CN101837970A - Method for preparing three-dimensional macro carbon nanometer pipe network - Google Patents
Method for preparing three-dimensional macro carbon nanometer pipe network Download PDFInfo
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- CN101837970A CN101837970A CN 201010175749 CN201010175749A CN101837970A CN 101837970 A CN101837970 A CN 101837970A CN 201010175749 CN201010175749 CN 201010175749 CN 201010175749 A CN201010175749 A CN 201010175749A CN 101837970 A CN101837970 A CN 101837970A
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Abstract
The invention provides a method for preparing a three-dimensional macro carbon nanometer pipe network. The method comprises the following steps of: preparing a precursor of the carbon nanometer pipe network by purification and filtration treatments; loading a catalyst used for connection; making external carbon atoms form a chemical bond connection on contact points among carbon nanometer pipes at the high temperature and under an inducing action of the catalyst so as to realize the connection among the carbon nanometer pipes in a mode of chemical bonds; and finally obtaining the three-dimensional macro carbon nanometer pipe network with the chemical bond connection. The carbon nanometer pipes of the three-dimensional macro carbon nanometer pipe network are connected by chemical bonds, so that the whole carbon nanometer pipe network has high conductive property and mechanical property.
Description
Technical field
The present invention relates to the preparation method of carbon nano-tube material.
Background technology
Since Japanese scientist lijima in 1991 finds carbon nanotube first, with its unique physics and chemical property and accurate one dimension shape molecular structure, become the focus of physics, chemistry and the research of Materials science crossing domain rapidly, in scientific research and industry application, more and more get more and more people's extensive concerning.
The preparation of carbon nanotube mainly contains following several method: graphite arc method, catalystic pyrolysis, laser evaporation method etc.The original carbon nanotube of preparing often presents agglomeration, twines mutually between the tube and tube, and interlaced, material monolithic often is difficult to show stability, mechanical property, the conductive capability of single-root carbon nano-tube excellence in this case.Though carbon nanotube is with a wide range of applications, but prepared carbon nanotube all is Powdered under macroscopic view under the general condition, and the just conducting of contact between the pipe-pipe of carbon nanotube, there is not the connection of chemical bond, cause outstanding conductive capability of carbon nanotube and mechanical property can't bring into play on the macroscopic carbon nanotube material, this has limited the further application of carbon nano-tube material greatly.
Existing investigator prepares T-shape, " Y " type carbon nanotube (as document Carbon nanotube Yjunctions:growth and properties, Diamond and Related Materials, 13 (2004) 241-249).But the valence bond that just is confined to two or three carbon nanotubes connects, and also has suitable distance and will numerous carbon nanotubes couple together formation 3 D stereo carbon nano-tube macroscopic network by chemical bond connection mode.
Recently people such as Wu De sea prepare the carbon nanotube sponge (document Carbon Nanotube Sponges, Advanced Materials, 2010,22:617-621).They come the disposable carbon nanotube sponge that grows by the condition of control catalytic chemical vapor deposition technique, but show from the data that article provides, its prepared carbon nanotube sponge also is being in contact with one another of carbon nanotube, does not generate chemical bond between the carbon nanotube of contact.The carbon nanotube sponge of its preparation is an absorption property (You Heshui) also, is improved.
Summary of the invention
Purpose of the present invention just provides a kind of preparation method of three-dimensional macroscopic carbon nano-tube network.Have chemical bond between the carbon nanotube of the carbon nano-tube network of this kind method preparation and connect, the conductivity of whole carbon nano-tube network is strong, mechanical property good.
The present invention realizes that the technical scheme that its goal of the invention adopts is, a kind of preparation method of three-dimensional macroscopic carbon nano-tube network, and its way is:
A, carbon nanotube powder is carried out purification process with nitric acid or sulfuric acid or the mixed solution of the two, ultra-sonic dispersion, filtration, vacuum-drying then obtains the carbon nano-tube network presoma;
The catalyzer that B, the load of carbon nano-tube network presoma are used to connect, described catalyzer is iron, cobalt or nickel, and the compound that can be reduced into iron, cobalt or nickel under 780～1200 ℃.
C, will be the carbon nano-tube network presoma of supported catalyst place the silica tube of tube type resistance furnace, in the process that heats up, in silica tube, feed argon gas or nitrogen; Change logical hydrogen when being warming up to 780～1200 ℃, insulation 5～300min; Then, under 600～1200 ℃ of conditions, feed a kind of and argon gas in a kind of and acetylene in acetylene, methane, the Sweet natural gas, methane, the Sweet natural gas or the gas mixture 5～300min of nitrogen; Feed argon gas at last or nitrogen is cooled to room temperature, obtain the three-dimensional macroscopic carbon nano-tube network that chemical bond connects.
