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Carbon Nanotubes for Hydrogen Storage

By Chiao Ku
11/31/02














Submitted in partial fulfillment of course
Requirement for MatE 115, Fall 2002
Instructor: Professor G. Selvaduray
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TABLE OF CONTENTS

1.0 Introduction……………………………………………………………….………3
1.1 Use of Carbon Nanotubes in Hydrogen Storage.…..………………………..3
1.2 History of Carbon Nanotubes………………………………………………..4
1.3 Structure of Carbon Nanotubes……………………………………………...5

2.0 Principles / Mechanism………………...…………………………………………6
2.1 Specific Surface Area and Gas absorption…………………...……………...6
2.2 Experiments on Hydrogen Storage………………………………………….8

3.0 Future Aspects…………………………………………………………………...11

4.0 Summary / Conclusion…………………………………………………………..12

5.0 Reference………………………………………………………………………...13
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1. Introduction
1.1 Use of Carbon Nanotubes in Hydrogen Storage
With the accelerating demand for cleaner and more efficient energy sources,
hydrogen research has attracted more attention in the scientific community. The focus
of some of the research has been the development of hydrogen fuel cells,
electrochemical devices that are able power buildings, cars and portable electric
devices.
Hydrogen is an ideal fuel; it is abundant, renewable and its combustion produces
only water vapor and heat. Until now, full implementation of a hydrogen-based
energy system has been hindered in part by the challenge of storing hydrogen gas,
especially onboard an automobile. New techniques being researched may soon make
hydrogen storage more compact, safe and efficient.
These new methods use carbon as a storage medium and bring us a step closer to
the widespread use of hydrogen as a fuel source. Some scientists are using various
approaches to shape carbon into microscopic cylindrical structures known as
Nanotubes.
One of the critical factors in Nanotubes’ usefulness as a hydrogen storage
medium is the ratio of stored hydrogen to carbon. According to the US Department of
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Energy, a carbon material needs to store 6.5%
[1]
of its own weight in hydrogen to
make fuel cells practical in cars. Such fuel cell cars could then travel 300 miles
between refueling stops.
1.2 History of Carbon Nanotubes
After Kroto and Smalley discovered Fullerene, one of carbon allotropes(a cluster
of 60 carbon atoms : C60) for the first time in 1985, Dr. Iijima
[2]
, a researcher for this
new material, at the NEC laboratories in Japan. In 1991, he discovered this thin and
long straw-shaped carbon Nanotubes during a TEM analysis of carbon clusters. This
discovery was published in Nature for the first time. The Nanotubes range in length
from a few tens of nanometers to several microns, and outer diameter from about 2.5
nm to 30 nm. A carbon atom in Nanotubes forms a hexagonal honeycomb lattice of
sp2 bond with 3 other carbon atoms. As the inner diameters of the tubes are extremely
thin down to about several nanometers, the tubes are called Nanotubes.




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1.3 Structure of Carbon Nanotubes
Fig. 1 Structures of Carbon Nanotubes
[3]

Carbon Nanotubes (CNTs) are formed by rolled graphite sheet
[4]
, with a least
inner diameter of 0.7nm up to several nm and a length of 10-100 micron. Tubes
formed by only one single graphite layer are called single wall Nanotubes (SWNT,
Fig.1). For tubes contains multiple concentric graphite layers are called Multiwall
Nanotubes (MWNT, Fig.1)
The interlayer distance in MWNTs is closer then interlayer distance in graphic
which has a unit cell parameter c (0.5c = 0.3355nm). The diameter of SWNTs varies
from 0.671 to 3nm, whereas MWNTs show typical diameters of 30-50 nm. The
helicity of the Nanotubes is usually described by Hamada vector
[5]
, which indicated
how the graphite sheet is rolled up along a lattice vector with components (n,m). The
value of n and m defines the geometry of SWNT. The Nanotubes with n = m are
referred as “armchair”, tubes with n = 0 or m = 0 are referred as “zigzag”. SWNTs
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tend to grow and form into bundles. The Nanotubes in the bundles tend to have 2
close packed dimensions and the inter-tube distance of 0.334nm
[6]
.
2. Principle / Mechanism
This section will start with the principles and mechanisms used to determine the
hydrogen capacity of carbon nanostructures, and then a general overview on the latest
developments and experiments will be provided.
2.1 Specific Surface Area and gas absorption
Graphite has a HCP structure with lattice parameter a = 0.24612nm and c =
0.6709nm, therefore the plane separation is 0.5c = 0.3355nm and the C-C bond length
is a / !3 = 0.14210nm at 298.15K. Using the density of graphite " = 1315 kg / m³ and
assuming that all the atoms are in one single plane the maximum specific surface area
S(one side) = 1315 m² / g or if both sides of the plane are considered S(two sides) =
2630 m² / g. the absorption of a gas on a surface is a consequence of the filed force at
the surface of the solid., call the adsorbent, which attracts the molecules of the gas or
vapor, called adsorbate. The force of attraction can be identified into two kinds, Van
der Waals and chemical absorption. Once a layer of adsorbate molecules is formed the
gaseous molecule which interacts with remaining adsorbate. Therefore, the binding
energy of the second layer can be approximated as the latent heat of vaporization of
the adsorbate. As a result, the adsorption at boiling temperature or above of the
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adsorbate at a given pressure will lead to the saturation of one single monolayer
[7]
.
In order to calculate the quantity of adsorbate in the monolayer we use the
density of the liquid adsorbate and compute the volume of the molecule:


