APPLIED PHYSICS LETTERS

VOLUME 80, NUMBER 13

1 APRIL 2002

Volumetric hydrogen storage in single-walled carbon nanotubes

C. Liu, Q. H. Yang, Y. Tong, H. T. Cong, and H. M. Chenga)
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

Received 26 November 2001; accepted for publication 4 February 2002 Macroscopically long ropes of aligned single-walled carbon nanotubes SWNTs , synthesized by a hydrogen and argon arc discharge method, were cold pressed into tablets without any binder for measurements of their volumetric hydrogen storage capacity. The typical apparent density of the tablets was measured to be around 1.7 g/cm3 with respect to a molding pressure of 0.75 Gpa. A volumetric and mass hydrogen storage capacity of 68 kg H2 /m3 and 4.0 wt %, respectively, was achieved at room temperature under a pressure of 11 MPa for suitably pretreated SWNT tablets, and more than 70% of the hydrogen adsorbed can be released under ambient pressure at room temperature. Pore structure analysis indicated that the molding process diminished the mesopore volume of the SWNT ropes, but exerts little inuence on their intrinsic pore textures. 2002 American Institute of Physics. DOI: 10.1063/1.1466517

The depletion of energy resources and environmental pollution are essential problems that are closely related to the sustainable development of human society and demand prompt solution. Hydrogen is considered to be an ideal energy carrier, since it is clean and abundantly reserved. To store and transport hydrogen safely and cheaply is a key step for the utilization of hydrogen energy. One-dimensional nanostructured carbons, including carbon nanobers,1,2 multiwalled carbon nanotubes,3 and single-walled carbon nanotubes SWNTs ,4 6 were reported to be promising candidates for hydrogen uptake, based on the investigations of their gravimetric hydrogen storage capacity. From the viewpoint of practical application, the volumetric hydrogen storage density of these nanostuctured carbon materials may be even more important, since their apparent density seems to be extremely low, and the Department of Energy of the United States has set a volumetric hydrogen storage density of 62 kg H2 /m3 to provide a 350 mile range driving for a fuel cell powered vehicle. However, probably limited by the small amount of samples or their poor moldability, no volumetric hydrogen storage capacity of carbon nanotubes has been reported yet. In this study, we found that macroscopically long SWNT ropes, synthesized by a hydrogen and argon arc discharge method,7 showed excellent molding properties, and they could be easily cold pressed into tablets not using any binder without damaging their intrinsic pore structure. Their volumetric hydrogen storage capacity was measured under modestly high pressure ( 11 MPa) at ambient temperature. A high volumetric hydrogen storage capacity of 68 kg H2 /m3 was achieved, and more than 70% of the adsorbed hydrogen can be released at room temperature. These results further open up the prospect for SWNTs as a promising hydrogen storage material, especially for hydrogenoxygen fuel cell vehicles. The SWNT bundles synthesized by laser ablation8 or the
a

traditional electric arc method9 are usually tens of microns in length and disorderly entangled with one another. In the present study, macroscopically long ropes of SWNTs were prepared by a hydrogen and argon arc discharge method.7 Basically, a suitable ratio of Ar and H2 typically, 50 Torr Ar and 150 Torr H2 was introduced into a vacuum chamber as buffer gases; the cathode was a graphite rod 10 mm in diameter, with one end sharpened , while the anode was 150 mm in diameter, 20 mm in height, and was made up of evenly dispersed graphite powder and a suitable amount of catalysts 2.5 at. % Ni, 1.0 at. % Co and growth promoter 0.8 at. % sulde ; the axis of the two electrodes were not on a line but made an oblique angle (30 50), which is benecial to the formation of a plasma ow and is critical to the synthesis of the SWNT ropes. The ropes thus obtained can be up to 100 mm in length, and the diameters of the ropes range from several microns to 100 m. Scanning electron microscopy SEM and transmission electron microscopy TEM observations showed that the ropes are made up of numerous soundly aligned, tightly packed, long and straight nanotube bundles.7 Figure 1 shows the TEM image of a SWNT bundle separated from a SWNT rope, whose diameter is approximately 200 nm. The results from resonant laser Raman measurements conrmed the high