The mechanism of the inventive method is: with the purified carbon nano-tube network presoma that becomes the carbon nanotube of typing to be in contact with one another with filtration treatment of existing macroscopic carbon nanotube powdered material, the inducing action by the catalyzer iron, cobalt or the nickel that are used to connect under 780～1200 ℃ of conditions then, make carbon atom in acetylene, methane, the Sweet natural gas on the point of contact between the carbon nanotube, form the connection of chemical bond, the mode with chemical bond links together between the carbon nanotube thereby make, and prepares the three-dimensional macroscopic carbon nano-tube network that the band chemical bond connects.
Compared with prior art, the invention has the beneficial effects as follows:
The preparation method of a kind of three-dimensional macroscopic carbon nano-tube network that the present invention proposes, by this method, make the three-dimensional macroscopic carbon nano-tube network that connects with chemical bond between the carbon nanotube tube and tube, form the carbon nano-tube network that extends in all direction that chemical bond connects, connect than the contact between the carbon nanotube, it connects firm more, tight.The excellent properties of carbon nanotube can be not fully exerted on macroscopic carbon nanotube net materials, as leading
The electricity energy storage material, its conductivity and mechanical property improve greatly; Be used for matrix material, it not only serves as conducting matrix grain but also serve as the enhancing skeleton, and the mechanical property and the electric property of matrix material obviously improve; At strongthener, electro-conductive material, energy storage material and field of compound material have a good application prospect.
Experiment is proof also, connects by chemical bond between the carbon nanotube of the carbon nano-tube network that the present invention makes, and has good mechanical performance and electric property:
One, stereoscan photograph (figure two) shows, three-dimensional macroscopic carbon nano-tube network of the present invention (the B place among the figure two) between the pipe pipe of carbon nanotube has chemical bond really and connects.
Two, energy-storage property test
The result proves, by the three-dimensional macroscopic carbon nano-tube network of the present invention preparation and existing carbon nano-tube material when being applied to energy-storage composite material, stability is better, and capacity is higher: it only is 2% that its loading capacity can reach the decay of 65F/g (organic electrolyte) cycle index in the time of 200 times; And without the carbon nano-tube network presoma of connect handling, its loading capacity can reach 32F/g (organic electrolyte), and cycle index decays to 4% in the time of 200 times.This mainly is to have benefited from not only having served as conducting matrix grain but also served as the enhancing skeleton with the three-dimensional macroscopic carbon nano-tube network that chemical bond connects in matrix material, given full play to the satisfactory electrical conductivity and the mechanical property of carbon nanotube, thus whole stability and the energy-storage property that improves material.
Three, electroconductibility test
The result proves, the good conductivity of the three-dimensional macroscopic carbon nano-tube network of the inventive method preparation, and its specific conductivity is higher than 15.0S/cm, and without connecting the carbon nano-tube network presoma of handling, its electric conductivity only is 5.7S/cm.
Four, Mechanics Performance Testing
The result proves, the mechanical property of the three-dimensional macroscopic carbon nano-tube network that the chemical bond of the inventive method preparation connects is good, the pulling force of its Elongation test is about 7N/mm, and without connecting the carbon nano-tube network presoma of handling, the pulling force of its Elongation test is less than 1N/mm.
Above-mentioned A is filtered into low pressure suction filtration and high-pressure filteration in the step.
Filter than normal pressure, low pressure suction filtration and high-pressure filteration, its filtration time is shorter, and the carbon nano-tube network presoma that forms is finer and close.
The present invention is further detailed explanation below in conjunction with accompanying drawing and concrete embodiment.
Description of drawings
Fig. 1 is the digital camera photo of the prepared 3 D stereo carbon nano-tube network of the embodiment of the invention one.
Fig. 2 is the stereoscan photograph (the B place is the tie point of its generation among the figure) of 3 D stereo carbon nano-tube network of the present invention.
Fig. 3 is the tensile test collection of illustrative plates of carbon nano-tube network presoma of the present invention.
Fig. 4 is the tensile test collection of illustrative plates of the 3 D stereo carbon nano-tube network of invention.
