CN104828808B - A kind of preparation method of graphene film - Google Patents
A kind of preparation method of graphene film Download PDFInfo
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- CN104828808B CN104828808B CN201510175961.0A CN201510175961A CN104828808B CN 104828808 B CN104828808 B CN 104828808B CN 201510175961 A CN201510175961 A CN 201510175961A CN 104828808 B CN104828808 B CN 104828808B
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Abstract
A kind of preparation method of graphene film, belongs to graphene film technical field.Graphene or graphite flake powder are uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel plate first, and then by multiple roll rolling, powder is pressed into film by mechanical force, prepares graphene or graphite flake film；Will compacting rear film it is coiled or say good-bye and be fixed in graphite furnace, high-temperature process is carried out under inert gas shielding, terminates rear natural cooling, complete graphited graphene film is produced.The inventive method obtains structurally consummate graphene film by high-temperature process on the basis of not losing film weight and not changing film morphology and thickness, effectively reduces its sheet resistance, increases substantially its thermal conductivity factor.The implementation process very simple of the present invention, it is easy to which procedure, pollution-free, industrial prospect is good.
Description
Technical field
The present invention relates to the preparation method of graphene film, a kind of raising graphene film electrical and thermal conductivity is related specifically to
The method of energy, belongs to graphene film technical field.
Background technology
Graphene is by sp2The monoatomic layer crystal that hydbridized carbon atoms are covalently constituted with two-dimension periodic honeycomb lattice structure,
Its unique two dimensional crystal structure makes graphene have many superior performances, such as high electron mobility, high current density, height
Mechanical strength etc., because these characteristics, graphene is considered as manufacture transparent conductive film, high frequency transistor, hydrogen storage battery, is
To the ideal material of integrated circuit, with wide market application foreground.
In graphene-structured, the p tracks of copline carbon atom mutually overlap mutually to form big pi bond, and the pi-electron of weak localization can be with
Planar freely jumped between adjacent carbon atom, impart the unique electronics transportation characterization of graphene and good electric conductivity.Stone
Black alkene has superior electron mobility in room temperature, and twice indium antimonide is nearly 100 times of monocrystalline silicon.Another note that induces one of graphene
Purpose thermal characteristics are exactly its superelevation thermal conductivity, and experiment value is up to 5000W/mK, are more than 10 times of copper thermal conductivity at room temperature, high
In CNT and diamond, preferable thermal interfacial material will be used as.However, in the perfect hexagon cellular lattice structure of graphene
Some defects are inevitably deposited, the Stone-Wales of five-membered ring and heptatomic ring including the hexa-atomic ring isomerism of carbon
Defect, carbon atom vacancy defect and hetero atom defect etc., this largely reduces the electrically and thermally property of graphene
Energy.
Film with graphite-structure can be used as the highly conductive film of high heat conduction.Use finished product polyimides more at present
Film is presoma, is prepared by high temperature cabonization and graphitization, prepared graphite film is widely used in electric equipment products
Radiating and conductive material.But the requirement of film prepared by this method to Kapton is higher, only a small number of kinds can
Meet and require；Overflowed in addition, having a large amount of hetero atoms in carbonization and graphitizing process, cause film shrunk, be difficult to realize continuous
Change.The preparation method of graphene mainly has mechanical stripping method, silicon carbide epitaxial growth method, oxidation-reduction method and chemical vapor deposition
Micron powder sheet is presented in method, the graphene prepared, so the present invention proposes this powder graphite alkene being pressed into film
Or sheet material, it is possible to as thermal conductivity film, but direct pressing film due to being simply physically contacted between graphene powder, do not have
Tangible integral continuous SP2Big pi bond structure, on the one hand can influence film heat conduction and electric conductivity, while can also influence film
Mechanical property, thus the present invention propose by the film of compacting further carbonization and graphitization, make the graphitization of film more perfect,
Defect sturcture is eliminated, the thermal conductivity of graphene film is improved.This method have it is simple, be easy to continuous and large-scale production
The features such as preparation, good product performance.
The content of the invention
In view of this, it is an object of the invention to provide a kind of side for preparing graphene film and improving its thermal conductivity
Method, after being handled by this method graphene film, is effectively reduced its sheet resistance, improves electrical and thermal conductivity performance.In order to realize
Above-mentioned purpose, the present invention uses following scheme：
Graphene or graphite flake powder are uniformly sprinkling upon fixed or uniform forward motion paper substrate, plastics base first thin
On film or steel strip substrate, and then by multiple roll rolling, powder is pressed into film by mechanical force, prepares graphene or graphite flake
Film；Demoulding, the film of compacting is coiled or say good-bye and be fixed in graphite furnace, high-temperature process is carried out under inert gas shielding,
Natural cooling after end, produces the complete graphited highly conductive graphene film of high heat conduction.
