CN107403658A - A kind of high conductivity graphene film and preparation method thereof - Google Patents
A kind of high conductivity graphene film and preparation method thereof Download PDFInfo
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- CN107403658A CN107403658A CN201710579772.9A CN201710579772A CN107403658A CN 107403658 A CN107403658 A CN 107403658A CN 201710579772 A CN201710579772 A CN 201710579772A CN 107403658 A CN107403658 A CN 107403658A
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- copper foil
- graphene film
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- membrane
- polyacrylonitrile fibre
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention discloses a kind of high conductivity graphene film and preparation method thereof.The preparation method comprises the following steps：Along the airflow direction of carrier gas, graphene film/copper foil structure of composite membrane and polyacrylonitrile fibre membrane/copper foil structure of composite membrane are sequentially placed into quartz chamber body, carrier gas is passed through and heats up, carries out gas phase reaction under vacuum, that is, obtains high conductivity graphene film；Graphene film/copper foil structure of composite membrane is the composite construction of copper foil and the graphene film being coated on copper foil surface；Polyacrylonitrile fibre membrane/copper foil composite membrane is the composite construction of copper foil and the polyacrylonitrile fibre membrane being coated on copper foil surface.Present invention process is simple and easy, and involved electrostatic spinning, low pressure chemical vapor deposition are all ripe technologies.Gas-phase chemical reaction is very efficient and homogeneous to the functionalization of graphene film.The electric conductivity for the functionalization graphene film that the present invention obtains improves more than 40%, highly significant, and the translucency of graphene film is influenceed very small.
Description
Technical field
The present invention relates to a kind of high conductivity graphene film and preparation method thereof.
Background technology
Graphene is with sp by single layer of carbon atom2The two-dimensional material that hydridization is formed, it has stable physicochemical properties,
Excellent mechanical strength, fabulous electrical and thermal conductivity performance, all it is widely used in numerous areas, can be especially used as flexible and transparent
Conductive film is applied to flexible electronic device of future generation, flexible touch screen etc..Compared to traditional transparent conductive film (ITO,
AZO, conducting polymer etc.), the electric conductivity of graphene film is less than normal.Therefore, development improves the steady of graphene film electric conductivity
The method of determining is very necessary.Improving the method for graphene film electric conductivity at present includes following several classes：1st, graphene lattice
Atom substitution, as nitrogen is mixed.This method can reduce mobility while the carrier concentration in increasing graphene film, by
Destroyed in the perfect lattice of graphene.2nd, graphene film adsorbed chemical species, such as MoOxFilm, Au nano particles and
Other organic molecules.This method is unstable, easily failure.3rd, the chemistry functional of graphene film, such as organic chemistry is utilized
Reaction.This method often relates to the chemical reaction of complexity, it is difficult to controls.
Therefore, development improves the high-efficient simple method of graphene film electric conductivity, for promoting graphene film in flexibility
Practical application in device is extremely important.
The content of the invention
It is an object of the invention to provide a kind of high conductivity graphene film and preparation method thereof, the present invention passes through step letter
Single gas-phase chemical reaction, directly can be carried out on CVD graphenes/copper foil of initial growth.
The preparation method of high conductivity graphene film provided by the present invention, comprises the following steps：
It is along the airflow direction of carrier gas, graphene film/copper foil structure of composite membrane and polyacrylonitrile fibre membrane/copper foil is compound
Membrane structure is sequentially placed into quartz chamber body, is passed through the carrier gas and is heated up, carries out gas phase reaction under vacuum, that is, obtain height
Electric conductivity graphene film；
The graphene film/copper foil structure of composite membrane is copper foil and the graphene film being coated on the copper foil surface
Composite construction；
The polyacrylonitrile fibre membrane/copper foil composite membrane is that copper foil and the polyacrylonitrile being coated on the copper foil surface are fine
Tie up the composite construction of film.
In above-mentioned preparation method, the carrier gas can be the inert gases such as argon gas；
The flow of the carrier gas can be 500~1000sccm, preferably 500sccm；
The speed of the heating is 5~10 DEG C/min, preferably 10 DEG C/min；
Temperature after the heating is 300~600 DEG C, preferably 500 DEG C.
In above-mentioned preparation method, the time of the gas phase reaction can be 10~60 minutes, preferably 30 minutes.
In above-mentioned preparation method, the gas phase reaction is carried out in low pressure CVD apparatus；
The vacuum of the vacuum condition is less than 5Pa.