Embodiment
Embodiment one
A kind of embodiment of the present invention is: a kind of preparation method of three-dimensional macroscopic carbon nano-tube network, and its way is:
A, carbon nanotube powder is carried out purification process with sulfuric acid, then ultra-sonic dispersion, take out press filtration, vacuum-drying, obtain the carbon nano-tube network presoma;
The catalyzer that B, the load of carbon nano-tube network presoma are used to connect.This routine catalyzer is selected iron nitrate for use, and the carbon nano-tube network presoma be impregnated in the iron nitrate solution, and the carbon nano-tube network presoma is soaked into fully, catalyzer iron nitrate that can load is used to connect on the carbon nano-tube network presoma.
C, will be the carbon nano-tube network presoma of supported catalyst place the silica tube of tube type resistance furnace, in the process that heats up, in silica tube, feed argon gas, with the air in the vent pipe; Change logical hydrogen when being warming up to 800 ℃, insulation 60min is so that iron nitrate is reduced into iron; Then, be cooled to 700 ℃, feed the gas mixture 60min of acetylene, argon gas (volume ratio is 1: 9), heat-treat reaction; Feed argon gas at last and be cooled to room temperature, obtain the three-dimensional macroscopic carbon nano-tube network that chemical bond connects.
Embodiment two
The making method of method that this is routine and embodiment one is basic identical, different only be:
The catalyzer that is used to connect of load was the mixture (mass ratio 1: 1) of iron nitrate and nickelous nitrate during B went on foot.
In C step, the temperature that feeds hydrogen is 950 ℃, and soaking time is 150min, and temperature is 900 ℃ during the thermal treatment reaction, feeding be natural-gas, reaction (insulation) time is 150min.
Embodiment three
This routine way is:
A, carbon nanotube powder is carried out purification process with nitric acid, then ultra-sonic dispersion, normal pressure filter, vacuum-drying, obtain the carbon nano-tube network presoma;
The catalyzer that B, the load of carbon nano-tube network presoma are used to connect.This routine catalyzer is selected nickel for use, adopt electrochemical deposition method supported catalyst metallic nickel, its concrete parameter is: with the carbon nano-tube network presoma as working electrode, with constant potential 2.05V in plating bath (containing in every 50mL solution: single nickel salt 15.00g, nickelous chloride 2.00g, boric acid 2.00g, sodium lauryl sulphate 0.05g, soluble saccharin 0.02g), carry out direct current electroless plating 5min (minute), be incubated 30min down with the secondary deionized water flushing and at 100 ℃ then, be about to metallic nickel and be deposited on the carbon nano-tube network presoma.
C, will be the carbon nano-tube network presoma of supported catalyst place the silica tube of tube type resistance furnace, in the process that heats up, in silica tube, feed nitrogen, with the air in the vent pipe; Change logical hydrogen when being warming up to 1200 ℃, insulation 5min, not oxidized to guarantee metallic nickel; Then, under same temperature (1200 ℃), feed methane gas 5min, heat-treat reaction; Feed nitrogen at last and be cooled to room temperature, obtain the three-dimensional macroscopic carbon nano-tube network that chemical bond connects.
Embodiment four
The making method of method that this is routine and embodiment three is basic identical, different only be:
The transition of A in the step is high-pressure filteration; In B step load be used to connect catalyzer and make cobalt metal into, single nickel salt, nickelous chloride in the corresponding plating bath change rose vitriol, cobalt chloride into; Temperature when feeding hydrogen in C step is 780 ℃, and soaking time is 300min, and the temperature during the thermal treatment reaction is 600 ℃, feeding be natural-gas, and reaction (insulation) time is 300min.
Embodiment five
The making method of method that this is routine and embodiment three is basic identical, different only be:
The transition of A in the step is high-pressure filteration; In B step load be used to connect catalyzer and make metallic iron into, single nickel salt, nickelous chloride in the corresponding plating bath change ferric sulfate, iron(ic) chloride into; Temperature in C step during the thermal treatment reaction is 800 ℃, feeding be acetylene gas, and reaction (insulation) time is 300min.
Embodiment six
The making method of method that this is routine and embodiment three is basic identical, different only be:
Temperature in C step during the thermal treatment reaction is 800 ℃, feeding be the mixed gas (volume ratio 1: 1) of methane and nitrogen, and reaction (insulation) time is 300min.
Table 1 is the conductivity data (four probe method) of carbon nano-tube network presoma of the present invention.
The conductivity data (four probe method) of the 3 D stereo carbon nano-tube network that table 2 makes for the present invention.
From table 1, table 2 as can be seen, the good conductivity of the three-dimensional macroscopic carbon nano-tube network of the inventive method preparation, its specific conductivity is higher than 15.0S/cm, and without connecting the carbon nano-tube network presoma of handling, its electric conductivity only is 5.7S/cm.