Author to whom correspondence should be addressed; electronic mail: cheng@imr.ac.cn 2389

FIG. 1. TEM image of a SWNT bundle separated from a rope with a diameter of about 200 nm. 2002 American Institute of Physics

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FIG. 2. Optical a and SEM image b of SWNT tablets used for hydrogen storage; the diameter of the tablets is 10 mm.

quality of the samples, and also indicated a larger mean diameter ( 1.7 nm) of the SWNTs,7 which is a characteristic of our SWNTs. And these SWNTs with larger diameter were considered to be more promising for hydrogen storage.10 Typically, 500 800 mg of the SWNT ropes were placed in a cylinder-shaped steel mould and a pressure of 0.75 GPa was applied, and then SWNT tablets with a diameter of 10 mm and a height of several millimeters were obtained. We found that the SWNT ropes showed excellent mouldability even without addition of any binder. The formed SWNT tablet has a glossy surface and is in a regular cylinder shape, as can be seen in Fig. 2 a . The compressive strength of the tablets was measured to be around 7.0 MPa. In Fig. 2 b , we show the SEM image of the fracture surface of the SWNT tablets. Numerous ber-like SWNT bundles can be seen, and some of the SWNT bundles are still in alignment to some extent. Typically, the apparent density of the tablets was measured to be around 1.7 g/cm3 . Since the theoretical density of SWNTs is predicted to be 1.4 g/cm3 , residue catalysts and some graphite powders introduced during the synthesis process may account for the relatively high density, and the purity of the SWNTs were estimated to be about 60 wt %, according to the results of thermogravimetric measurements and SEM observations. The gravimetric hydrogen storage capacities of the SWNTs were measured by a volumetric method.6 The amount of stored hydrogen was determined by the pressure drop in the testing chamber, which was monitored by a pressure sensor. Usually, SWNT samples with a weight of about 500 mg were employed and the hydrogen adsorption experiment was performed under a moderate high pressure of about 11.0 MPa. Since the weight and volume of the tablets can be easily determined, their apparent density can be then obtained. Thus, the volumetric hydrogen storage capacity can be calculated by 1 ,

listed in Table I. Comparing the gravimetric hydrogen storage capacity of samples 1 and 2, almost no change from 2.6 to 2.5 wt % was found after the SWNTs were cold pressed, which indicates that the access of hydrogen to the SWNTs was not prohibited by the molding process. However, for the tablet samples samples 2 and 3 , a longer adsorption time of 7 h, about two more hours than that for sample 1, was needed to achieve the adsorption equilibrium. We note that the hydrogen storage capacity of the SWNTs was notably improved from 2.5 wt % and 45 kg H2 /m3 to 4.0 wt % and 68 kg H2 /m3 after a high-temperature heat treatment in argon ow. This result indicates that suitable heat treatment can modify the surface state of SWNTs and, hence, improve their hydrogen storage capacity. Nitrogen cryoadsorption measurements of the SWNT ropes and the molded SWNT tablets were carried out to investigate their pore structure and surface characteristics. In Fig. 3, we show the obtained isotherms of samples 1 and 3 in comparison. We can see that the SWNT rope and the molded tablet show almost coincident isotherms in the low relative pressure region, suggesting similar intrinsic porosity inner tube core and intertube cavity inside a bundle structure of the SWNTs before and after molding. The specic surface areas of the SWNT rope and the tablet were calculated to be 110 and 108 m2 /g, respectively. In the high-relative-pressure region, the SWNT ropes show apparent hysteresis loop and high capillarity, which indicates the existence of aggregated mesopores that may be formed by the interaction of SWNT bundles and nanoparticles. However, no hysteresis loop can be found for the molded tablets. The above results indicate that the molding process destroys the aggregated pore texture but exerts little inuence on the intrinsic porosity and surface area of the SWNTs. In addition, analysis of the isotherms showed higher surface energy of the SWNTs, in comparison to other carbonaceous materials. In fact, the ropes we obtained tend to adhere strongly to tweezers and glass vessels.
TABLE I. Hydrogen storage capacities of three kinds of SWNT samples. : gravimetric hydrogen storage capacity; : volumetric hydrogen storage capacity. Sample 1: as-synthesized SWNT ropes; sample 2: SWNT tablet obtained from the as-synthesized SWNT ropes; and sample 3: SWNT tablet from the heat-treated SWNT ropes. The hydrogen storage capacities have an error of 0.3%. Sample No. 1 2 3 Density (g/cm3 ) 1.75 1.64

