The DGCNT not only has low internal
resistance but also promotes the electrocatalyst
utilization, which is a good electrocatalyst support
applied in the DMFC.
Figure 6. The polarization curves of MEAs using the
Pt-Ru/DGCNT and the Pt-Ru/C.
ACKNOWLEDGEMENTS
The authors would like to thank the National
Science Council and Ministry of Education in Taiwan
for financially supporting. Technical assistance from Dr.
Cheng-Hsien Hsu, Dr. Ning-Yih Hsu and Mr.
Yao-Sheng Hsu are gratefully acknowledged.
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10 20 nm

3.54 nm0.20 mg cm
-2

4.0 mg cm
-2

Nafion 117
MEAmembrane-electrode assembly
1 M
60 1.52
W Pt-mg
-1