CN103086360A - Method for continuously preparing graphene - Google Patents
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- CN103086360A CN103086360A CN2011103399749A CN201110339974A CN103086360A CN 103086360 A CN103086360 A CN 103086360A CN 2011103399749 A CN2011103399749 A CN 2011103399749A CN 201110339974 A CN201110339974 A CN 201110339974A CN 103086360 A CN103086360 A CN 103086360A
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Abstract
The invention provides a method for continuously preparing graphene. The method comprises the steps that: a metal deposition mesh with a pore size of 50-325meshes is washed; the washed metal deposition mesh is arranged in a reaction chamber; protective gas is delivered into the reaction chamber, and the state is maintained for 1-60min; the reaction chamber is heated to 600-1100 DEG C; a gas-state carbon-containing substance is delivered in, and the gas-state carbon-containing substance is subjected to a reaction for 30-60min under the catalyzing of the metal deposition mesh, such that graphene is prepared, wherein the graphene accumulates at a collection mesh with a pore size of 200-325meshes; the collection mesh is replaced, and graphene collection is continued. The method provided by the invention has the advantage of non-intermittent continuous preparation, simple equipment, and simple and feasible operations. Compared with graphene prepared with a common reduction method, the graphene prepared with the method provided by the invention has the advantages of low defect rate and good conductivity.
Description
Technical field
The present invention relates to the method for process for preparing graphenes by chemical vapour deposition, particularly relate to a kind of method of continuous production Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) etc. is found, is the carbon material as thin as a wafer of single or multiple lift.Single-layer graphene has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g (A Peigney, Ch Laurent, et al.Carbon, 2001,39,507) can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.The structure of Graphene uniqueness and photoelectric property make it become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials.
The research of Graphene and the preparation in enormous quantities, low-cost of using it have proposed an urgent demand.The method for preparing at present Graphene mainly contain graphite breakaway (et al.Science 2004,306,666 for Novoselov K S, Geim A K), chemistry redox method (D A Dikin, et al.Nature 2007,448,457; Sasha Stankovich, Dmitriy A Dikin, Richard D Piner, et al.Carbon 2007,45,1558), ultrasonic stripping method (Guohua Chen, Wengui Weng, Dajun Wu, et al.Carbon.2004,42,753) etc.Yet the shape of the Graphene that these methods are prepared is all irregular basically, and the number of plies is indefinite, and pattern is restive.
Chemical Vapor deposition process has been realized the batch production of carbon nanotube, is expected to utilize chemical Vapor deposition process to realize the batch production of Graphene.So people begin to utilize process for preparing graphenes by chemical vapour deposition (Alexander N, Obraztsov.Nature nanotechnology.2009,4,212), but just a small amount of preparation of the method.Publication number is a kind of method that the Chinese patent application of CN101285175A discloses process for preparing graphenes by chemical vapour deposition film, need in this method the catalyzer uniform deposition on substrate, not only can introduce unnecessary impurity, but also can strengthen the complicacy of operation and unnecessary equipment, cause high cost, and can not realize continuously uninterrupted preparation.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of method of continuous production Graphene, and the method has advantages of uninterrupted continuous production, and equipment is simple, and the operation simple and feasible easily is automated and suitability for industrialized production.
The method of a kind of continuous production Graphene provided by the invention comprises the following steps:
(1) be that 50～325 purpose metal deposition nets clean to the aperture;
(2) cleaned metal deposition net is arranged in reaction chamber, passes into toward reaction chamber the protective gas that airshed is 10～1000sccm, and kept 1～60 minute; Reaction chamber is heated to 600～1100 ℃ subsequently, passing into airshed is the gaseous state carbonaceous material of 10～200sccm, this gaseous state carbonaceous material reacts 30～60 minutes in the catalytic process of metal deposition net after, make Graphene, it is on 200～325 purpose collecting nets that described Graphene is gathered in an aperture;
(3) change collecting net, continue to collect Graphene.
In the method for continuous production Graphene, in described step (1):
Preferably, described metal deposition net is any in copper mesh, iron net, nickel screen and cobalt net.
