CN108751172A - A kind of preparation method of graphene film and products thereof and purposes - Google Patents
A kind of preparation method of graphene film and products thereof and purposes Download PDFInfo
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- CN108751172A CN108751172A CN201810667847.3A CN201810667847A CN108751172A CN 108751172 A CN108751172 A CN 108751172A CN 201810667847 A CN201810667847 A CN 201810667847A CN 108751172 A CN108751172 A CN 108751172A
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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
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
Abstract
The present invention relates to a kind of preparation method of graphene film and products thereof and purposes.The preparation method includes the following steps：(1) graphene oxide is dispersed in water, obtains graphene oxide suspension；(2) coating is on substrate, dry, obtains the graphene oxide membrane of substrate load；(3) it is warming up to 800~1000K in inert gas, is passed through ammonia, is restored under constant temperature, obtains the graphene film of substrate load；(4) substrate is dissolved with acid, obtains graphene film.It is reducing gas and controlled at 800~1000K that the present invention, which directly selects ammonia, and compared to for other reducing agents such as hydrogen, the removal rate of epoxy group greatly improves.And it is 780~850W/mK that the graphene film after restoring, which has extraordinary integrality, thermal conductivity, tensile strength values are 37.8~57.9MPa, and performance is more stable.
Description
Technical field
The present invention relates to graphene film technical fields more particularly to a kind of preparation method of graphene film and products thereof
And purposes.
Background technology
2004, two scientists of Univ Manchester UK separated graphite flake from highly oriented pyrolytic graphite, so
The two sides of thin slice is sticked on a kind of special adhesive tape afterwards, adhesive tape is torn, graphite flake can be divided into two.Constantly grasp in this way
Make, then thin slice is more and more thinner, and finally, they have obtained the thin slice being only made of one layer of carbon atom, and here it is graphenes.Graphite
Alkene is a kind of cellular flat film formed with sp2 hybrid forms by carbon atom, due to its very good intensity, it is flexible,
Conduction, heat conduction, optical characteristics are obtained for considerable in fields such as physics, materialogy, electronic information, computer, aerospaces
Development.
Graphene film is one of important application of graphene, and it is saturating to be mainly used in touch screen, solar cell, OLED etc.
Bright conduction field, since its is resourceful, and has good chemical stability and flexibility, it is possible to resource be replaced to lack
Weary, brittle indium tin oxide (ITO) becomes the transparent conductive film of a new generation.
Graphene oxide (GO) has good water solubility, is easy to form a film.Therefore, first with GO solution film formings, then to GO
Film carries out reduction treatment, can prepare the Flexible graphene transparent conductive film of low capital large area.Graphene is in oxidation
Can introduce some chemical groups, such as carboxyl, hydroxyl, carbonyl, epoxy group in the process, the generations of these groups change C-C it
Between combination, cause the electric conductivity of graphene drastically to decline, and the various excellent properties having is made also to disappear therewith.It closes
Key is what restoring method to be effectively removed the oxygen-containing functional group on the surfaces GO using, obtain graphene with high conductivity and its
Thin-film material.
CN104445170A discloses a kind of preparation method of graphene film, is coated with using graphene oxide acid solution
Onto magnesium film, there is the magnesium film of graphene oxide to dry deposition, then magnesium film is dissolved with diluted acid, it is thin to obtain graphene
Film.Magnesium and acid reaction generate proton hydrogen [H] in the process, are restored graphene oxide using proton hydrogen [H] stronger reproducibility, but
It is the unstability due to proton hydrogen [H], H can be combined into quickly2, reducing power is caused to weaken.
CN107758644A discloses a kind of method that super-pressure thermal reduction prepares graphene film, and the graphene film is by big
Piece graphene oxide, few layer graphene or nanoscale graphite microplate are by solution film forming, electronation, super-pressure thermal reduction etc.
Step obtains.This graphene film is height-oriented, structure particularly compact, has certain flexibility.But there are graphite for this method
The problem of alkene piece interlayer is easily reunited.
CN107651670A discloses a kind of no folding line graphene film preparation method, which is passed through by graphene oxide
Solution film forming, electronation and high temperature sintering step is crossed to obtain.The graphene film has fabulous flexibility, repeatedly doubling 100,000
It does not leave a trace more than secondary, and the fast quick-recovery of shape.This high flexible graphene film is resistant to bend repeatedly 10,000 times or more, horizontal
Elastic failure elongation is 30-50%, and elastic and vertical compression ratio is 80-90%, and conductivity 400-7000S/cm can be used as height
Play conductive and heat-conductive device.But this method the problem of easily reuniting there is also graphene film interlayer.