In above-mentioned preparation method, the graphene film/copper foil structure of composite membrane and the polyacrylonitrile fibre membrane/copper
The distance between paper tinsel structure of composite membrane is preferably smaller than 1cm.
In above-mentioned preparation method, PAN (polyacrylonitrile) tunica fibrosas put PAN reacting precursors as reacting precursor
In the upstream of the graphene film/copper foil structure of composite membrane, to be guaranteed at the graphene film in carrier gas downstream by effectively
Chemistry functional.
The inventive method is based on following principle：PAN (polyacrylonitrile) precursor cracks to form active specy at a certain temperature,
This active specy is carried to the graphene film in downstream by carrier gas, and carries out functional modification to graphene film.
It is thin using graphene described in superficial growth of the chemical vapour deposition technique in the copper foil in above-mentioned preparation method
Film, can be single-layer graphene；
The chemical vapour deposition technique can be carried out under normal conditions, such as：
Selecting hydrogen, it is 100~300sccm to be passed through flow as carrier gas；
Selecting methane, it is 1~10sccm to be passed through flow as carbon source gas；
Growth temperature is 980 DEG C~1050 DEG C.
In above-mentioned preparation method, the polyacrylonitrile fibre is prepared on the surface of the copper foil using the method for electrostatic spinning
Film is tieed up, its thickness can be 100nm~1000nm；
The electrostatic spinning can be carried out under conditions of routine, such as：
Using PAN DMF (dimethylformamide) solution, its mass concentration is that 6%~8%, PAN molecular weight is
150000；
Spacing between spinning nozzle and the copper foil is 25~30cm；
Voltage is 15~20kV；
The spinning time is 3~10 minutes.
In above-mentioned preparation method, the thickness of the copper foil is preferably 18~50 μm.
The inventive method also includes the step being transferred to obtained high conductivity film in dielectric base；
It can specifically carry out in accordance with the following steps：
Polymethyl methacrylate (PMMA) is coated on the functionalization graphene film/copper foil being prepared, by copper foil
The functionalization graphene film that surface obtains is transferred on other dielectric bases (Si/SiOx substrates, glass, plastics etc.) surface；
Specifically used mass fraction is 2~5%PMMA ethyl lactate solution), it is 1000~4000rpm to be coated with speed, the time 30
~60s, more than 60s baking is then carried out at 170 DEG C, can specifically toast 5~15min, concentration is not less than the three of 1M
Acidic Ferric Chloride Solution or persulfate solution perform etching as the etching agent of copper to substrate copper foil, etch period be 5~
30min, obtain the graphene film supported by PMMA；The film is placed in other substrates and dries and removes PMMA using acetone
The graphene film in other dielectric bases is can obtain afterwards.
The high conductivity graphene film being prepared by the above method of the present invention falls within protection scope of the present invention.
" high conductivity " graphene film of the present invention refers to that " gas-phase chemical reaction " step through the present invention obtains
The graphene film that improves of electric conductivity.
The invention has the advantages that：
1st, present invention process is simple and easy, and involved electrostatic spinning, low pressure chemical vapor deposition are all ripe technologies.It is vapor-phase
The functionalization that reaction is learned to graphene film is very efficient and homogeneous.
2nd, the electric conductivity of functionalization graphene film that the present invention obtains improves more than 40%, highly significant, and right
The translucency of graphene film influences very small.
Brief description of the drawings
Fig. 1 is the gas-phase chemical reaction schematic diagram of graphene film functionalization of the present invention.
Fig. 2 is the process unit schematic diagram that the inventive method uses.
Fig. 3 is that SEM of the graphene film before and after gas-phase chemical reaction is characterized in the embodiment of the present invention 1 and Raman characterizes.
Fig. 4 is electric conductivity (surface resistance) contrast of the graphene film before and after functionalization in the embodiment of the present invention 1.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
The metallic substrates that graphene is grown in following embodiments use copper foil (AlfaAesar chemical company, purity
99.8%, 25 microns of thickness), before growing graphene, chemical polishing processing is carried out to copper foil.
Electrospun polymer uses PAN (polyacrylonitrile) DMF (dimethylformamide) solution in following embodiments,
PAN molecular weight is 150000, and concentration of polymer solution is 6%~8%.
In following embodiments, copper foil etching liquid is the aqueous solution of 0.2mol/L sodium peroxydisulfate.
Graphene film before and after chemistry functional is characterized, including the morphology characterization of graphene film, graphene
The spectral quality of film characterizes and the electric conductivity of graphene film characterizes.Measuring method is as follows：
The morphology characterization of graphene film：Using the Lower patterns of ESEM (Hitachi S-4800), (pattern is poor
It is different) it can significantly characterize pattern change of the graphene film before and after functionalization.
