CN103569992A - Preparation method of carbon nanotube - Google Patents
Preparation method of carbon nanotube Download PDFInfo
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- CN103569992A CN103569992A CN201210248544.0A CN201210248544A CN103569992A CN 103569992 A CN103569992 A CN 103569992A CN 201210248544 A CN201210248544 A CN 201210248544A CN 103569992 A CN103569992 A CN 103569992A
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Abstract
The invention provides a preparation method of a carbon nanotube. The method comprises the steps of: providing a clean metal substrate, employing a chemical vapor deposition method to grow graphene on the surface of the substrate; coating a catalyst on the graphene surface, placing the metal substrate in a chemical vapor deposition device, sealing it, starting a vacuum system, introducing hydrogen to a pressure of 1-100Pa, starting heating to 600-900DEG C, then starting plasma equipment, introducing a carbon-containing gas, keeping the status for 30-300min, at the end of the reaction, stopping heating, stopping introducing the carbon-containing gas, performing cooling to room temperature under hydrogen protection, and stopping introducing hydrogen, thus obtaining the carbon nanotube perpendicularly growing on the graphene surface. The preparation method of the carbon nanotube provided by the invention has a simple preparation process, the prepared carbon nanotube is perpendicular to the graphene surface, is well bonded with the graphene, has complete crystal structure, high uniformity and good consistency, can be the entirely transferred together with the graphene, and can be applied to field emission devices, etc.
Description
Technical field
The present invention relates to the synthetic field of novel material, particularly relate to a kind of preparation method of carbon nanotube.
Background technology
Carbon nanotube is to find the carbon fiber that uses Analytical high resolution Electronic Speculum to produce from arc process by physicist's Sumio Iijima of building ripple NEC laboratory in 1991, because its peculiar property is expected to replace conventional wires in unicircuit, can further improve degree of integration.Orthotropic carbon nanotube because of its regular arrangement and diameter little, in feds, have good application prospect.Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), and obtains the physics Nobel prize in 2010, again causes carbon material research boom.Because its unique structure and photoelectric property become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, many scientific workers have been attracted.The method of the carbon nanotube of preparation vertical substrates surface alignment has much at present, but the carbon nanotube that these methods prepare needs to be transplanted in conductive substrates in application process, make like this distribution of carbon nanotube be difficult to control, and in migration process, easily introduce other impurity components, thereby affect the field emissive power of carbon nanotube.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of preparation method of carbon nanotube, the method can make perpendicular to the epontic carbon nanotube of Graphene, gained orthogonal array carbon nanotube and Graphene associativity are good, high conformity, highly evenly, be convenient to global transfer, can be applicable to feds.
The preparation method of carbon nanotube provided by the invention, comprises the following steps:
(1) provide clean metal substrate, described metal substrate is placed in chemical vapor depsotition equipment, sealing, pass into protective gas and drain after air, be heated to 800～1000 ℃, pass into carbonaceous gas, keep 10～100min, stopped reaction, obtains the metal substrate that surface growth has Graphene;
(2) by after the Graphene surface coated catalyzer of (1) gained metal substrate; be placed in described chemical vapor depsotition equipment; sealing; open vacuum system; passing into hydrogen to air pressure is that 1 ~ 100Pa starts heating; after being heated to 600 ~ 900 ℃, open plasma apparatus; pass into carbonaceous gas; keep 30～300min, after question response finishes, stop heating; stop passing into described carbonaceous gas; under described hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in described Graphene surface.
The object of step (1) is to provide clean metal substrate, carries out the preparation of graphene layer in metal substrate.
The clean operation of metal substrate is: with ethanol, acetone and deionized water, carry out ultrasonic cleaning respectively.
Preferably, metal substrate is iron foil, Copper Foil, cobalt paper tinsel or nickel foil.
Preferably, carbonaceous gas is methane, ethane, acetylene, propane, carbon monoxide or ethanol.
Preferably, the flow of carbonaceous gas is 100～1000sccm.
Preferably, protective gas is hydrogen, nitrogen or argon gas.
Preferably, the flow of protection gonosome is 50～100sccm.
Step (2) is under catalyst action, and preparation is perpendicular to the process of the epontic carbon nanotube of Graphene.