" it is organic that Liu Hongtao, Zheng Jian, Liu Yun boundary ammonium hydroxide and ammonia vapor reduction method prepare the 8th, the whole nations graphene [C]
The discussion of solid electronic process and Chinese's organic photoelectric functional material science abstract collection, 2010. " are gone back using the reproducibility of ammonium hydroxide
Former graphene oxide.Similar to hydrazine hydrate steam, ammonia vapor can also realize reduction.But ammonia vapor easily causes the residual of N
It stays, if remained in the network structure of graphene, is unfavorable for it and plays excellent electrical and thermal conductivity.
Therefore it needs to develop a kind of preparation method of graphene film, obtains the graphene film of low oxygen content, while not
The internal networking structure for damaging graphene, to ensure good electric conductivity, thermal conductivity and mechanical strength.
Invention content
In view of the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of preparations of graphene film
Method, obtains the graphene film of low oxygen content, does not damage the internal networking structure of graphene, to ensure good conduction
Property, thermal conductivity and mechanical strength.
For this purpose, the present invention adopts the following technical scheme that：
In a first aspect, the present invention provides a kind of preparation method of graphene film, include the following steps：
(1) graphene oxide is dispersed in water, obtains graphene oxide suspension；
(2) on substrate by graphene oxide suspension coating, dry, obtain the graphene oxide membrane of substrate load；
(3) graphene oxide membrane by substrate load obtained by step (2) is warming up to 800~1000K, example in inert gas
Such as 800K, 820K, 850K, 900K, 920K, 950K, 980K or 1000K are passed through ammonia, are restored, served as a contrast under constant temperature
The graphene film of bed load；
(4) substrate in the graphene film of substrate load obtained by step (3) is dissolved with acid, obtains graphene film.
" comprising " of the present invention, it is intended that it can also include other steps, these other steps in addition to the step
Assign the graphene film different characteristics.In addition to this, " comprising " of the present invention may be replaced by enclosed
" for " or " by ... form ".
Being restored in the prior art to graphene oxide as reducing agent using ammonia or ammonia vapor can occur centainly
The nitrogen of degree remains or N doping phenomenon, forms a variety of doped structures, if nitrogen remains in carbon network, the Fermi surface of graphene
It can change, then be unfavorable for the electrical and thermal conductivity performance of graphite.It is reducing gas that the present invention, which directly selects ammonia, controlled at
800~1000K, ammonia generates a variety of free radical N under the conditions of thisxHy(predominantly N2H), epoxy can be changed into hydroxyl by these by base
Base, and hydroxyl is easier to be reduced, compared to for other reducing agents such as hydrogen, the removal rate of epoxy group is much higher for this.
And the graphene film after restoring has extraordinary integrality, and very excellent electric conductivity is shown, performance is more stable.
Preferably, in step (1) mass volume ratio of graphene oxide and water be 0.01~1g/L, such as 0.01g/L,
0.02g/L, 0.05g/L, 0.1g/L, 0.2g/L, 0.5g/L, 0.8g/L or 1g/L etc..
Preferably, step (1) described graphene oxide is the graphene oxide filtered by vibrating screen.It is sieved through using vibration
The impurity or bulky grain in graphene oxide are filtered, in order to avoid being unevenly coated, bulky grain is generated, influences Painting effect.
Preferably, the mesh size of the vibrating screen be 100~500 mesh, such as 100 mesh, 120 mesh, 140 mesh, 170 mesh,
200 mesh, 230 mesh, 270 mesh, 325 mesh, 400 mesh or 500 mesh etc..
Preferably, step (2) described substrate includes Copper thin film.
Preferably, the thickness of the Copper thin film be 20~60 μm, such as 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm,
50 μm, 55 μm or 60 μm etc..