In described step (2):
Preferably, described protective gas is a kind of or its arbitrary combination in hydrogen, nitrogen and argon gas;
Preferably, kept 20～30 minutes after passing into protective gas in the reaction chamber;
Preferably, reaction chamber is heated to 700～1050 ℃;
Preferably, described gaseous state carbonaceous material is a kind of or its arbitrary combination in methane, ethane, acetylene and ethene;
Preferably, described collecting net is any in stainless (steel) wire, copper mesh and iron net;
Preferably, the flow direction of described gaseous carbon material and plane, described metal deposition net place are perpendicular;
More preferably, described collecting net is that insert is arranged on the reaction chamber venting port, and this collecting net and described metal deposition net be arranged in parallel.
And preferably, the present invention also comprises the steps (4):
There is the collecting net of Graphene to be put in solution ultrasonic concussion 10～30 minutes collection, forms finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
The method of utilizing chemical Vapor deposition process continuous production Graphene provided by the invention has advantages of uninterrupted continuous production, and equipment is simple, and the operation simple and feasible easily is automated and suitability for industrialized production.In addition, the Graphene that makes by preparation method of the present invention is compared with the Graphene of common reduction method preparation has the few and advantage such as conduct electricity very well of defective.
Description of drawings
Fig. 1 is Graphene continuous production process flow sheet of the present invention;
Fig. 2 is the SEM Electronic Speculum figure of the prepared Graphene of the embodiment of the present invention one.
Embodiment
The following stated is the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
A kind of method of continuous production Graphene as shown in Figure 1, comprises the following steps:
(1) be that 50～325 purpose metal deposition nets clean to the aperture;
(2) cleaned metal deposition net is arranged in reaction chamber, passes into toward reaction chamber the protective gas that airshed is 10～1000sccm, and kept 1～60 minute; Reaction chamber is heated to 600～1100 ℃ subsequently, passing into airshed is the gaseous state carbonaceous material of 10～200sccm, this gaseous state carbonaceous material reacts 30～60 minutes in the catalytic process of metal deposition net after, make Graphene, it is on 200～325 purpose collecting nets that described Graphene is gathered in an aperture;
(3) change collecting net, continue to collect Graphene;
(4) be put in solution ultrasonic concussion 10～30 minutes with collecting the collecting net that Graphene is arranged in step (3), form finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
For the method for above-mentioned continuous production Graphene, in described step (1), any in copper mesh, iron net, nickel screen and cobalt net elected in the metal deposition network optimization as; The metal deposition net can be also Copper Foil, iron foil, nickel foil or cobalt paper tinsel.
The method of above-mentioned continuous production Graphene, in described step (2):
Described protective gas is preferably a kind of or its arbitrary combination in hydrogen, nitrogen and argon gas, the more preferably gas mixture of 5v% hydrogen and 95v% nitrogen, and this gas mixture has week reduction; The aeration time that passes into protective gas in reaction chamber is preferably holds 20～30 minutes;
The Heating temperature of reaction chamber is 700～1050 ℃;
Described gaseous state carbonaceous material is a kind of or its arbitrary combination in methane, ethane, acetylene and ethene, can be also the carbonaceous organic material of other gaseous states, or the carbonaceous organic material through gasifying, as, ethanol, glucose solution etc.;
Described collecting net is any in stainless (steel) wire, copper mesh and iron net, also can Copper Foil, iron foil or nickel foil;
The flow direction of described gaseous carbon material and plane, described metal deposition net place are perpendicular, and such being designed with is beneficial to the gaseous carbon material and fully contacts with the metal deposition net, thereby obtain the production of maximum Graphene;
Described collecting net is that insert is arranged on the reaction chamber venting port, and this collecting net and described metal deposition net be arranged in parallel.
The method of utilizing chemical Vapor deposition process continuous production Graphene provided by the invention has advantages of uninterrupted continuous production, and equipment is simple, and the operation simple and feasible easily is automated and suitability for industrialized production.In addition, the Graphene that makes by preparation method of the present invention is compared with the Graphene of common reduction method preparation has the few and advantage such as conduct electricity very well of defective.