where is the volumetric hydrogen storage capacity of the SWNT tablets (kg H2 /m3 ), is the apparent density of the tablet (kg/m3 ), and is the gravimetric hydrogen storage capacity of the SWNT tablet. Totally, three kinds of SWNT samples were employed in our experiments. Sample 1 is the as-synthesized SWNT ropes, sample 2 is a SWNT tablet from the as-synthesized SWNT ropes, and sample 3 is a SWNT tablet from the SWNT ropes that was heat treated under argon ow at 1473 K for 2 h, and their measured hydrogen storage capacities are

wt % 2.6 2.5 4.0

(kg H2 /m3 ) 45 68

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FIG. 4. Relation between the amount of hydrogen released from SWNT samples and pressure. FIG. 3. Cryoadsorption isotherm of nitrogen of the SWNT ropes sample 1 and the moulded SWNT tablet sample 3 .

The unique surface character and excellent mouldability of the SWNT ropes can be attributed to their relative high surface energy, which may be related to the uniqueness of our synthesis technique, such as the introduction of hydrogen gas and the addition of sulfur-containing growth promoter. Since the SWNT rope and the SWNT tablet showed a similar intrinsic porosity structure and similar gravimetric hydrogen storage capacity, it can be inferred that it is the micropores, such as inner tube core and inter-tube cavity inside a bundle of SWNTs, rather than aggregated mesopores, that account for the high hydrogen storage capacity of SWNTs. Moreover, samples 2 and 3 showed similar nitrogen cryoadsorption isotherms. Therefore, the higher hydrogen storage capacity of sample 3 4.0 wt % and 68 kg H2 /m3 is considered to be related to the high-temperature 1473 K heat treatment under argon ow. By the heat treatment, the adsorbed species and functional groups on the surface of carbon nanotubes can be removed, which is benecial to improve the hydrogen storage capacity of carbon nanotubes from our observations and measurements on both SWNTs and multiwalled carbon nanotubes, although the detailed mechanism is still not clear. Experiments of hydrogen release from the SWNT tablets were performed at room temperature with a water discharge method. When the hydrogen was admitted to the volumetric cylinder, water was pressed into the water reservoir, so the amount of released hydrogen can be expressed by the volume change of water in the volumetric cylinder. We performed the above experiments with or without the SWNT tablet in the sample cell at different hydrogen gas pressures. By comparison, the absolute amounts of released hydrogen for the samples at different pressures were obtained, as shown in Fig. 4. Usually, more than 70% of the adsorbed hydrogen can be released at ambient pressure and temperature. It is worthy to note that there was almost no hydrogen release from SWNTs when the system pressure was higher than 6.0 MPa, but when the pressure was less than 4 MPa the amount of released hydrogen dramatically increased. This

result indicates that the adsorption and desorption of hydrogen may achieve an equilibrium when the pressure is higher than 6 MPa; when the pressure is lower than 4 MPa, the desorption effect plays a leading role. This is consistent with theoretical and experimental reports that little hydrogen can be stored in SWNTs when the pressure is lower than 5 MPa.5,11 A volumetric hydrogen storage capacity of 68 kg H2 /m3 was achieved for the cold-pressed binderless SWNT tablet, and more than 70% of the adsorbed hydrogen could be released under ambient pressure at room temperature. The hydrogen storage properties of the bulk SWNT material are expected to be further improved via optimization of the molding and pretreatment processes to satisfy the requirements for onboard hydrogen storage systems in fuel cell powered vehicles. The authors acknowledge the Special Funds for Major State Basic Research Projects of China G2000026403, National Natural Science Foundation of China 50032020 and 50025204 , and WENET of Japan.
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