Wherein, used raw material is graphene powder or the ultra-thin graphite slice powder by peeling off.
The thickness of press membrane is controlled by the consumption of unit area powder, is moved ahead by continuous uniform sprinkling and continuously
By pressure roller, continuous film can be made.
Demoulding, the film of compacting is coiled or say good-bye and be fixed in graphite furnace i.e.：Prepared film is removed from matrix,
Monolithic is wound or be cut into, graphitizing furnace is put into.
By the film of compacting it is coiled or say good-bye be fixed in graphite furnace carry out high-temperature process when graphitizing furnace temperature from room
Temperature rise uses inert gas shielding to heat treatment temperature in high-temperature process is carried out, and inert gas is nitrogen or argon gas, lazy
The flow velocity 100-10000ml/min of property gas.
Heat treatment condition is 2-30 DEG C of heating rate/min, and temperature is 1000-2800 DEG C, and is incubated at the final temperature
10-180min.By to Different Heat Treatment Conditions control, realizing the preparation of different conductive and heat-conductive graphene films.
Compared with prior art, remarkable advantage of the invention is：Do not destroying the base of graphene film pattern and thickness
On plinth, graphene film crystal structure is effectively improved, its sheet resistance is reduced, electrical and thermal conductivity performance is improved；By controlling heating speed
The conditions such as rate, temperature and soaking time, prepare the graphene film with different electrical and thermal conductivity performances, and gained film thickness is reachable
10-50μm；Implementation process very simple, it is easy to procedure, pollution-free, industrial prospect is good.
Brief description of the drawings
Fig. 1：Graphene film surface Scanning Electron microscope figure；
Wherein (a) and (b) is respectively not to be heat-treated and the graphene film surface Scanning Electron microscope figure of embodiment 2；
Fig. 2：Graphene film Raman spectrogram；
Wherein (a) and (b) is respectively not to be heat-treated and the graphene film Raman spectrogram of embodiment 2；
Table 1：The graphene film resistance and thermal conductivity for not being heat-treated and being prepared under embodiment 1-6 different conditions.
Embodiment：
With reference to specific embodiment, invention is expanded on further.It should be noted that：Following examples are only to illustrate this hair
It is bright and not limit technical scheme described in the invention；Therefore, although this specification with reference to following embodiments to the present invention
Detailed description is had been carried out, still, it will be understood by those within the art that, still the present invention can be modified
Or equivalent；And technical scheme that all do not depart from the spirit and scope of the present invention and its improvement, it all should cover in this hair
Among bright right.
Embodiment 1
Graphene powder is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel band,
And then by multiple roll rolling, powder is pressed into film by mechanical force；Compacting rear film is placed in graphite furnace；In N2Gas is protected
Shield is lower to carry out high-temperature process, N2Flow velocity is 200ml/min, and 1000 DEG C, and final guarantor are warming up to 10 DEG C/min heating rate
Warm 60min, terminates rear natural cooling, produces the graphene film of electric-conductivity heat-conductivity high, 33.8 μm of film thickness.
Embodiment 2
Graphene powder is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel band,
And then by multiple roll rolling, powder is pressed into film by mechanical force, compacting rear film is placed in graphite furnace；In N2Gas
Protection is lower to carry out high-temperature process, N2Flow velocity is 200ml/min, and 1500 DEG C are warming up to 10 DEG C/min heating rate, and finally
60min is incubated, terminates rear natural cooling, produces the graphene film of electric-conductivity heat-conductivity high, 33.8 μm of film thickness.
Embodiment 3
Graphene powder is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel band,
And then by multiple roll rolling, powder is pressed into film by mechanical force, compacting rear film is placed in graphite furnace；In argon gas gas
Body protection is lower to carry out high-temperature process, and argon gas flow velocity is 200ml/min, and 2000 DEG C are warming up to 10 DEG C/min heating rate, and
Final insulation 60min, terminates rear natural cooling, produces the graphene film of electric-conductivity heat-conductivity high, 33.8 μm of film thickness.
Embodiment 4
Graphene powder is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel band,
And then by multiple roll rolling, powder is pressed into film by mechanical force, compacting rear film is placed in graphite furnace；In argon gas gas
Body protection is lower to carry out high-temperature process, and argon gas flow velocity is 200ml/min, and 2800 DEG C are warming up to 10 DEG C/min heating rate, and
Final insulation 60min, terminates rear natural cooling, produces the graphene film of electric-conductivity heat-conductivity high, 33.8 μm of film thickness.
Embodiment 5
Graphene powder is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel band,
And then by multiple roll rolling, powder is pressed into film by mechanical force, compacting rear film is placed in graphite furnace；In N2Gas
Protection is lower to carry out high-temperature process, N2Flow velocity is 200ml/min, and 1500 DEG C, and final guarantor are warming up to 2 DEG C/min heating rate
Warm 60min, terminates rear natural cooling, produces the graphene film of electric-conductivity heat-conductivity high, 33.8 μm of film thickness.