Preferably, catalyzer is iron nitrate, iron(ic) chloride, ferric sulfate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, rose vitriol, nickelous nitrate, nickelous chloride or single nickel salt.
Preferably, the concentration of catalyzer is 0.01～1mol/L.
More preferably, the concentration of catalyzer is 0.1～0.5mol/L.
Catalyzer itself does not participate in reaction; but at high temperature; granules of catalyst can cracking be also reduced into metallic particles under hydrogen effect, and these metal pair carbon have certain solid solubility (limit of solubility of solute in sosoloid), thereby provides place for the nucleation and growth of carbon nanotube.
To the object that passes into hydrogen in chemical vapor depsotition equipment, the initial stage is that the later stage is in the process of carbon nano tube growth in order to drain the air in equipment, hydrogen can water down the concentration of carbonaceous gas, be beneficial to the growth of carbon nanotube, in addition, hydrogen can also become metallic particles by catalyst reduction.
Preferably, the flow of hydrogen is 50～200sccm.
Under the high temperature of 600～900 ℃; open plasma apparatus; pass into carbonaceous gas; start to occur to answer, react after 30～300min, stop heating; stop passing into carbonaceous gas; under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, just obtain at the orthotropic carbon nanotube in Graphene surface.
Preferably, plasma apparatus is radio-frequency plasma equipment, and the power of radio frequency adaptation is 500W.
Plasma apparatus provides carbon nano tube growth institute energy requirement, and plasma body provides orthotropic motivating force in carbon nano tube growth process, thereby has guaranteed the array growth of carbon nanotube.
Preferably, carbonaceous gas is methane, ethane, acetylene, propane, carbon monoxide or ethanol.
Preferably, the flow of carbonaceous gas is 100～1000sccm.
Under the high temperature of 600～900 ℃; granules of catalyst meeting cracking is also reduced into metallic particles under hydrogen effect; after carbonaceous gas enters; in surface of metal particles cracking; carbon starts to be dissolved in metal, after certain hour, reaches capacity, and now carbon nanotube starts forming core; vertical-growth in the environment of plasma body, slowly grows into the carbon nanotube of array arrangement.
Preferably, this preparation method also comprises the operation of removing as follows metal substrate: the acid solution that is 0.01～1mol/L by concentration or FeCl
3the carbon nanotube that solution soaking makes.
Preferably, acid solution is one or more in hydrochloric acid, sulfuric acid and nitric acid.
Acid solution can make metal substrate dissolve, thereby is removed, and acid solution can also be removed residual catalyzer simultaneously.Wherein, for metal copper foil, adopt FeCl
3solution soaks to be removed.
The Graphene growing out from metal substrate and perpendicular to the epontic carbon nanotube of Graphene, both associativities are good, and Graphene has high conductivity, carbon nanotube high conformity, highly even.Because the generation of carbon nanotube is to rely on the reduce deposition of carbonaceous gas to obtain, crystalline structure is complete, has superperformance.Because graphene layer has high conduction performance, therefore the carbon nanotube making like this in application process without being transplanted to one by one in conductive substrates, can directly carry out global transfer, be applied to the fields such as feds, effectively avoid migration process to introduce other impurity components, and the carbon nanotube problem rambunctious that distributes, thereby guarantee the field emissive power of carbon nanotube.
The method of orthogonal array carbon nanotube of preparing on Graphene surface based on chemical Vapor deposition process provided by the invention, whole reaction process is the high temperature gas phase reduce deposition under catalyst action, and preparation technology is simple, and raw material sources are extensive, cost is low, is easy to realize large-scale industrial and produces; The chemical reagent that whole process is used can be recycled, substantially can be to environment; And the carbon nanotube making by preparation method of the present invention, perpendicular to Graphene surface growth, good with the associativity of Graphene, crystalline structure is complete, high conformity, highly evenly, be convenient to global transfer, can be applicable to feds.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention one prepared carbon nanotube.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment mono-
A preparation method for carbon nanotube, comprises the following steps:
(1) provide clean Copper Foil, Copper Foil is placed in chemical vapor depsotition equipment, sealing, the hydrogen that passes into 100sccm drains after air, is heated to 1000 ℃, passes into the methane of 50sccm, keeps 100min, and stopped reaction, obtains the Copper Foil that surface growth has Graphene;
(2) by after the Graphene surface coated 0.01mol/L iron nitrate of (1) gained Copper Foil; again be placed in chemical vapor depsotition equipment; sealing; open vacuum system; hydrogen to the air pressure that passes into 50sccm is that 1Pa starts heating; after being heated to 700 ℃, open radio-frequency plasma equipment (radio frequency adaptation power is 500w); pass into the methane of 100sccm; keep 300min, after question response finishes, stop heating; stop passing into methane; under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in Graphene surface.