Preferably, the rare earth element containing 0.03~0.05wt% in the Copper thin film, such as 0.03wt%,
0.032wt%, 0.035wt%, 0.038wt%, 0.04wt%, 0.042wt%, 0.045wt%, 0.048wt% or
0.05wt% etc..Substrate material of the Copper thin film as coating graphene suspension, mixes the rare earth element of 0.03~0.05wt%
Grain refining effect is optimised afterwards, is conducive to grow the graphene film that crystallinity is more preferable and surface is more smooth.Addition is suitable
The adhesive force for measuring the copper foil slurry after rare earth is big, and the resistance of Copper thin film is small, more preferable to the attachment of active material；More resistant to ammonia under high temperature
The corrosion of gas improves hardness (HB), is conducive to be coated with, and be conducive to the separation of follow-up graphene film and substrate, is conducive to height
Speed centrifugation obtains the graphene oxide of single layer.Volume by controlling rare earth element can be into one within the scope of 0.03~0.05wt%
The degree of refinement of copper tissue and metal crystalline substance are situated between in step optimization Copper thin film, the good Copper thin film of comprehensive mechanical property are obtained, to more have
Conducive to the graphene film of acquisition flat smooth so that graphene film integrality is more preferable, electric conductivity, thermal conductivity and mechanical performance
It advanced optimizes.
Preferably, the rare earth element include in lanthanum, neodymium, erbium or cerium any one or at least two combination, wherein
It is typical but non-limiting to be combined as：The combination of the combination of lanthanum and neodymium, erbium and cerium, the combination of lanthanum, neodymium and erbium, neodymium, erbium and cerium
Combination, the combination of lanthanum, neodymium, erbium and cerium；It is preferred that cerium.
Preferably, step (3) described inert gas includes any one in argon gas, helium or neon or at least two
Combination, wherein typical but non-limiting be combined as：The combination of the combination of argon gas and helium, argon gas and neon, helium and neon
Combination, the combination of argon gas, helium and neon.
Preferably, the rate of step (3) described heating be 5~20 DEG C/min, such as 5 DEG C/min, 8 DEG C/min, 10 DEG C/
Min, 12 DEG C/min, 15 DEG C/min, 18 DEG C/min or 20 DEG C/min etc., the graphene defect that heating rate obtains sooner is less,
Graphene is close to single layer, and the graphene quality synthesized on copper foil is better, preferably 9.5~10.5 DEG C/min.
Preferably, step (3) ammonia and the mass ratio of graphene oxide used in step (1) of being passed through is (10~20):
(80~90), such as 20:90,10:90,11:89,12:88,13:87,14:86,15:85,16:84,17:83,18:82,19:
81,20:80 or 10:80 etc., preferably (12~16):(84~88).
Preferably, the step (3) carries out in tube furnace.
Preferably, the time of step (3) described constant temperature be 6~8h, such as 6h, 6.2h, 6.5h, 6.8h, 7h, 7.2h,
7.5h, 7.8h or 8h etc..
Preferably, step (4) acid includes salpeter solution.
Preferably, a concentration of 4~6mol/L of the salpeter solution, for example, 4mol/L, 4.2mol/L, 4.5mol/L,
4.8mol/L, 5mol/L, 5.2mol/L, 5.5mol/L, 5.8mol/L or 6mol/L etc..
Preferably, the thickness of graphene film obtained by step (4) is 1~20 μm, such as 12510121518 or 20 etc.；It leads
Heating rate be 780~850W/mK, such as 780W/mK, 790W/mK, 800W/mK, 810W/mK, 820W/mK,
830W/mK, 840W/mK or 850W/mK etc.；Tensile strength values be 37.8~57.9MPa, such as 37.8MPa, 38MPa,
40MPa, 42MPa, 45MPa, 48MPa, 50MPa, 52MPa, 55MPa or 57.9MPa etc..
Preferably, the O/C molar ratios of graphene film obtained by step (4) are 1:(20~30), such as 1:20,1:22,1:
25,1:28 or 1:30 etc..
As currently preferred technical solution, the preparation method of the graphene film includes the following steps：
(1) graphene oxide is dispersed in water, the mass volume ratio of graphene oxide and water is 0.01~1g/L, is obtained
Graphene oxide suspension；
(2) graphene oxide suspension is coated on thickness and contains 0.03~0.05wt% rare earth elements for 20~60 μm
Copper thin film on, it is dry, obtain the graphene oxide membrane of substrate load；
(3) graphene oxide membrane by substrate load obtained by step (2) is placed in tube furnace, in argon gas, helium or neon
In any one or at least two combination gas in 800~1000K is warming up to the rate of 5~20 DEG C/min, be passed through ammonia
Gas, the mass ratio for being passed through ammonia and graphene oxide used in step (1) is (10~20):(80~90), 6~8h of constant temperature are gone back
Original obtains the graphene film of substrate load；
(4) Copper thin film in the graphene film of substrate load obtained by step (3) is dissolved with the salpeter solution of 4~6mol/L
Fall, obtain thickness be 1~20 μm, thermal conductivity be 780~850W/mK, tensile strength values be 37.8~57.9MPa, O/C moles
Than being 1:The graphene film of (20~30).
