Electrochimica Acta 45 (2000) 4511 4515

www.elsevier.nl/locate/electacta

Electrochemical investigation of single-walled carbon

nanotubes for hydrogen storage
N. Rajalakshmi a,*, K.S. Dhathathreyan a, A. Govindaraj b,c,
B.C. Satishkumar c
a
Centre for Electrochemical and Energy Research, SPIC Science Foundation, 111 Mount Road, Guindy, Madras 600032, India
b
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 064, India
c
Jawaharlal Nehru Centre for Ad6anced Scientific Research, Jakkur, Bangalore 560 064, India

Received 1 March 2000; received in revised form 26 April 2000

Abstract

Electrodes made of purified and open single walled carbon nanotubes behave like metal hydride electrodes in
NiMH batteries, showing high electrochemical reversible charging capacity up to 800 mAh g 1 corresponding to a
hydrogen storage capacity of 2.9 wt% compared to known AB5, AB2 metal hydride electrodes. 2000 Elsevier
Science Ltd. All rights reserved.

Keywords: Electrochemical investigation; Carbon nanotubes; Hydrogen storage

1. Introduction monodisperse product, it has been possible to obtain

The recent discovery [1] of the storage of hydrogen in
carbon nanotubes and graphite nanofibres by gas phase
measurements and electrochemical measurements has
stimulated interest in the reversible electrochemical
storage of hydrogen in single-walled carbon nanotubes.
The safe storage of hydrogen is also critical to hydro-
genair fuel cells. The storage of hydrogen in metal
hydrides has the drawback of relatively low weight
density. To overcome this problem, there is consider-
able effort to study light metal hydrides and storage in
light elements such as carbon. The capillarity of carbon
nanotubes thus offers a good prospect for hydrogen
storage. Single-walled nanotube (SWNTs) constitute
the simplest tubular form of carbon wherein a single
graphite sheet is rolled into a tube. While most methods
of synthesis of the SWNTs do not generally produce a
* Corresponding author. Tel.: +91-44-2352342 fax: +91-
44-2351504.
E-mail address: raji@energy.smi.ernet.in (N. Rajalakshmi).
relatively large quantities of SWNTs of uniform pore
diameter [1]. In recent times, a study has revealed that
these are good microporous materials with relatively
large total surface areas [2].
Dillon et al. [3] have reported that crystalline
SWNTs have hydrogen storage capacity of 5 10 wt%
at pressures less than 1 bar near room temperature (r.t.)
Such a hydrogen storage capacity would be a significant
advance for the use of hydrogen as a fuel when high
gravimetric density of hydrogen is a figure of merit. The
best value of hydrogen absorption in carbon nanomate-
rials reported so far has been 5.3 wt% or 0.64 hydro-
gen carbon (H C) at a temperature of 77 K. Recently
Chambers et al. [4] have claimed that graphite
nanofibres have a capacity of 24 H C at 300 K which
is yet to be fully confirmed. Ye et al. [5] have shown
recently that hydrogen absorption on crystalline ropes
of single walled carbon nanotubes exceeds 8 wt%,
which is the highest capacity obtained so far. These
workers have calculated the cohesive energy and found
it to be strongly affected by the quality of crystalline

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4512 N. Rajalakshmi et al. / Electrochimica Acta 45 (2000) 45114515

order in the ropes. These studies suggest the possible
use of SWNTs for reversible electrochemical storage. A
recent report of Nutzenadel et al. [6] shows that a
commercial sample of carbon web produced by arc-dis-
charge and containing some nanotubes, can electro-
chemically store relatively large amounts (110 mAh
g 1) of hydrogen, corresponding to a hydrogen storage
capacity of 0.39 wt%. The reaction is reversible indicat-
ing that the nanotubes can be used to produce elec-
trodes for rechargeable batteries. In metal hydride
batteries, the hydrogen is stored reversibly in the inter-
stitial sites of a host metal. The electric energy is
produced by direct electrochemical conversion [7,8].
The decomposition of water molecules is an essential
step in the charging mechanism and the chargedis-
charge processes occur at the electrode through solid
state charge transfer mechanisms [9]. We considered it
most worthwhile to investigate the electrochemical hy-
drogen storage capacity of pure SWNTs and report the
preliminary results of such a study in this
communication.
2. Experimental
SWNTs were produced by the dc arc discharge
method using a composite graphite rod containing
Y2O3 (1 at%) and Ni (4.2 at%) as anode and a graphite
rod as cathode under a helium pressure of 660 torr with
a current of 100 A and 30 V as reported earlier [1]. The
mass obtained was heated at 300C in air for about 24
h to remove amorphous carbonaceous materials. The