The catalyzer that the present invention is used for the carbon nanotube connection removes above embodiment iron, cobalt, nickel and iron nitrate, nickelous nitrate, can also be any any compound that can be generated iron, cobalt or nickel under 780～1200 ℃ by hydrogen reducing; The gas that feeds in the temperature-rise period in C step and the last process of cooling can also be other rare gas element that shields, as helium except that being argon gas and the nitrogen.
Claims (2)
1. the preparation method of a three-dimensional macroscopic carbon nano-tube network, its way is:
A, carbon nanotube powder is carried out purification process with nitric acid or sulfuric acid or the mixed solution of the two, ultra-sonic dispersion, filtration, vacuum-drying then obtains the carbon nano-tube network presoma;
The catalyzer that B, the load of carbon nano-tube network presoma are used to connect, described catalyzer is iron, cobalt or nickel, and the compound that can be reduced into iron, cobalt or nickel under 780～1200 ℃.
C, will be the carbon nano-tube network presoma of supported catalyst place the silica tube of tube type resistance furnace, in the process that heats up, in silica tube, feed argon gas or nitrogen; Change logical hydrogen when being warming up to 780～1200 ℃, insulation 5～300min; Then, under 600～1200 ℃ of conditions, feed a kind of and argon gas in a kind of and acetylene in acetylene, methane, the Sweet natural gas, methane, the Sweet natural gas or the gas mixture 5～300min of nitrogen; Feed argon gas at last or nitrogen is cooled to room temperature, obtain the three-dimensional macroscopic carbon nano-tube network that chemical bond connects.
2. the preparation method of a kind of three-dimensional macroscopic carbon nano-tube network according to claim 1 is characterized in that: described A is filtered into low pressure suction filtration and high-pressure filteration in the step.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814345A (en) * | 2010-05-22 | 2010-08-25 | 西南交通大学 | Method for preparing loose three-dimensional macroscopic carbon nano-tube network |
| CN102424377A (en) * | 2011-09-15 | 2012-04-25 | 西南交通大学 | Method for preparing coiled carbon nanotube macroscopic body |
| CN103496688A (en) * | 2013-09-18 | 2014-01-08 | 西南交通大学 | Method for preparing carbon-based ternary network composite material |
Citations (4)
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| US6761870B1 (en) * | 1998-11-03 | 2004-07-13 | William Marsh Rice University | Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO |
| EP1797950A1 (en) * | 2005-12-14 | 2007-06-20 | Nanocyl S.A. | Catalyst for a multi-walled carbon nanotube production process |
| CN101003144A (en) * | 2006-01-22 | 2007-07-25 | 浙江省德清县莫干山竹胶板厂 | Composite board of small pieces of bamboo reinforcement, and manufacturing method |
| WO2007126412A2 (en) * | 2006-03-03 | 2007-11-08 | The Board Of Trustees Of The University Of Illinois | Methods of making spatially aligned nanotubes and nanotube arrays |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6761870B1 (en) * | 1998-11-03 | 2004-07-13 | William Marsh Rice University | Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure CO |
| EP1797950A1 (en) * | 2005-12-14 | 2007-06-20 | Nanocyl S.A. | Catalyst for a multi-walled carbon nanotube production process |
| CN101003144A (en) * | 2006-01-22 | 2007-07-25 | 浙江省德清县莫干山竹胶板厂 | Composite board of small pieces of bamboo reinforcement, and manufacturing method |
| WO2007126412A2 (en) * | 2006-03-03 | 2007-11-08 | The Board Of Trustees Of The University Of Illinois | Methods of making spatially aligned nanotubes and nanotube arrays |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814345A (en) * | 2010-05-22 | 2010-08-25 | 西南交通大学 | Method for preparing loose three-dimensional macroscopic carbon nano-tube network |
| CN102424377A (en) * | 2011-09-15 | 2012-04-25 | 西南交通大学 | Method for preparing coiled carbon nanotube macroscopic body |
| CN102424377B (en) * | 2011-09-15 | 2013-04-03 | 西南交通大学 | Method for preparing coiled carbon nanotube macroscopic body |
| CN103496688A (en) * | 2013-09-18 | 2014-01-08 | 西南交通大学 | Method for preparing carbon-based ternary network composite material |
| CN103496688B (en) * | 2013-09-18 | 2015-08-05 | 西南交通大学 | A kind of method preparing carbon system ternary network composite material |
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| CN101837970B (en) | 2011-08-24 |
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