A adsorbate
adsorbate
adsorbate
N
M
V
ρ
= (1)

Where M stands for the molar mass of the adsorbate, " is the density of the
adsorbate and V is the volume for each molecule in liquid phase. With the general
assumption that the molecules are spherical and close-packed, the volume of the
sphere can be represented as:


A adsorbate
adsorbate
M
N
M
V
ρ
π
2 3
= (2)

Table 1 The properties of hydrogen as adsorbate*
Properties Hydrogen
M (g / mol) 2.0159
" (g / cm³) 0.0708
Vm (nm³) 0.0350
d (nm) 0.4059
Sm (nm²) 0.1294
1 / S (mol / m²) 1.2834e-05
1 / S (g / m²) 2.5668e-05
* M is the molar mass, " is the density of the adsorbate at boiling point, Vm is the volume of the
molecule, d is the diameter of the molecules, Sm is the surface area occupied by the molecule. 1 / S is
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the amount of adsorbate per surface area in a monolayer.
From the volume of the spherical molecule, the diameter can be calculated under
the assumption of close packed molecules at the surface area Sm:

3 3
2 6
A adsorbate
adsorbate m
m
N
M V
d
ρ π
= = (3)

3
2
2
2
3








=
A adsorbate
adsorbate
M
N
M
S
ρ
(4)
The above values parameters for hydrogen are calculated and presented in Table
1. The condensation of a monolayer of hydrogen on a graphite sheet with a specific
area of S(one side) = 1315 m² / g leads to:

034 . 0
12
0159 . 2
) (
) (
) (
2
= = =
A
adsorbate
M
oneside
N
M
S
S
C m
H m
(5)

Therefore the theoretical maximum condensation is 3.4 wt%, and it is not enough
to meet out requirements for a hydrogen cell. However, the scientists have discovered
an overlap of these monolayers (SWNTs) can actually hold more hydrogen inside the
CNT. The details are explained in the experiments on hydrogen storage.
2.2 Experiments on hydrogen Storage
In 1997, Dillon et al.
[8]
discovered that SWNTs have a high reversible hydrogen
storage capacity. Thereafter, many research groups started to conduct hydrogen
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storage researches and have made remarkable progresses. Most of the current
experimental results of hydrogen storage in carbon Nanotubes are summarized in
Table 2.
Table 2
Summary of experimentally reported storage capacities in carbon Nanotubes

In their pioneering work, Dillon et al. showed that hydrogen can condense to
high capacity (estimated to 5~10 wt%) inside narrow SWNTs, and predicted that
SWNTs with diameters of 16.3 to 20 Å would come close to the target capacity of 6.5
wt%. The adsorption of H
2
in SWNT was investigated with temperature programmed
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desorption (TPD) spectroscopy and it suggested that physical adsorption of hydrogen
mainly occurred within the cavities of SWNTs.
According to Dillon’s prediction, this kind of SWNT may be promising as
hydrogen storage medium. Figure 2
[9]
shows the change of hydrogen pressures as a
function of time for SWNTs under an initial hydrogen pressure of 10 MPa in the first
adsorption cycle at room temperature. The hydrogen uptake is complete within few
hours. It has been proved that notable changes occur for pore structure in the course of
hydrogen uptake in SWNTs. All the above facts indicate that the inner hollow cavity
takes part in the hydrogen adsorption.