Second aspect, the present invention provide graphite prepared by a kind of preparation method of graphene film as described in relation to the first aspect
Alkene film.
The third aspect, the present invention provide the purposes of the graphene film as described in second aspect, and the graphene film is used
In touch screen, solar cell, the transparent conductive film of OLED or transparent heat conducting film.
Compared with prior art, the present invention at least has the advantages that：
1. it is reducing gas and controlled at 800~1000K that the present invention, which directly selects ammonia, compared to hydrogen etc. other
For reducing agent, the removal rate of epoxy group greatly improves.And the graphene film after restoring has extraordinary integrality, heat conduction
Rate is 780~850W/mK, and tensile strength values are 37.8~57.9MPa, and performance is more stable.
2. present invention process is simple, manufactured graphene film thickness is uniform, is 1~20 μm, and light transmittance is high, and environmental protection is without dirt
Dye, is conducive to the large-scale production of graphene film.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.But following embodiments are only
The simple example of the present invention, does not represent or limits the scope of the present invention, and protection scope of the present invention is wanted with right
It asks subject to book.
Embodiment 1
A kind of preparation method of graphene film, steps are as follows：
Take graphene oxide, using mesh size be 500 mesh vibrating screen filter graphene oxide in impurity or big
Grain, weighs the graphene oxide 5g of filtering, and 5L water is added thereto, and ultrasound impregnates 1h, graphene oxide is made to be scattered in aqueous solvent
In, 2h is at the uniform velocity then stirred using magnetic stirring apparatus, so that it is sufficiently mixed.It is with the copper foil (cerium containing 0.04wt%) of 20 μ m-thicks
Substrate is coated with, and is then dried in vacuum drying chamber, the temperature inside the box rises to 100 DEG C, and drying time is set as 2h.Graphene oxide
Reduction process is happened in tube furnace, and argon gas is continually fed into tube furnace and is protected, and temperature-rise period is with the heating speed of 5 DEG C/min
Rate rises to 800K from room temperature, and reducing gas NH is then passed through into tube furnace3, the mass ratio of ammonia and graphene oxide used is
20:80,8h is kept the temperature, ensures that graphene oxide is fully restored.With concentration of nitric acid for 6mol/L salpeter solution by Copper thin film
Then dissolving is rinsed well the remaining acid solution of film surface with deionized water, then dried to get graphite in 60 DEG C of baking ovens
Alkene film.Prepared graphene film thickness is 20 μm, thermal conductivity 786.5W/mK, and tensile strength values are
40.2MPa。
Embodiment 2
A kind of preparation method of graphene film, steps are as follows：
Graphene oxide 5g is weighed, 50L water is added thereto, ultrasound impregnates 1h, graphene oxide is made to be scattered in aqueous solvent
In, 2h is at the uniform velocity then stirred using magnetic stirring apparatus, so that it is sufficiently mixed.It is coated with by substrate of the copper foil of 40 μ m-thicks, then
It is dried in vacuum drying chamber, the temperature inside the box rises to 100 DEG C, and drying time is set as 2h.The reduction process of graphene oxide occurs
Argon gas is continually fed into tube furnace, in tube furnace to be protected, temperature-rise period is with the heating rate of 20 DEG C/min from room temperature liter
To 900K, reducing gas NH is then passed through into tube furnace3, the mass ratio of ammonia and graphene oxide used is 12:88, heat preservation
7h ensures that graphene oxide is fully restored.Then salpeter solution with concentration of nitric acid for 5mol/L, which dissolves Copper thin film, to be used
Deionized water rinses the remaining acid solution of film surface well, is then dried to get graphene film in 60 DEG C of baking ovens.It is made
It it is 3 μm, thermal conductivity 821.4W/mK, tensile strength values 57.9MPa for the graphene film thickness gone out.