Embodiment 6
Graphene powder is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel band,
And then by multiple roll rolling, powder is pressed into film by mechanical force, compacting rear film is placed in graphite furnace；In N2Gas
Protection is lower to carry out high-temperature process, N2Flow velocity is 200ml/min, and 1500 DEG C are warming up to 10 DEG C/min heating rate, and finally
120min is incubated, terminates rear natural cooling, produces the graphene film of electric-conductivity heat-conductivity high, 33.8 μm of film thickness.
Table 1 is not heat-treated and implemented 1-6 graphene films resistance and thermal conductivity
The present invention is prepared for the graphene film of electric-conductivity heat-conductivity high performance.Table 1：Bars different with embodiment 1-6 are not heat-treated
The graphene film resistance and thermal conductivity prepared under part, wherein 20 μm of nonheat-treated film thickness.
Fig. 1 is untreated and the scanning electron microscope diagram of graphene film is obtained after the processing of embodiment 2, through high temperature
Processing rear film pattern is substantially unchanged, and surface smoothness is uprised.Fig. 2 is untreated and obtains stone after the processing of embodiment 2
The Raman spectrogram of black alkene film, it can be seen that untreated graphene film has two peaks:D peaks (1350cm-1)
With G peaks (1950cm-1).D peaks producing cause is the lattice fracture of symmetrical graphite structure cell and causes plane graphite A1g to vibrate, and is introduced
Little crystal grain and structure disturbance are unordered, that is, characterize incomplete graphite-structure；G peaks producing cause is the E2g vibrations of graphite lattice, table
Levy perfect graphite-structure.There is D peaks in untreated graphene film, show the crystal structure defects of former film.At high temperature
Graphene film D peaks after reason disappear, and show that crystal structure tends to be perfect, so as to reduce sheet resistance, improve its conductive and heat-conductive
Performance.And graphene film electrical and thermal conductivity performance prepared by Different Heat Treatment Conditions is different.
Claims (4)
1. a kind of preparation method of graphene film, it is characterised in that comprise the following steps：First by graphene or graphite flake powder
End is uniformly sprinkling upon on fixed or uniform forward motion paper substrate, plastics base film or steel strip substrate, and then by multiple roll rolling
Pressure, powder is pressed into film by mechanical force, prepares graphene or graphite flake film；The film of compacting is coiled or say good-bye solid
Due in graphite furnace, high-temperature process is carried out under inert gas shielding, terminates rear natural cooling, complete graphited height is produced and leads
The highly conductive graphene film of heat；High-temperature process condition is 2-30 DEG C of heating rate/min, and temperature is 1000-2800 DEG C, and most
10-180min is incubated under finishing temperature.
2. according to the method for claim 1, it is characterised in that raw material is graphene powder or the ultra-thin graphite slice by peeling off
Powder.
3. according to the method for claim 1, it is characterised in that the film of compacting is coiled or say good-bye to be fixed in graphite furnace and carry out
The temperature of graphitizing furnace rises to heat treatment temperature from room temperature during high-temperature process, and inert gas is used in high-temperature process is carried out
Protection, inert gas is nitrogen or argon gas, the flow velocity 100-10000ml/min of inert gas.
4. according to the method for claim 1, it is characterised in that the thickness of press membrane is controlled by the consumption of unit area powder
System, it is by continuous uniform sprinkling and continuously forward by pressure roller, continuous film is made.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108862249A (en) * | 2018-08-23 | 2018-11-23 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene film |
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| CN105271209A (en) * | 2015-11-05 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuously producing graphene film |
| CN107344853A (en) * | 2017-06-29 | 2017-11-14 | 邱成峰 | A kind of low temperature preparation method of high heat conduction carbon film |
| CN108859300B (en) * | 2018-06-14 | 2020-09-29 | 沈阳航空航天大学 | High-sensitivity graphene flexible strain sensor and preparation method thereof |
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| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
| CN104505148B (en) * | 2014-11-13 | 2017-09-29 | 中国科学院重庆绿色智能技术研究院 | A kind of preparation method of the three-dimensional coplanar shape graphene film of flexible base |
| CN104495821B (en) * | 2014-12-16 | 2016-06-15 | 重庆墨希科技有限公司 | The preparation method of a kind of monolayer continuous graphite alkene film coil and device |
| CN104477903A (en) * | 2014-12-22 | 2015-04-01 | 上海集成电路研发中心有限公司 | Preparation method of graphene film |
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| CN108862249A (en) * | 2018-08-23 | 2018-11-23 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene film |
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