CN1557702A - Fullerene hydrogen storage material etched by microwave plasma and method for preparing the same - Google Patents
Fullerene hydrogen storage material etched by microwave plasma and method for preparing the same Download PDFInfo
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- CN1557702A CN1557702A CNA2004100127028A CN200410012702A CN1557702A CN 1557702 A CN1557702 A CN 1557702A CN A2004100127028 A CNA2004100127028 A CN A2004100127028A CN 200410012702 A CN200410012702 A CN 200410012702A CN 1557702 A CN1557702 A CN 1557702A
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- hydrogen
- etching
- hydrogen storage
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- soccerballene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The present invention features that fullerene surface is etched through microwave plasma process to increase the diffusion passage of hydrogen molecule to carbon cage center and to make more hydrogen enter inside of fullerene to raise the hydrogen storing capacity. The present invention has etching power of 0.3-3 Kw, etching temperature of 300-1500 deg.c, processing pressure of 600-6000 Pa, etching gas of hydrogen, etching condition gas being nitrogen, argon or their mixture. The etching gas includes hydrogen more than 80 vol%, and nitrogen and/or argon less than 20 vol%. The hydrogen storing fullerene material of the present invention has hydrogen storing capacity of 1.0-3.0 wt%.
Description
Technical field
The present invention relates to a kind of soccerballene hydrogen storage material and technology of preparing thereof, particularly relate to the method for modifying that adopts microwave plasma-etching and prepare soccerballene hydrogen storage material and technology of preparing thereof through modification.
Background technology
The development Hydrogen Energy, what primarily capture is this big bottleneck of scale accumulating of hydrogen.USDOE (DOE) is decided to be 6.5wt% (63kg/m with the commercialization index of hydrogen storage material
3), if consider economic target, also there are not any hydrogen storage material or hydrogen storage method can reach target at present.In current numerous storage medium, porous carbon materials (as gac, carbon nanofiber, carbon nanotube etc.) Chu Qing, because of its operating pressure is low, in light weight, advantage such as the shape choice is big has caused people's very big concern.
1997, reported first such as the U.S. Dillon hydrogen adsorption characteristic of Single Walled Carbon Nanotube (SWNTs), infer that the SWNTs hydrogen storage capability is 5～10wt%.1998, U.S. Chambers etc. report carbon nano fibers (CNFs) under 12MPa hydrogen storage capability up to 22.3 liters of hydrogen/gram CNFs.1999, Singapore Chen etc. reported through the adulterated multi-walled carbon nano-tubes of Li, K (MWNTs), and hydrogen storage capability reaches 20wt% and 14wt% respectively.1999, reported in the patent of invention of Shenyang metal institute of the Chinese Academy of Sciences that the hydrogen storage capability of the SWNTs of preparation is 4.2wt% (ZL991122902.4), CNFs has the hydrogen storage capability (ZL12779953A) up to 10～12wt%.(JP 10-072201) reported the technology of preparing of a kind of hydrogen storage alloy/carbon nanotube (carbon nano fiber) matrix material in the patent of invention of Japan Toyota Company, and at ambient temperature, its hydrogen storage capability is up to more than the 10wt%.In addition, Toshiba also prepares alkali doped ionic hydrogen storage alloy/carbon nanotube (carbon nano fiber) matrix material, and its hydrogen storage capability is 1～8wt% (JP 2001-146408).In recent years, China is obtaining certain progress aspect the Chu Qing of one-dimensional nano carbon.Nankai University adopts with Toyota Company's diverse ways and prepares hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material, hydrogen storage capability be 2.5～5.2wt% (WO01/53550A1, CN00100500.7).Wuhan University of Technology (ZL02138977.2) using plasma lithographic technique carries out stripped etchings such as hydrogen to 1-dimention nano carbon materials such as carbon nanotube, CNFs, and it has been carried out hydrogen storage alloy/hydrogen storage metal modified, make the hydrogen storage capability of one-dimensional nano carbon reach 5.5wt%.
Soccerballene (Fullerene) is the novel ball structural carbon molecule of finding the eighties in last century.Because structure is special, has peculiar physics and chemical property.The boring volume that is surrounded by carbon atom has bigger pore volume, is considered to good hydrogen storing unit.At present, the hydrogenation reaction fullerene synthesis hydride (C of the carbon atom by the surface
2nH
2m, the method for m≤n) can be stored a part of hydrogen, but the reaction of hydrogen and C atom must be carried out under 400-500 ℃ and 60-80MPa.Reduce temperature of reaction and pressure (Loutfy R O, et al.2001) though adopt being doped with of basic metal or catalyzer to be beneficial to, hydrogen uptake condition is still comparatively harsh, and importantly, its inner pore volume is not fully utilized.Toyota Motor company (JP10-072201) passes through at C
60After the coating of the hydrogen storage metal Pd of the about 20nm of modification one bed thickness, successfully hydrogen has been introduced C on the surface
60Inside, but its hydrogen storage temperature all-below the 196K, the storage hydrogen condition is comparatively harsh.