The spectral quality of graphene film characterizes：Measured using Raman spectrum (Horiba, JY800), it is thin to obtain graphene
Structural information before and after film chemical modification.
The electric conductivity of graphene film characterizes：Measured using surface resistance tester (CDE, Resmap), obtain graphene
Surface resistance value of the film before and after chemistry functional.
Embodiment 1, the chemistry functional method for improving graphene film electric conductivity
As shown in figure 1, the schematic diagram for the inventive method.
As shown in Fig. 2 for the process device figure of the inventive method, comprise the following steps that：
1) in copper foil substrate graphene growth, using low-pressure chemical vapor deposition system (LPCVD).
By copper foil (purity 99.8%, 25 microns of thickness) at 1000 DEG C, first anneal 30 minutes under a hydrogen atmosphere, hydrogen stream
Measure and be maintained at 350Pa for 300sccm, system pressure, then anneal 30 minutes, argon flow amount 500sccm under an argon, body
It is that pressure is maintained at 500Pa.The effect annealed under nitrogen atmosphere is to reduce the oxide layer of copper foil surface, the effect annealed under argon atmospher
It is the active nucleation site for reducing copper foil surface, improves the crystal domain size of graphene film.After the completion of process annealed above, continue
The growth of graphene film is carried out at 1000 DEG C, condition is 200sccm hydrogen+1sccm methane (carbon-source gas), growth time
For 1 hour.Finally growth obtains graphene film on copper foil, and thickness is individual layer.
2) PAN spinning fibre films are made in another naked copper foil surface.
Naked copper paper tinsel is placed on the negative pole sample stage of electrostatic spinning, the positive pole shower nozzle of electrostatic spinning is placed in the upper of naked copper paper tinsel
About 25 centimeters of side, spinning macromolecule is from the DMF solution for the PAN that molecular weight is 150000, concentration 8%.During electrostatic spinning
Add 15kV voltages, the spinning time is 5 minutes, ultimately forms PAN fiber film/copper foil, the wherein thickness of PAN fiber film is 200nm.
3) as shown in the process device figure in Fig. 2, two samples of PAN fiber film/copper foil and graphene/copper foil are put successively
In the quartz chamber body of low pressure chemical vapor deposition, wherein PAN fiber film/copper foil is in the upstream of carrier gas stream, and graphene/copper foil is close to
Downstream in carrier gas stream (spacing between the two is 1mm).After closing cavity, below 5Pa is evacuated to, is passed through
500sccm argon gas (Ar), 500 DEG C are risen to 10 DEG C/min heating rate by quartz chamber body temperature, then in this temperature and
Gas phase reaction is carried out under above argon carrier flow, the reaction time is 30 minutes.Room temperature is naturally cooling to after the completion of reaction, is opened
Quartz chamber body, sample is taken out, carries out a series of signs.
4) graphene film of above-mentioned completion chemistry functional is transferred to Si/SiOx dielectric bases from copper foil substrate
On, detailed process is as follows：
By spin coating polymethyl methacrylate (PMMA) on the above-mentioned graphene film/copper foil taken out from quartz chamber body,
Specifically used mass fraction is 6%PMMA ethyl lactate solution, and spin coating speed is 4000rpm, spin-coating time 60s, then
By the baking of PMMA spin-coating films progress 3 minutes at 170 DEG C.Copper foil substrate is performed etching using copper foil etching liquid, during etching
Between be 30min, after obtain the graphene film supported by PMMA, the film is placed in Si/SiOx substrates and dried and using third
The graphene film of chemistry functional can be transferred in dielectric base by ketone after removing PMMA.
Sign is measured to the graphene film of chemistry functional below：
The morphology characterization of graphene film：Such as Fig. 3 a) shown in, it is that the SEM in the graphene single crystal domains area just grown schemes, figure
3b) be the later graphene single crystal domains area of chemistry functional SEM figure, from it is front and rear contrast as can be seen that graphene vapor-phase
Learn reaction and still maintain pattern integrality afterwards, while can see the graphenic surface after reaction and become more coarse.