Finally, the FeCl that is 0.1mol/L by concentration
3carbon nanotube is soaked, can remove Copper Foil, can remove the iron powder generating after iron nitrate reduction simultaneously.
Fig. 1 is the SEM figure of the embodiment of the present invention one prepared carbon nanotube.As can be seen from Figure 1, carbon nanotube is successfully preparation, and prepared carbon nanotube, perpendicular to substrate grown, presents array distribution, highly even, and caliber is 20～80nm.
Embodiment bis-
A preparation method for carbon nanotube, comprises the following steps:
(1) provide clean iron foil, iron foil is placed in chemical vapor depsotition equipment, sealing, the nitrogen that passes into 50sccm drains after air, is heated to 900 ℃, passes into the acetylene of 200sccm, keeps 10min, and stopped reaction, obtains the iron foil that surface growth has Graphene;
(2) by after the Graphene surface coated 0.01mol/L Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of (1) gained iron foil; again be placed in chemical vapor depsotition equipment; sealing; open vacuum system; hydrogen to the air pressure that passes into 100sccm is that 100Pa starts heating; after being heated to 600 ℃, open radio-frequency plasma equipment (radio frequency adaptation power is 500w); pass into the acetylene of 200sccm; keep 150min, after question response finishes, stop heating; stop passing into acetylene; under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in Graphene surface.
Finally, with the hydrochloric acid that concentration is 0.01mol/L, carbon nanotube is soaked, can remove iron foil, can remove the cobalt powder generating after Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES reduction simultaneously.
Embodiment tri-
A preparation method for carbon nanotube, comprises the following steps:
(1) provide clean cobalt paper tinsel, cobalt paper tinsel is placed in chemical vapor depsotition equipment, sealing, the argon gas that passes into 80sccm drains after air, is heated to 800 ℃, passes into the ethane of 150sccm, keeps 80min, and stopped reaction, obtains the cobalt paper tinsel that surface growth has Graphene;
(2) by after the Graphene surface coated 0.01mol/L nickelous nitrate of (1) gained cobalt paper tinsel; again be placed in chemical vapor depsotition equipment; sealing; open vacuum system; hydrogen to the air pressure that passes into 150sccm is that 50Pa starts heating; after being heated to 900 ℃, open radio-frequency plasma equipment (radio frequency adaptation power is 500w); pass into the ethane of 750sccm; keep 120min, after question response finishes, stop heating; stop passing into ethane; under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in Graphene surface.
Finally, with the sulfuric acid that concentration is 0.5mol/L, carbon nanotube is soaked, can remove cobalt paper tinsel, can remove the nickel powder generating after nickelous nitrate reduction simultaneously.
Embodiment tetra-
A preparation method for carbon nanotube, comprises the following steps:
(1) provide clean nickel foil, nickel foil is placed in chemical vapor depsotition equipment, sealing, the argon gas that passes into 80sccm drains after air, is heated to 850 ℃, passes into the propane of 100sccm, keeps 50min, and stopped reaction, obtains the nickel foil that surface growth has Graphene;
(2) by after the Graphene surface coated 0.01mol/L ferric sulfate of (1) gained nickel foil; again be placed in chemical vapor depsotition equipment; sealing; open vacuum system; hydrogen to the air pressure that passes into 200sccm is that 10Pa starts heating; after being heated to 800 ℃, open radio-frequency plasma equipment (radio frequency adaptation power is 500w); pass into the propane of 800sccm; keep 60min, after question response finishes, stop heating; stop passing into propane; under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in Graphene surface.
Finally, with the hydrochloric acid that concentration is 1mol/L, carbon nanotube is soaked, can remove nickel foil, can remove the iron powder generating after ferric sulfate reduction simultaneously.