Summary of the invention
The purpose of this invention is to provide a kind of soccerballene hydrogen storage material and preparation method thereof, this hydrogen storage material fullerene-based material that is untreated is greatly improved aspect the hydrogen condition storing, and preparation technology grasps easily.
Soccerballene hydrogen storage material of the present invention is C
60Passed through the hydrogen storage material that microwave plasma-etching is handled on the fullerene-based material surface.Described fullerene-based material is a series of globosity carbon molecule or Fuller olefins of being made up of to thousands of even carbon atoms dozens of, and chemical general formula is C
2N, wherein n is the natural number more than or equal to 30.
Soccerballene of the present invention can be a kind of globosity carbon molecule or Fuller olefin, also can be two or more globosity carbon molecule or Fuller olefin by the mixture of arbitrary proportion proportioning.
The present invention adopts the method for microwave plasma-etching that etching is carried out on the surface of soccerballene hydrogen storage material, thereby opens the diffusion admittance of hydrogen, makes more hydrogen enter the inside of fullerene molecule, improves the hydrogen storage capability of soccerballene.
The preparation method of soccerballene hydrogen storage material of the present invention, be soccerballene to be carried out microwave plasma-etching handle on microwave plasma generation device, the power of etching is 0.3～3kW, and etching gas is a hydrogen, 300～1500 ℃ of etching temperatures are handled air pressure 6.0 * 10
2～6.0 * 10
3Pa; Condition gas is nitrogen or argon gas or the gas mixture of the two.Under the condition gas of nitrogen or argon gas or the gas mixture of the two, the hydrogen ratio is greater than 80% (volume), and nitrogen or argon gas be less than 20% (volume), and for the mixing condition gas of nitrogen and argon gas, the summation of nitrogen and argon gas is not more than 20% (volume).
The concrete preparation technology of soccerballene hydrogen storage material is as follows:
Fullerene-based material is by commercial, and soccerballene purity is 30-100%.
Soccerballene is carried out microwave plasma-etching, and microwave plasma generation device as shown in Figure 1.The normal power of etching is 0.3～3kW, and 300～1500 ℃ of etching temperatures are handled air pressure 6.0 * 10
2～6.0 * 10
3Pa; Etching gas is a hydrogen, and condition gas is nitrogen or argon gas or the gas mixture of the two.Under nitrogen or argon gas condition, the hydrogen ratio is usually greater than 80% (volume), and nitrogen or argon gas are less than 20% (volume); For mixing condition gas, the summation of nitrogen and argon gas should be not more than 20% (volume).
Microwave plasma-etching of the present invention mainly carries out on microwave plasma generation device.This device mainly contains parts such as microwave source, circulator, tuner, coupled antenna and vacuum extractor and forms, its principle of work is: microwave energy along rectangular waveguide with the TE10 mode propagation, under the acting in conjunction of circulator, tuner and coupled antenna etc., the microwave propagation pattern is converted to the TE01 pattern of propagating along circular waveguide, becomes the homogeneous plasma ball at microwave cavity underexcitation gas wherein afterwards.The normal power of microwave plasma-etching is 0.3～3kW, and 300～1500 ℃ of etching temperatures are handled air pressure 6.0 * 10
2～6.0 * 10
3Pa, etching gas are hydrogen, and condition gas is nitrogen or argon gas or the gas mixture of the two.Under nitrogen or argon gas condition, the hydrogen ratio is greater than 80% (volume), and nitrogen or argon gas are less than 20% (volume), and for mixing condition gas, the summation of nitrogen and argon gas is not more than 20% (volume).
The hydrogen experimental installation that stores of the present invention is Sieverts ' instrument (referring to Fig. 2).Experimental installation mainly contains sources of hydrogen system, pumped vacuum systems, example reaction system, data collecting system and hydrogen discharge system etc. and partly forms.Adopt pressure differential method to measure the hydrogen storage capability of described soccerballene, adopt drainage to measure the desorption rate of hydrogen.The hydrogen purity of test is 99.999%, and original pressure is normal pressure～20MPa, and temperature is room temperature～250 ℃.
The present invention adopts stripped technology such as microwave that the spherical molecule of soccerballene is carried out plasma etching, generates certain defective on its surface, is diffused into spherical intramolecular passage for hydrogen molecule provides.The hydrogen condition that stores of the soccerballene hydrogen storage material of preparation is greatly improved.Experiment shows that the suction hydrogen effect of the hydrogen storage material of preparation can be carried out under the condition of room temperature, 1-10MPa.Under normal pressure, low-temperature heat condition, major part is adsorbed hydrogen and can obtains discharging.
Description of drawings
Fig. 1 is the microwave plasma generation device synoptic diagram.
Fig. 2 is the hydrogen test set equipment that the stores synoptic diagram of soccerballene.