Fig. 1. High resolution electron microscope images of (a) as produced SWNT bundles, (b) purified SWNT bundles.
 N. Rajalakshmi et al. / Electrochimica Acta 45 (2000) 45114515 4513

heat-treated material was stirred with concentrated ni-
tric acid at 60C for about 12 h and washed with
distilled water to remove the dissolved metal particles.
This treatment has been used to open the carbon
nanotubes [10,11]. The SWNT material so obtained was
suspended in ethanol by using a ultrasonicator and
filtered through a micropore filter paper (0.3 mm) from
Millipore to remove polyhedral carbon nanoparticles
present. The product was then dried at 150C for about
12 h. The SWNT content of the product was found to
be 80% by thermogravimetric analysis. High-resolution
electron microscopic (HREM) examination showed
that the SWNTs with an average diameter of 1.4 mm
were present as bundles of 5 50 nanotubes. The elec-
trochemical measurements were carried out using a
EG&G galvanostat/potentiostat model 273, with the

Fig. 2. Chargedischarge hydrogen storage capacity of the SWNT electrode at 10 mA current.

Fig. 3. Comparison of the electrochemical hydrogen storage capacity of the two purified SWNT electrodes.
4514 N. Rajalakshmi et al. / Electrochimica Acta 45 (2000) 45114515
help of a three electrode system using SWNTs as work-
ing electrode, Platinum as counter electrode and satu-
rated calomel as reference electrode. Electrochemical
measurements were carried out in a flooded electrolyte
condition in open cells. The electrolyte 30% KOH,
which is the same as that used in alkaline batteries, was
prepared from reagent grade KOH and de-ionised wa-
ter. Chronopotentiometry, controlled potential cou-
lometry, and cyclic voltammetry were used to gather
the electrochemical data reported here. Electrodes were
prepared by mixing 10 mg of the SWNTs with Cu
powder in the ratio of 1:3 with a polyte-
trafluoroethylene (PTFE) binder. The putty form of the
mixture was mechanically pressed on to a current col-
lector (Ni mesh) at r.t. Then the electrode was sintered
at 200C for about 1 h under vacuum. The geometric
area of the electrode was about 2 cm2. The electrodes
were tested for their chargedischarge characteristics,
initial capacity and cycle life.
3. Results and discussion
The web produced from the arc-discharge contained
SWNT bundles, amorphous carbon along with metal
encapsulated carbon particles as can be seen from the
high resolution electron microscope (HREM) image in
Fig. 1a. In Fig. 1b we show the HREM image of the
SWNTs after purification. The electrodes made of the
Fig. 4. Variation of the electrochemical capacity of SWNT electrodes with respect to the charging current. Inset shows the
electrochemical hydrogen storage capacity as a function of number of cycles.
as-produced web showed an electrochemical charging
capacity of 87 mAh g 1, comparable to the value of
110 mAh g 1 reported by Nutzenadel et al. [6] for the
commercial sample of the web. Electrodes made of the
purified SWNTs, however showed a tremendous elec-
trochemical hydrogen storage capacity of around 800
mAh g 1 at a charging and discharging rate of 10 mA
current. Fig. 2 shows the charge (lower curve) and
discharge (upper curve) curve for pure SWNTs. The
charging and discharging potential was around 0.8
and 0.6 V versus SCE, respectively. The coulombic
efficiency was found to be 85%. The equilibrium curves
were measured in the normal mode at a constant