Embodiment one
A kind of method of continuous production Graphene comprises the following steps:
(1) be that 50 purpose copper mesh clean with deionized water, ethanol and acetone to the aperture successively;
(2) cleaned copper mesh is arranged in reaction chamber, passes into toward reaction chamber the argon gas that airshed is 200sccm, and kept 10 minutes; Reaction chamber is heated to 1000 ℃ subsequently, passes into the methane that airshed is 50sccm, this methane reacts after 60 minutes in the catalytic process of copper mesh, makes Graphene, and it is on 200 purpose stainless (steel) wires that described Graphene is gathered in an aperture;
(3) change stainless (steel) wire, continue to collect Graphene;
(4) be put into deionized water for ultrasonic concussion 10 minutes with collecting the stainless (steel) wire that Graphene is arranged in step (3), form finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
Fig. 2 is the SEM Electronic Speculum figure of the prepared Graphene of embodiment one, can obviously find out successfully to grow Graphene from Fig. 2, and thickness mostly is 3～6 layers, and length is about 0.5～5um.
Embodiment two
A kind of method of continuous production Graphene comprises the following steps:
(1) be that 325 purpose nickel screens clean with deionized water, ethanol and acetone to the aperture successively;
(2) cleaned nickel screen is arranged in reaction chamber, passes into toward reaction chamber the hydrogen that airshed is 10sccm, and kept 60 minutes; Reaction chamber is heated to 750 ℃ subsequently, passes into the acetylene that airshed is 10sccm, this acetylene reacts after 30 minutes in the catalytic process of nickel screen, makes Graphene, and it is on 325 purpose copper mesh that described Graphene is gathered in an aperture;
(3) change copper mesh, continue to collect Graphene;
(4) be put into deionized water for ultrasonic concussion 30 minutes with collecting the copper mesh that Graphene is arranged in step (3), form finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
Embodiment three
A kind of method of continuous production Graphene comprises the following steps:
(1) be that 200 purpose cobalt nets clean with deionized water, ethanol and acetone to the aperture successively;
(2) cleaned cobalt net is arranged in reaction chamber, passes into toward reaction chamber the nitrogen that airshed is 1000sccm, and kept 3 minutes; Reaction chamber is heated to 1100 ℃ subsequently, passes into the ethene that airshed is 200sccm, this ethene reacts after 50 minutes in the catalytic process of cobalt net, makes Graphene, and it is on 325 purpose copper mesh that described Graphene is gathered in an aperture;
(3) change copper mesh, continue to collect Graphene;
(4) be put into deionized water for ultrasonic concussion 20 minutes with collecting the copper mesh that Graphene is arranged in step (3), form finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
Embodiment four
A kind of method of continuous production Graphene comprises the following steps:
(1) be that 100 purpose iron nets clean with deionized water, ethanol and acetone to the aperture successively;
(2) cleaned iron net is arranged in reaction chamber, passes into toward reaction chamber the nitrogen that airshed is 500sccm, and kept 20 minutes; Reaction chamber is heated to 900 ℃ subsequently, passes into the ethane that airshed is 100sccm, this ethane reacts after 40 minutes in the catalytic process of iron net, makes Graphene, and it is on 300 purpose stainless (steel) wires that described Graphene is gathered in an aperture;
(3) change stainless (steel) wire, continue to collect Graphene;
(4) be put into deionized water for ultrasonic concussion 10 minutes with collecting the stainless (steel) wire that Graphene is arranged in step (3), form finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
Claims (10)
1. the method for a continuous production Graphene, is characterized in that, comprises the following steps:
(1) be that 50～325 purpose metal deposition nets clean to the aperture;
(2) cleaned metal deposition net is arranged in reaction chamber, passes into toward reaction chamber the protective gas that airshed is 10～1000sccm, and kept 1～60 minute; Reaction chamber is heated to 600～1100 ℃ subsequently, passing into airshed is the gaseous state carbonaceous material of 10～200sccm, this gaseous state carbonaceous material reacts 30～60 minutes in the catalytic process of metal deposition net after, make Graphene, it is on 200～325 purpose collecting nets that described Graphene is gathered in an aperture;
(3) change collecting net, continue to collect Graphene.