Number in the figure implication: 1 microwave source, 2 microwave plasma balls, 3 microwave cavities, 4 condition gases, 5 sources of hydrogen systems, 6 pumped vacuum systems, 7 example reaction systems, 8 data collecting systems, 9 hydrogen discharge systems.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Device for carrying out said as shown in Figure 1 and Figure 2.
Fullerene-based material is by commercial, and soccerballene purity is 60%, and 99% is C in the globosity carbon molecule
60, all the other 1% are C
70In hydrogen purity is 99.999%, and original pressure is under 7Mpa and the room temperature condition, and after tested, its hydrogen storage capability only is 0.1wt%.Sample is carried out microwave plasma-etching, and etching power is 2.5kW, 1200 ℃ of temperature, and time 2h handles air pressure 6.0 * 10
2Pa, etching gas are hydrogen.Under identical test condition, hydrogen storage capability is 2.0wt%.Desorption experiment under normal pressure, the 100 ℃ of heating conditions shows that wherein 85% the hydrogen that is adsorbed has obtained release.
Embodiment 2
Soccerballene sample, microwave plasma-etching technology and to store the hydrogen experiment condition identical with example 1, but the time of microwave plasma-etching is 4h.The hydrogen storage capability of etching sample is 3.0wt%, and wherein 89% the hydrogen that is adsorbed has obtained release.
Embodiment 3
Soccerballene sample, microwave plasma-etching technology and to store the hydrogen experiment condition identical with example 1, but the temperature of microwave plasma-etching is 1000 ℃, and etching time is 6h.The hydrogen storage capability of the sample of etching is 1.0wt%, and wherein 91% the hydrogen that is adsorbed has obtained release.
Embodiment 4
Soccerballene sample, microwave plasma-etching technology and to store the hydrogen experiment condition identical with example 2, but condition gas is the nitrogen of 20% (volume), hydrogen 80% (volume).The hydrogen storage capability of etching sample is 2.5wt%, and wherein 88% the hydrogen that is adsorbed has obtained release.
Soccerballene sample, microwave plasma-etching technology and to store the hydrogen experiment condition identical with example 2, but condition gas is the argon gas of the nitrogen and 10% (volume) of 10% (volume), hydrogen 80% (volume).The hydrogen storage capability of etching sample is 2.8wt%.Wherein 82% the hydrogen that is adsorbed has obtained release.
Claims (4)
1, a kind of soccerballene hydrogen storage material, it is characterized in that it is that the hydrogen storage material that microwave plasma-etching is handled has been passed through on the soccerballene surface, described soccerballene is a series of globosity carbon molecule or Fuller olefins of being made up of to thousands of even carbon atoms dozens of, and chemical general formula is C
2n, wherein n is the natural number more than or equal to 30.
2, by the described hydrogen storage material of claim 1, it is characterized in that described soccerballene can be a kind of globosity carbon molecule or Fuller olefin, also can be two or more globosity carbon molecule or Fuller olefin by the mixture of arbitrary proportion proportioning.
3, the preparation method of the described hydrogen storage material of claim 1, it is characterized in that soccerballene carries out microwave plasma-etching and handles on microwave plasma generation device, the power of etching is 0.3～3kW, and etching gas is a hydrogen, 300～1500 ℃ of etching temperatures are handled air pressure 6.0 * 10
2～6.0 * 10
3Pa, condition gas are nitrogen or argon gas or the gas mixture of the two.
4, press the preparation method of the described hydrogen storage material of claim 3, it is characterized in that under the condition gas of nitrogen or argon gas or the gas mixture of the two, the hydrogen ratio is greater than 80% (volume), and nitrogen or argon gas are less than 20% (volume), for the mixing condition gas of nitrogen and argon gas, the summation of nitrogen and argon gas is not more than 20% (volume).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100237295A1 (en) * | 2009-03-19 | 2010-09-23 | Bose Anima B | Microspheres and their methods of preparation |
| CN112624087A (en) * | 2020-12-22 | 2021-04-09 | 同济大学 | Aluminum ion battery positive electrode material prepared from hydrogenated fullerene material, and preparation and application thereof |
-
2004
- 2004-02-05 CN CNA2004100127028A patent/CN1557702A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100237295A1 (en) * | 2009-03-19 | 2010-09-23 | Bose Anima B | Microspheres and their methods of preparation |
| US8986836B2 (en) * | 2009-03-19 | 2015-03-24 | Ohio University | Microspheres and their methods of preparation |
| CN112624087A (en) * | 2020-12-22 | 2021-04-09 | 同济大学 | Aluminum ion battery positive electrode material prepared from hydrogenated fullerene material, and preparation and application thereof |
| CN112624087B (en) * | 2020-12-22 | 2022-12-16 | 同济大学 | Aluminum ion battery positive electrode material prepared from hydrogenated fullerene material, and preparation and application thereof |
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