discharge current of 10 mA. The shape of the charge
discharge equilibrium curve is not much different from
that of the metal hydride electrodes. In order to check
for the reproducibility, a few electrodes made with
different weights of SWNTs were examined and they
gave nearly the same electrochemical capacity. Fig. 3
shows the charging curve of the electrodes after the
eighth cycle, since first few cycles were used to activate
the samples. Here, from the eighth cycle onwards, the
electrodes started giving almost the same electrochemi-
cal capacity. The small difference in weight of the
electrodes is reflected in the charging time.
The electrodes were charged and discharged also at
different current ratings from 10 to 100 mA. The
variation in the charging capacity was found to be only
50 mAh g 1 in the range studied as shown in Fig. 4.
 N. Rajalakshmi et al. / Electrochimica Acta 45 (2000) 45114515
This behavior is in contrast to that of a metal hydride
electrodes where the capacity decreases steeply at higher
discharging currents. The maximum electrochemical hy-
drogen absorption capacity was found to occur after 20
cycles of charge and discharge, with the capacity re-
maining constant for almost 50 cycles (see inset of Fig.
4). It is to be noted that the samples investigated by
Nutzenadel et al. [6] contained only a few percent of
nanotubes, showing an electrochemical capacity of 0.39
wt%, but the sample investigated by us contains 80% of
SWNTs giving eight times higher capacity (2.9 wt%). It
is possible that the opened SWNTs facilitate absorption
of hydrogen electrochemically. Hydrogen may be
packed within the tubes at a higher density than as-
sumed, if repulsive interactions between the hydrogen
molecules were either screened or additional hydrogen
is adsorbed by the exterior surfaces of SWNTs and/or
the interstitial spaces between the bundled tubes. The
present study reveals that SWNTs may indeed be useful
in battery technology for the replacement of metal
hydride electrodes. Further experiments are in progress
for the study of the mechanism of chargedischarge
process, cycle life and for the evaluation of diffusion
coefficients of hydrogen in these nanotubes.
Acknowledgements
We thank the management of SPIC Science founda-
4515
tion, for financial support. We thank Professor C.N.R.
Rao for encouragement and guidance.
References
[1] C. Journet, W.K. Maser, P. Bernier, A. Loiseau, M.
Lamy de la Chapelle, S. Lefrant, P. Denierd, R. Lee, J.E.
Fischer, Nature 388 (1997) 756.
[2] M. Eswaramoorthy, R. Sen, C.N.R. Rao, Chem. Phys.
Lett. 304 (1999) 207.
[3] A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang,
D.S. Bethune, M.J. Heben, Nature 386 (1997) 377.
[4] A. Chambers, C. Park, R.T.K. Baker, N.M. Rodriguez, J.
Phys. Chem. 102 (1998) 4253.
[5] Y. Ye, C.C. Ahn, C. Witham, B. Fultz, J. Liu, A.G.
Rinzler, D.T. Colbert, K.A. Smith, R.E. Smalley, Appl.
Phys. Lett. 74 (1999) 2307
[6] C. Nutzenadel, A. Zuttel, D. Chartouni, L. Schlapbach,
Electrochem. Solid State Lett. 2 (1999) 30.
[7] J.M. Evjen, A.J. Catotti, in: D. Linden (Ed.), Handbook
of Batteries, 2nd ed., Mc Graw Hill, New York, 1995
chapter 27.
[8] M.A. Fetcenko, S. Venkatesan, Prog. Batter. Sol. Cells 9
(1990) 259.
[9] T. Sakai, H. Miyamura, N. Kuriyama, H. Ishikawa, J.
Uehara, Z. Phys. Chem. 183 (1994) 333.
[10] C.N.R. Rao, A. Govindaraj, R. Sen, B.C. Satishkumar,
Mater. Res. Innov. 2 (1998) 128.
[11] C.N.R. Rao, A. Govindaraj, B.C. Satishkumar, J. Chem.
Soc. Chem. Commun. (1996) 1525.