KR20120130442A - Thin film graphene manufactured by electro spray deposition and preparation method thereof - Google Patents
Thin film graphene manufactured by electro spray deposition and preparation method thereof Download PDFInfo
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- KR20120130442A KR20120130442A KR1020110048365A KR20110048365A KR20120130442A KR 20120130442 A KR20120130442 A KR 20120130442A KR 1020110048365 A KR1020110048365 A KR 1020110048365A KR 20110048365 A KR20110048365 A KR 20110048365A KR 20120130442 A KR20120130442 A KR 20120130442A
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- graphene
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- dispersion
- electrospray
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
Description
The present invention relates to a graphene thin film prepared by an electrospray method and a method for manufacturing the same, and more particularly, to a graphene thin film having excellent uniformity by electrospraying a solution in which the graphene is dispersed onto a substrate using an electrospray apparatus. It relates to a method that can be produced in a large area and a graphene thin film prepared accordingly.
Recent explosive research on graphene has led to a surge in the general scientific community's interest in graphene.
Created by Andre Gaim at the University of Manchester in 2004, graphene is a two-dimensional carbon structure with a thickness of one atom, and is emerging as the next generation of promising nanomaterials.
The unique physical properties of graphene show that electrons in graphene behave like relativistic particles without static mass and move at about 1 million meters per second, resulting in electron transfer speeds more than 100 times that of silicon, and 100 times stronger than steel. It is transparent enough to pass 98% of light, and the graphene surface is expected to be applicable to various fields by inducing specific binding with various organic / bio materials by π-π stacking.
For such graphene applications, a uniform large area graphene film is required. However, the most widely used method of producing graphene is to peel off the graphite crystals one by one using scotch tape to reach the last layer, a single layer, and make a few pieces of these single layer graphene. However, this approach is difficult to mass produce and small in size, making it difficult to apply to commercial applications. For this reason, many researchers are conducting research to produce large-area graphene, and various synthetic methods have recently been announced through Sungkyunkwan University, Rutgers University, and MIT.
The prior art for producing graphene is as follows.
First, as described above, a method of mechanically peeling high-quality graphite using a scotch tape or the like, which cannot synthesize high-quality graphene in large quantities, and has a problem that its size is limited to several μm? Mm. .
Secondly, a method of manufacturing a graphene film using selective sublimation of Si from a SiC wafer, more specifically, carbon adsorbed or contained in a crystal such as SiC at high temperature grows to graphene along the surface of the grain. That's how. When epitaxial synthesis is used, large area graphene can be patterned, but there is a problem in that it is an expensive process.
Third, a method for preparing graphene using chemical vapor deposition, more specifically, first depositing a catalyst layer such as nickel / copper and reacting with a mixture of methane and hydrogen at a high temperature to allow carbon to be adsorbed and then cooled. Graphene is manufactured by crystallizing carbon adsorbed through the process. Graphene manufacturing method using the above-described chemical vapor deposition method has the advantage that can be prepared a large area graphene and the graphene layer number can be adjusted according to the reaction conditions, there is a difficulty in controlling the uniform crystal surface.
In addition, Korean Patent Publication No. 2010-0121978 discloses a method of preparing a graphene thin film by preparing and dispersing a graphene dispersion by air spray deposition, but in the case of a pneumatic spray deposition method, coating is performed when the air pressure is not constant. The uniformity of is considerably inferior and it is difficult to obtain a uniform coating surface without the movement of the substrate or the nozzle. In particular, when the metal base material is used as a substrate, the adhesion to the substrate is reduced without the addition of a dispersant, and the coating surface may be easily dropped with only a slight physical force on the outside. In addition, organic solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide are harmful to humans and may cause environmental pollution.
An object of the present invention is to provide a large-area graphene thin film produced by the electrospray method with excellent uniformity.
Another object of the present invention is to provide a method for producing an environmentally friendly graphene thin film that can produce a graphene thin film having excellent uniformity in a large area and at a low cost.
In order to achieve the above object, the present invention,
Preparing a graphene dispersion (step 1);
Heating the substrate to which the graphene dispersion is to be electrosprayed (step 2); And
It provides a graphene thin film manufacturing method using an electrospray method comprising the step (step 3) of electrospraying the graphene dispersion on a heated substrate.
The graphene dispersion used to prepare the graphene thin film in the present invention may be prepared by adding graphene and a conductive polymer to an alcohol solvent and mixing them.
In one embodiment of the present invention, the graphene dispersion is prepared by adding 0.1 to 1 part by weight of graphene and 5 to 10 parts by weight of conductive polymer, mixing and stirring, followed by ultrasonication, based on 100 parts by weight of an alcohol solvent. It is preferable to be.