Fig. 2. The amount of H
2
in weight for SWNT samples, and the pressure change versus the adsorption
time. Sample 1 was used as synthesized. Sample 2 was soaked in 37% HCI acid for 48 h, rinsed with
deionized water, and dried at 423 K. Sample 3 was pretreated in the same way as sample 2, the vacuum
heat-treated for 2 h at 773 K
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Another striking experimental result on hydrogen storage is in graphite
nanofibers (GNFs) were reported by Chambers et al.
[10]
They claimed that tubular,
platelet, and herringbone forms of GNFs have the capacity of 11, 45, and 67 wt% H
2
,
respectively, at room temperature and 12MPa. Their recent research further explains
about the interaction between hydrogen and GNFs, and concluded that the GNFs have
special structure, which produces a material composed entirely of nano-pores that
hold hydrogen molecules, and the non-rigid pore walls can expand to accommodate
hydrogen molecules in a multiplayer conformation.
Chen et al.
[11]
reported in their TPD experiments that a high H
2
uptake of 20 and
14 wt% can be achieved in milligram quantities of Li-doped and K-doped MWNTs,
respectively, under room pressure. The K-doped MWNTs can adsorb H
2
at room
temperature, but they are chemically unstable, whereas the Li-doped MWNTs are
chemically stable, but require elevated temperatures (473 to 673 K) for maximum
adsorption and desorption of H
2
.
3. Future Aspects
There are more and more reproducible evidences prove that carbon Nanotubes
are potential hydrogen storage medium.
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However, it is still unpractical due to the limitation on mass production and
utilization of carbon Nanotubes. And the following obstacles still needed to be solved
by Scientists
[12]
:
1. Mass production of carbon nanostructures with a controlled microstructure at a
reasonable cost.
2. Purification of CNTs, development and optimization of pretreatment methods for
opening the caps at the tube ends to improve their hydrogen storage capacity.
3. Elucidation of the microstructure of Nanotubes, especially pore structure and
surface microstructure in the viewpoint of hydrogen adsorption/desorption.
4. Elucidation of volume storage capacity and how to improve it.
5. Further investigation of adsorption/desorption process, thermodynamics, kinetics
and cycling behaviors of carbon Nanotubes.
6. A more practical hydrogen adsorption model to design a CNT based hydrogen
storage medium.
4. Summary / Conclusion
In conclusion, hydrogen fuel is clean, versatile, efficient and safe, and it will play
an important role in the future world energy structure. Preliminary experimental
results and some of the theoretical predictions indicate that Carbon Nanostructures
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(CNTs and CNFs) can be a promising candidate for hydrogen storage, which may be
the solution hydrogen fuel cell-driven vehicles. Nevertheless, many efforts still have
to be made to reproduce and verify the hydrogen storage capacity of carbon
Nanotubes both theoretically and experimentally, to investigate their storage capacity,
absorption and desorption behaviors, and finally to clarify the feasibility of carbon
nanostructures as a practical hydrogen storage medium.


5. Reference

[1]
http://www.energy.gov

[2]
R. Saito, G. Dresselhaus and M.S. Dresselhaus. “Physical Properties of Carbon
Nanotubes” (Imperial College Press, London 1998) pp. 2-7

[3]
http://www.iljinnanotech.co.kr

[4]
S. Iijima, “Nature,” 1991;345;56-58

[5]
A. Zuttel, P. Sudan, Ph. Mauron, T. Kiyobayashi, Ch. Emmenegger, L. Schlabach.
“Hydrogen storage in carbon nanostructures,” (International Journal of Hydrogen
Energy 27, 2002) pp 203-204.

[6]
ibid, p 205-206.

[7]
ibid, p 207.

[8]
A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang, D.S. Bethune and M.J.
Heben, “Storage of hydrogen in single-walled carbon nanotubes.” Nature 386 (1997),
pp. 377–379.

[9]
C. Liu, Y.Y. Fan, M. Liu, H.T. Cong, H.M. Cheng and M.S. Dresselhaus,
“Hydrogen storage in single-walled carbon Nanotubes at room temperature.” Science
286 (1999), pp. 1127–1129.

[10]
A. Chambers, C. Park, R.T.K. Baker and N.M. Rodriguez, “Hydrogen storage in
graphite nanofibers.” J. Phys. Chem. B 102 (1998), pp. 4253–4256.

[11]
P. Chen, X. Wu, J. Lin and K.L. Tan, “High H
2
uptake by alkali-doped carbon
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Nanotubes under ambient pressure and moderate temperatures.” Science 285 (1999),
pp. 91–93.

[12]
T. Huang, “Nanotechnology That Will Change the World,” (Enlighten Noah
Publishing, 2002) pp. 38-50