2. the method for claim 1, is characterized in that, metal deposition net described in step (1) is any in copper mesh, iron net, nickel screen and cobalt net.
3. the method for claim 1, is characterized in that, protective gas described in step (2) is a kind of or its arbitrary combination in hydrogen, nitrogen and argon gas.
4. method as described in claim 1 or 3, is characterized in that, kept 20～30 minutes after passing into protective gas in the reaction chamber in step (2).
5. the method for claim 1, is characterized in that, in step (2), reaction chamber is heated to 700～1050 ℃.
6. the method for claim 1, is characterized in that, gaseous state carbonaceous material described in step (2) is a kind of or its arbitrary combination in methane, ethane, acetylene and ethene.
7. the method for claim 1, is characterized in that, collecting net described in step (2) is any in stainless (steel) wire, copper mesh and iron net.
8. the method for claim 1, is characterized in that, the flow direction of gaseous carbon material described in step (2) and plane, described metal deposition net place are perpendicular.
9. method as claimed in claim 8, is characterized in that, collecting net described in step (2) is that insert is arranged on the reaction chamber venting port, and this collecting net and described metal deposition net be arranged in parallel.
10. the method for claim 1, is characterized in that, also comprises the steps (4):
There is the collecting net of Graphene to be put in solution ultrasonic concussion 10～30 minutes collection, forms finely dispersed suspension, filtering suspension liquid, and screening is carried out drying and processing, obtain Graphene.
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Cited By (8)
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|---|---|---|---|---|
| CN103232034A (en) * | 2013-05-23 | 2013-08-07 | 中国石油大学(北京) | Method and device for continuously preparing large-area graphene thin film |
| CN103407996A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | High conductivity graphene preparation method |
| CN103409728A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Method for preparing graphene through chemical vapor deposition |
| CN104817072A (en) * | 2015-03-27 | 2015-08-05 | 中国科学技术大学 | High mechanical strength multilayer graphene and preparation method thereof |
| CN106587029A (en) * | 2016-12-30 | 2017-04-26 | 无锡格菲电子薄膜科技有限公司 | Method and growth substrate for preparing three-dimensional structure graphene membrane |
| CN106904601A (en) * | 2017-03-02 | 2017-06-30 | 南京航空航天大学 | A kind of preparation method of arch Graphene three-dimensional network |
| CN107140621A (en) * | 2017-05-09 | 2017-09-08 | 福建师范大学 | A kind of preparation method of ultra-thin layer graphene micro-pipe |
| CN108545722A (en) * | 2018-06-28 | 2018-09-18 | 上海交通大学 | Serialization prepares the method and device of graphene and graphite microchip |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232034A (en) * | 2013-05-23 | 2013-08-07 | 中国石油大学(北京) | Method and device for continuously preparing large-area graphene thin film |
| CN103407996A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | High conductivity graphene preparation method |
| CN103409728A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Method for preparing graphene through chemical vapor deposition |
| CN104817072A (en) * | 2015-03-27 | 2015-08-05 | 中国科学技术大学 | High mechanical strength multilayer graphene and preparation method thereof |
| CN106587029A (en) * | 2016-12-30 | 2017-04-26 | 无锡格菲电子薄膜科技有限公司 | Method and growth substrate for preparing three-dimensional structure graphene membrane |
| CN106587029B (en) * | 2016-12-30 | 2018-09-18 | 无锡格菲电子薄膜科技有限公司 | A kind of preparation method and its preparation growth substrates of three-dimensional structure graphene film |
| CN106904601A (en) * | 2017-03-02 | 2017-06-30 | 南京航空航天大学 | A kind of preparation method of arch Graphene three-dimensional network |
| CN107140621A (en) * | 2017-05-09 | 2017-09-08 | 福建师范大学 | A kind of preparation method of ultra-thin layer graphene micro-pipe |
| CN108545722A (en) * | 2018-06-28 | 2018-09-18 | 上海交通大学 | Serialization prepares the method and device of graphene and graphite microchip |
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