Ethanol or ethyl ether may be used as the alcohol solvent, and the conductive polymer may be polypyrrole, polyaniline, polythiophene, or the like, but is not limited thereto.
In one embodiment of the present invention, in step 3, the graphene dispersion is applied on the substrate in an amount of 50 to 300 μl / min by applying a voltage of 10 to 20 kV to the nozzle at a height of 10 to 50 cm from the substrate. Preference is given to spraying.
In addition, in the method for manufacturing a graphene thin film of the present invention, after forming the graphene thin film by electrospraying the graphene dispersion liquid on the heated substrate in step 3, the step of heat treatment at 200 ~ 300 ℃ can be further performed. .
The present invention can provide a graphene thin film produced by the electrospray method and a method for producing the graphene thin film having excellent uniformity can be produced in a large area and at a low cost can be utilized in various commercial applications.
1 is a view schematically showing a manufacturing process of a graphene thin film using an electrospray method according to an embodiment of the present invention.
2 is a scanning electron microscope photograph of the surface of the graphene thin film prepared in Example 1 according to the present invention at different magnifications.
3 is a scanning electron microscope photograph of the side cross-section of the graphene thin film prepared in Example 1 according to the present invention at different magnifications.
In order to solve the problems of the prior art related to the manufacturing method of the above-described graphene, the present inventors have prepared a method for producing a graphene thin film by spraying it on a substrate using an electrospray apparatus after preparing a solution in which the graphene is dispersed. Suggest. According to the inventors, the above-described method is excellent in the uniformity of the coating because there is little aggregation phenomenon in the solution in which the graphene is dispersed, there is no residue after the graphene thin film production, environmental pollution does not occur, and the manufacturing process is simple The advantage is that a large area graphene thin film can be manufactured at a low cost.
Hereinafter, a method for manufacturing a graphene thin film using an electrospray method according to an embodiment of the present invention will be described in detail.
First, a graphene dispersion is prepared (step 1). The graphene dispersion is prepared by adding graphene and a conductive polymer to an alcohol solvent, mixing and stirring them, and performing an ultrasonic treatment to improve the dispersibility of graphene.
In one embodiment of the present invention, the graphene dispersion is preferably prepared by mixing and stirring by adding 0.1 to 1 parts by weight of graphene and 5 to 10 parts by weight of the conductive polymer with respect to 100 parts by weight of the alcohol solvent.
The alcohol solvent may be ethanol or ethyl ether, but is not necessarily limited thereto.
In the embodiment of the present invention by preparing a graphene dispersion by the addition of a conductive polymer in the preparation of the graphene dispersion, the dispersion of the graphene in the graphene dispersion by the conductive polymer as well as the graphene thin film and The adhesion to the substrate can be improved, and the conductivity of the graphene solution can be further improved.
In one embodiment of the present invention, the polypyrrole, polyaniline, polythiophene and the like can be used, but are not necessarily limited thereto.
Next, the substrate to be sprayed with the graphene dispersion is heated (step 2).
In an embodiment of the present invention, before the graphene thin film is prepared by electrospraying the graphene dispersion prepared as described above, the substrate to which the graphene dispersion is sprayed is heated to a temperature of 25 to 150 ° C.
Before the graphene thin film is prepared by the electrospraying method as in step 2, the graphene thin film is heated by heating the substrate to which the graphene dispersion is sprayed at a temperature of 25 ° C. to 150 ° C., and no residual solvent remains. Affinity between the thin film and the substrate can be improved.
Finally, the graphene dispersion is electrosprayed onto a heated substrate to prepare a graphene thin film (step 3).
As shown in FIG. 1, after injecting the graphene dispersion prepared in Step 1 into the electrospray device, the graphene dispersion is electrosprayed onto the
In one embodiment of the present invention, in the process of electrospraying the graphene dispersion through the
In the case where the graphene dispersion is electrosprayed on the substrate according to the conditions described above, a uniform graphene thin film is formed in a large area by mitigating the aggregation of particles in the graphene dispersion due to the potential difference between the graphene dispersion and the substrate. can do.
In one embodiment of the present invention, in step 3, the graphene dispersion may be electrosprayed on the heated substrate to form a graphene thin film, and then further heat treatment at 200 ~ 300 ℃.
After forming the graphene thin film by electrospraying on the substrate as described above, by heat treatment at 200 ~ 300 ℃ can improve the adhesion between the substrate and the graphene thin film and can remove the residue after the process.