The spectral quality of graphene film characterizes：Such as Fig. 3 c) shown in, it is the graphene film for not carrying out gas-phase chemical reaction
Raman spectrum, it can be seen that almost exist without D peaks, and 2D peak intensities/G peak intensities>2, so this graphene film is
Defect concentration is very low, the good high quality monolayer graphene of crystallization degree.Fig. 3 d) it is that graphene after gas-phase chemical reaction is thin
The Raman spectrum of film, it can be seen that strong D peaks, illustrate that the graphene film of chemistry functional introduces many defects, while 2D
Peak maintains stronger signal, illustrates that the lattice structure of graphene film keeps complete.
The electric conductivity of graphene film characterizes：Such as Fig. 4 a) electric conductivity of original graphite alkene film is illustrated, to multiple
Sample prepared by sample (repeat the above steps 1)) retest discovery is carried out, the surface resistance value of original graphite alkene film is
872Ω/□.Fig. 4 b) illustrate by the present invention gas-phase chemical reaction functionalization graphene film electric conductivity, it is multiple
Sample (repeat the above steps 1) -4) sample for preparing) retest result show that its surface resistance value is 510 Ω/, is led
Electrical property improves more than 40%, highly significant.
Claims (7)
1. a kind of preparation method of high conductivity graphene film, comprises the following steps：
Along the airflow direction of carrier gas, by graphene film/copper foil structure of composite membrane and polyacrylonitrile fibre membrane/copper foil composite membrane knot
Structure is sequentially placed into quartz chamber body, is passed through the carrier gas and is heated up, carry out gas phase reaction under vacuum, that is, obtains highly conductive
Property graphene film；
The graphene film/copper foil structure of composite membrane is copper foil and the graphene film that is coated on the copper foil surface is answered
Close structure；
The polyacrylonitrile fibre membrane/copper foil composite membrane is copper foil and the polyacrylonitrile fibre membrane being coated on the copper foil surface
Composite construction.
2. preparation method according to claim 1, it is characterised in that：The carrier gas is inert gas；
The flow of the carrier gas is 500~1000sccm；
The speed of the heating is 5~10 DEG C/min；
Temperature after the heating is 300~600 DEG C.
3. preparation method according to claim 1 or 2, it is characterised in that：The time of the gas phase reaction is 10~60 points
Clock.
4. according to the preparation method any one of claim 1-3, it is characterised in that：The gas phase reaction is in low pressure chemical vapor deposition
Carried out in device；
The vacuum of the vacuum condition is less than 5Pa.
5. according to the preparation method any one of claim 1-4, it is characterised in that：Using chemical vapour deposition technique in institute
State graphene film described in the superficial growth of copper foil.
6. according to the preparation method any one of claim 1-5, it is characterised in that：Using the method for electrostatic spinning in institute
The surface for stating copper foil prepares the polyacrylonitrile fibre membrane.
7. high conductivity graphene film prepared by method any one of claim 1-6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666691A (en) * | 2009-10-15 | 2012-09-12 | 拜尔技术服务有限责任公司 | Composite materials having graphene layers and production and use thereof |
| CN104269516A (en) * | 2014-10-11 | 2015-01-07 | 南京中储新能源有限公司 | Composite positive electrode for secondary battery based on vertically-oriented graphene |
| CN104651802A (en) * | 2015-01-19 | 2015-05-27 | 重庆大学 | Method for directly synthesising nitrogen-doped graphene by simply using solid nitrogen source |
| CN104979038A (en) * | 2015-06-08 | 2015-10-14 | 北京大学 | Topological insulator/graphene compound flexible transparent conductive thin film and preparation method and application thereof |
| CA2957918A1 (en) * | 2014-08-11 | 2016-02-18 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Aligned graphene-carbon nanotube porous carbon composite |
-
2017
- 2017-07-17 CN CN201710579772.9A patent/CN107403658B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666691A (en) * | 2009-10-15 | 2012-09-12 | 拜尔技术服务有限责任公司 | Composite materials having graphene layers and production and use thereof |
| CA2957918A1 (en) * | 2014-08-11 | 2016-02-18 | The Arizona Board Of Regents On Behalf Of The University Of Arizona | Aligned graphene-carbon nanotube porous carbon composite |
| CN104269516A (en) * | 2014-10-11 | 2015-01-07 | 南京中储新能源有限公司 | Composite positive electrode for secondary battery based on vertically-oriented graphene |
| CN104651802A (en) * | 2015-01-19 | 2015-05-27 | 重庆大学 | Method for directly synthesising nitrogen-doped graphene by simply using solid nitrogen source |
| CN104979038A (en) * | 2015-06-08 | 2015-10-14 | 北京大学 | Topological insulator/graphene compound flexible transparent conductive thin film and preparation method and application thereof |
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