Embodiment five
A preparation method for carbon nanotube, comprises the following steps:
(1) provide clean Copper Foil, Copper Foil is placed in chemical vapor depsotition equipment, sealing, the nitrogen that passes into 100sccm drains after air, is heated to 950 ℃, passes into the carbon monoxide of 150sccm, keep 20min, stopped reaction, obtains the Copper Foil that surface growth has Graphene;
(2) by after the Graphene surface coated 0.01mol/L iron(ic) chloride of (1) gained Copper Foil, again be placed in chemical vapor depsotition equipment, sealing, open vacuum system, hydrogen to the air pressure that passes into 50sccm is that 30Pa starts heating, after being heated to 750 ℃, open radio-frequency plasma equipment (radio frequency adaptation power is 500w), pass into the carbon monoxide of 1000sccm, keep 30min, after question response finishes, stop heating, stop passing into carbon monoxide, under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in Graphene surface.
Finally, the FeCl that is 1mol/L by concentration
3carbon nanotube is soaked, can remove Copper Foil, can remove the iron powder generating after iron(ic) chloride reduction simultaneously.
Embodiment six
A preparation method for carbon nanotube, comprises the following steps:
(1) provide clean nickel foil, nickel foil is placed in chemical vapor depsotition equipment, sealing, the hydrogen that passes into 50sccm drains after air, is heated to 1000 ℃, passes into the ethanol of 200sccm, keeps 200min, and stopped reaction, obtains the nickel foil that surface growth has Graphene;
(2) by after the Graphene surface coated 0.01mol/L cobalt chloride of (1) gained nickel foil; again be placed in chemical vapor depsotition equipment; sealing; open vacuum system; hydrogen to the air pressure that passes into 150sccm is that 100Pa starts heating; after being heated to 850 ℃, open radio-frequency plasma equipment (radio frequency adaptation power is 500w); pass into the ethanol of 500sccm; keep 100min, after question response finishes, stop heating; stop passing into ethanol; under hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in Graphene surface.
Finally, with the hydrochloric acid that concentration is 1mol/L, carbon nanotube is soaked, can remove nickel foil, can remove the cobalt powder generating after cobalt chloride reduction simultaneously.
By preparation method of the present invention, make perpendicular to the epontic carbon nanotube of Graphene, good with the associativity of Graphene, crystalline structure is complete, high conformity, highly evenly, be convenient to global transfer, can be applicable to feds.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for carbon nanotube, is characterized in that, comprises the following steps:
(1) provide clean metal substrate, described metal substrate is placed in chemical vapor depsotition equipment, sealing, pass into protective gas and drain after air, be heated to 800～1000 ℃, pass into carbonaceous gas, keep 10～100min, stopped reaction, obtains the metal substrate that surface growth has Graphene;
(2) by after the Graphene surface coated catalyzer of (1) gained metal substrate; be placed in described chemical vapor depsotition equipment; sealing; open vacuum system; passing into hydrogen to air pressure is that 1 ~ 100Pa starts heating; after being heated to 600 ~ 900 ℃, open plasma apparatus; pass into carbonaceous gas; keep 30～300min, after question response finishes, stop heating; stop passing into described carbonaceous gas; under described hydrogen shield, be cooled to room temperature, stop passing into hydrogen, obtain at the orthotropic carbon nanotube in described Graphene surface.
2. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, described metal substrate is iron foil, Copper Foil, cobalt paper tinsel or nickel foil.
3. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, described protective gas is hydrogen, nitrogen or argon gas.
4. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, described catalyzer is iron nitrate, iron(ic) chloride, ferric sulfate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, rose vitriol, nickelous nitrate, nickelous chloride or single nickel salt.
5. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, the concentration of described catalyzer is 0.01～1mol/L.
6. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, described plasma apparatus is radio-frequency plasma equipment, and the power of radio frequency adaptation is 500w.
7. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, described carbonaceous gas is methane, ethane, acetylene, propane, carbon monoxide or ethanol.
8. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, the flow of described carbonaceous gas is 100～1000sccm.
9. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, the flow of described hydrogen is 50～200sccm.
10. the preparation method of carbon nanotube as claimed in claim 1, is characterized in that, also comprises the operation of removing as follows described metal substrate: the described carbon nanotube that the acid solution that is 0.01～1mol/L by concentration or FeCl3 solution soaking make.