Embodiment 3
A kind of preparation method of graphene film, steps are as follows：
Graphene oxide is taken, the impurity or bulky grain in graphene oxide are filtered using 100 mesh vibrating screens, in case coating is not
Uniformly, bulky grain is generated, Painting effect is influenced.The graphene oxide 5g of filtering is weighed, 100L water is added thereto, ultrasound is impregnated
1h makes graphene oxide be scattered in aqueous solvent, then at the uniform velocity stirs 2h using magnetic stirring apparatus, so that it is sufficiently mixed.With
The copper foil (neodymium containing 0.05wt%) of 60 μ m-thicks is coated with for substrate, is then dried in vacuum drying chamber, the temperature inside the box rises to 100
DEG C, drying time is set as 2h.The reduction process of graphene oxide is happened in tube furnace, and argon gas progress is continually fed into tube furnace
Protection, temperature-rise period rise to 1000K from room temperature with the heating rate of 10 DEG C/min, reducing gas are then passed through into tube furnace
NH3, the mass ratio of ammonia and graphene oxide used is 10:90,6h is kept the temperature, ensures that graphene oxide is fully restored.With
Then the salpeter solution that concentration of nitric acid is 4mol/L, which dissolves Copper thin film, to be rinsed the remaining acid solution of film surface with deionized water
Totally, it is then dried to get graphene film in 60 DEG C of baking ovens.Prepared graphene film thickness is 10 μm, heat conduction
Rate is 794.7W/mK, tensile strength values 37.8MPa.
Comparative example 1
With differing only in for embodiment 1：Ammonia is replaced with to the hydrogen of equimolar amounts.
Comparative example 2
With differing only in for embodiment 1：Ammonia is replaced with to the ammonia vapor of equimolar amounts.
Comparative example 3
With differing only in for embodiment 1：Reduction temperature is 600K.
Comparative example 4
With differing only in for embodiment 1：Reduction temperature is 1200K.
Comparative example 5
With differing only in for embodiment 1：Reduction temperature is 2500K.
Embodiment 4
With differing only in for embodiment 1：Other metals are not mixed in Copper thin film.
The performance of 1~5 gained graphene film of embodiment 1,5 and comparative example is arranged in table 1.
Table 1
| Graphene film | Thickness (μm) | Thermal conductivity (W/mK) | Tensile strength (MPa) |
| Embodiment 1 | 20 | 786.5 | 40.2 |
| Embodiment 4 | 20 | 750.2 | 36.6 |
| Comparative example 1 | 20 | 352.3 | 30.5 |
| Comparative example 2 | 20 | 454.5 | 32.5 |
| Comparative example 3 | 20 | 565.7 | 35.7 |
| Comparative example 4 | 20 | 527.6 | 36.6 |
| Comparative example 5 | 20 | 581.4 | 35.4 |
As it can be seen from table 1 doping phenomenon when why the present invention can overcome ammonia redox graphene film, be because
For at a certain temperature be 800~1000K, temperature not in this range when, the thermal conductivity and tensile strength of gained graphene film
Decline, when this illustrates temperature not in this range, a degree of N doping occurs and makes the carbon network of graphene film complete
Property is destroyed.When replacing ammonia with other reducing gas, such as hydrogen and ammonia vapor, even if maintaining the temperature at 800 simultaneously
~1000K, the thermal conductivity and mechanical strength of gained graphite film also all decline to a great extent, the reason is that graphene film obtained by hydrogen reducing
Oxygen content is high and a degree of N doping still occurs in this temperature and makes the carbon network of graphene film complete for ammonia vapor
Property is destroyed.Therefore the present invention overcomes the technology prejudice of this field, passes through the cooperation of temperature so that ammonia avoids generation nitrogen from mixing
It is miscellaneous, achieve unexpected technique effect.
Comparative examples 5 are with embodiment 1 it is found that can further increase stone by mixing a certain amount of rare earth metal in substrate
The quality of black alkene film optimizes mechanical strength and thermal conductivity.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of preparation method of graphene film, which is characterized in that include the following steps：
(1) graphene oxide is dispersed in water, obtains graphene oxide suspension；
(2) on substrate by graphene oxide suspension coating, dry, obtain the graphene oxide membrane of substrate load；
(3) graphene oxide membrane by substrate load obtained by step (2) is warming up to 800~1000K in inert gas, is passed through ammonia
Gas is restored under constant temperature, and the graphene film of substrate load is obtained；
(4) substrate in the graphene film of substrate load obtained by step (3) is dissolved with acid, obtains graphene film.
2. the preparation method of graphene film as described in claim 1, which is characterized in that in step (1) graphene oxide with
The mass volume ratio of water is 0.01~1g/L.
3. the preparation method of graphene film as claimed in claim 1 or 2, which is characterized in that step (1) described graphite oxide
Alkene is the graphene oxide filtered by vibrating screen；
Preferably, the mesh size of the vibrating screen is 100~500 mesh.