In addition, the present invention provides a graphene thin film prepared according to the method for producing a graphene thin film using the above-described electrospray method.
Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
Example: Preparation of Graphene Thin Film by Electrospray Method
0.5g of self-made graphene Add to 500 ml of ethanol with polyaniline, mix and stir 24 Dispersion over time gave a graphene dispersion. After injecting the graphene dispersion into an electrospray device (self-made), the graphene dispersion is electrosprayed on the substrate in an amount of about 50 μl / min at a height of 20 cm from the substrate heated to 50 ℃ 200 minutes While the experiment was performed to form a graphene thin film. A voltage of 15 kV was applied to the nozzle to which the graphene dispersion was injected during the electrospray. The surface of the graphene thin film formed is photographed with a scanning electron microscope, and is shown in FIG.
2 to 3, it can be seen that the surface and the cross-section of the graphene thin film prepared using the electrospray method according to the present invention is uniformly deposited on the substrate.
Description of the Related Art [0002]
10: nozzle of electric spray device 20: voltage applied wire
30
Claims (8)
(b) heating the substrate to which the graphene dispersion is to be electrosprayed; And
(c) electrospraying the graphene dispersion onto the heated substrate;
Containing
Graphene thin film manufacturing method using the electrospray method.
The graphene dispersion is a graphene thin film manufacturing method using an electrospray method characterized in that the graphene and the conductive polymer is added to an alcohol solvent and prepared by mixing them.
The graphene dispersion is prepared by adding and mixing 0.1 to 1 part by weight of the graphene and 5 to 10 parts by weight of the conductive polymer, mixing and stirring, and then ultrasonically treating the graphene dispersion with respect to 100 parts by weight of the alcohol solvent. Graphene thin film manufacturing method using the spray method.
The alcohol solvent is a method for producing a graphene thin film using an electrospray method, characterized in that the ethanol or ethyl ether.
The conductive polymer is a method for producing a graphene thin film using an electrospray method, characterized in that any one selected from the group consisting of polypyrrole, polyaniline (polyaniline) and polythiophene (polythiophene).
In the step (b) the substrate is a graphene thin film manufacturing method using an electrospray, characterized in that heated to a temperature of 25 to 150 ℃.
In step (c), the graphene dispersion is electrosprayed on the substrate in an amount of 50 to 300 μl / min by applying a voltage of 10 to 20 kV to the nozzle at a height of 10 to 50 cm from the substrate. Method for producing a graphene thin film using an electrospray method.
The graphene using the electrospray method characterized in that it further comprises the step of electro-spraying the graphene dispersion in the step (c) on the heated substrate to form a graphene thin film, the heat treatment at 200 to 300 ℃ Method for producing a thin film.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018112A (en) * | 2014-06-05 | 2014-09-03 | 北京科技大学 | Preparation method of rubidium-caesium doped metal-based graphene cold cathode for field emission |
| KR101508202B1 (en) * | 2013-09-13 | 2015-04-07 | 한국생산기술연구원 | Fabrication method of thermal coating layer comprising vertical-aligned graphene |
| KR20170067684A (en) * | 2015-11-12 | 2017-06-16 | 코넬 유니버시티 | Air controlled electrospray manufacturing and products thereof |
| WO2017188527A1 (en) * | 2016-04-25 | 2017-11-02 | 인천대학교 산학협력단 | Three-dimensional graphene structure synthesizing method using spraying |
| KR101837996B1 (en) * | 2012-12-28 | 2018-03-14 | 재단법인 포항산업과학연구원 | Method of Preparing graphene reinforced composite material and device thereof |
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2011
- 2011-05-23 KR KR1020110048365A patent/KR20120130442A/en active Search and Examination
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101837996B1 (en) * | 2012-12-28 | 2018-03-14 | 재단법인 포항산업과학연구원 | Method of Preparing graphene reinforced composite material and device thereof |
| KR101508202B1 (en) * | 2013-09-13 | 2015-04-07 | 한국생산기술연구원 | Fabrication method of thermal coating layer comprising vertical-aligned graphene |
| CN104018112A (en) * | 2014-06-05 | 2014-09-03 | 北京科技大学 | Preparation method of rubidium-caesium doped metal-based graphene cold cathode for field emission |
| KR20170067684A (en) * | 2015-11-12 | 2017-06-16 | 코넬 유니버시티 | Air controlled electrospray manufacturing and products thereof |
| WO2017188527A1 (en) * | 2016-04-25 | 2017-11-02 | 인천대학교 산학협력단 | Three-dimensional graphene structure synthesizing method using spraying |
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