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Cited By (10)
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| CN105803420A (en) * | 2016-03-21 | 2016-07-27 | 中南大学 | Diamond composite wrapped by graphene and/or carbon nanotubes and preparation method and application of diamond composite wrapped by graphene and/or carbon nanotubes |
| CN105836730A (en) * | 2016-04-20 | 2016-08-10 | 上海交通大学 | Method for synthesizing carbon nanotubes in situ on graphite material surface |
| CN106145082A (en) * | 2015-03-30 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Narrow chirality distribution SWCN horizontal array and preparation method thereof |
| CN106672947A (en) * | 2016-12-28 | 2017-05-17 | 江苏中亚新材料股份有限公司 | Preparation method of multilayered graphene with ultrahigh conductivity |
| CN107400928A (en) * | 2017-07-25 | 2017-11-28 | 东北石油大学 | A kind of simple and easy method of direct growth carbon nano pipe array on metal and application |
| CN108538623A (en) * | 2018-05-15 | 2018-09-14 | 兰州理工大学 | A kind of preparation method of manganese bioxide/carbon nano tube combination electrode material |
| CN109956462A (en) * | 2019-03-14 | 2019-07-02 | 北京航空航天大学 | Carbon nano-particle preparation system, carbon nano-particle aerosol generate system and method |
| CN111170310A (en) * | 2020-01-15 | 2020-05-19 | 北京科技大学 | Three-dimensional graphene/carbon nanotube composite material and preparation method thereof |
| CN113912043A (en) * | 2021-11-30 | 2022-01-11 | 南昌大学 | Preparation method of graphene/carbon nanotube composite array material |
| CN115432695A (en) * | 2022-10-10 | 2022-12-06 | 四川天人化学工程有限公司 | Method for manufacturing carbon nano tube by replacing methane with high-concentration carbon monoxide |
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| CN106145082A (en) * | 2015-03-30 | 2016-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Narrow chirality distribution SWCN horizontal array and preparation method thereof |
| CN105803420A (en) * | 2016-03-21 | 2016-07-27 | 中南大学 | Diamond composite wrapped by graphene and/or carbon nanotubes and preparation method and application of diamond composite wrapped by graphene and/or carbon nanotubes |
| CN105803420B (en) * | 2016-03-21 | 2018-03-06 | 中南大学 | Graphene and/or CNT cladding diamond composite and preparation method and application |
| CN105836730A (en) * | 2016-04-20 | 2016-08-10 | 上海交通大学 | Method for synthesizing carbon nanotubes in situ on graphite material surface |
| CN105836730B (en) * | 2016-04-20 | 2019-04-19 | 上海交通大学 | A kind of method of the spontaneous carbon nanotube of graphite material surface in situ |
| CN106672947A (en) * | 2016-12-28 | 2017-05-17 | 江苏中亚新材料股份有限公司 | Preparation method of multilayered graphene with ultrahigh conductivity |
| CN107400928A (en) * | 2017-07-25 | 2017-11-28 | 东北石油大学 | A kind of simple and easy method of direct growth carbon nano pipe array on metal and application |
| CN107400928B (en) * | 2017-07-25 | 2019-08-06 | 东北石油大学 | A kind of simple and easy method directly growing carbon nano pipe array on metal and application |
| CN108538623A (en) * | 2018-05-15 | 2018-09-14 | 兰州理工大学 | A kind of preparation method of manganese bioxide/carbon nano tube combination electrode material |
| CN109956462A (en) * | 2019-03-14 | 2019-07-02 | 北京航空航天大学 | Carbon nano-particle preparation system, carbon nano-particle aerosol generate system and method |
| CN111170310A (en) * | 2020-01-15 | 2020-05-19 | 北京科技大学 | Three-dimensional graphene/carbon nanotube composite material and preparation method thereof |
| CN111170310B (en) * | 2020-01-15 | 2022-02-25 | 北京科技大学 | Three-dimensional graphene/carbon nanotube composite material and preparation method thereof |
| CN113912043A (en) * | 2021-11-30 | 2022-01-11 | 南昌大学 | Preparation method of graphene/carbon nanotube composite array material |
| CN115432695A (en) * | 2022-10-10 | 2022-12-06 | 四川天人化学工程有限公司 | Method for manufacturing carbon nano tube by replacing methane with high-concentration carbon monoxide |
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Application publication date: 20140212 |