4. such as the preparation method of claims 1 to 3 any one of them graphene film, which is characterized in that step (2) described lining
Bottom includes Copper thin film；
Preferably；The thickness of the Copper thin film is 20~60 μm；
Preferably, the rare earth element containing 0.03~0.05wt% in the Copper thin film；
Preferably, the rare earth element include in lanthanum, neodymium, erbium or cerium any one or at least two combination, preferred cerium.
5. such as the preparation method of Claims 1 to 4 any one of them graphene film, which is characterized in that step (3) is described lazy
Property gas includes the combination of any one or at least two in argon gas, helium or neon；
Preferably, the rate of step (3) described heating is 5~20 DEG C/min, preferably 9.5~10.5 DEG C/min；
Preferably, step (3) ammonia and the mass ratio of graphene oxide used in step (1) of being passed through is (10~20):(80~
90), preferably (12~16):(84~88)；
Preferably, the step (3) carries out in tube furnace；
Preferably, the time of step (3) described constant temperature is 6~8h.
6. such as the preparation method of Claims 1 to 5 any one of them graphene film, which is characterized in that step (4) described acid
Including salpeter solution；
Preferably, a concentration of 4~6mol/L of the salpeter solution.
7. such as the preparation method of claim 1~6 any one of them graphene film, which is characterized in that stone obtained by step (4)
The thickness of black alkene film is 1~20 μm, and thermal conductivity is 780~850W/mK, and tensile strength values are 37.8~57.9MPa；
Preferably, the O/C molar ratios of graphene film obtained by step (4) are 1:(20~30).
8. such as the preparation method of claim 1~7 any one of them graphene film, which is characterized in that the preparation method
Include the following steps：
(1) graphene oxide is dispersed in water, the mass volume ratio of graphene oxide and water is 0.01~1g/L, is aoxidized
Graphene suspension；
(2) graphene oxide suspension is coated on the copper containing 0.03~0.05wt% rare earth elements that thickness is 20~60 μm
It is dry on film, obtain the graphene oxide membrane of substrate load；
(3) graphene oxide membrane by substrate load obtained by step (2) is placed in tube furnace, in argon gas, helium or neon
800~1000K is warming up to the rate of 5~20 DEG C/min in any one or at least two combination gas, is passed through ammonia, is led to
The mass ratio for entering ammonia and graphene oxide used in step (1) is (10~20):(80~90), 6~8h of constant temperature are restored, are obtained
The graphene film loaded to substrate；
(4) Copper thin film in the graphene film of substrate load obtained by step (3) is dissolved with the salpeter solution of 4~6mol/L,
It is 1~20 μm to obtain thickness, and thermal conductivity is 780~850W/mK, and tensile strength values are 37.8~57.9MPa, O/C molar ratios
It is 1:The graphene film of (20~30).
9. graphene film prepared by a kind of preparation method such as claim 1~8 any one of them graphene film.
10. the purposes of graphene film as claimed in claim 9, which is characterized in that the graphene film for touch screen,
Solar cell, the transparent conductive film of OLED or transparent heat conducting film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437182A (en) * | 2018-12-25 | 2019-03-08 | 吉林大学 | A method of enhancing graphene oxide shines |
| CN111137879A (en) * | 2020-01-10 | 2020-05-12 | 南京工业大学 | Method for preparing graphene heat dissipation film by using self-propagating stripping technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120161192A1 (en) * | 2010-12-22 | 2012-06-28 | Korea Advanced Institute Of Science And Technology | Nitrogen-doped transparent graphene film and manufacturing method thereof |
| 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 |
-
2018
- 2018-06-26 CN CN201810667847.3A patent/CN108751172A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120161192A1 (en) * | 2010-12-22 | 2012-06-28 | Korea Advanced Institute Of Science And Technology | Nitrogen-doped transparent graphene film and manufacturing method thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 董家玮: "氧化石墨烯气相还原与掺杂机制研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 邢焰等: "《航天器材料》", 31 May 2018, 北京理工大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437182A (en) * | 2018-12-25 | 2019-03-08 | 吉林大学 | A method of enhancing graphene oxide shines |
| CN109437182B (en) * | 2018-12-25 | 2021-09-28 | 吉林大学 | Method for enhancing graphene oxide luminescence |
| CN111137879A (en) * | 2020-01-10 | 2020-05-12 | 南京工业大学 | Method for preparing graphene heat dissipation film by using self-propagating stripping technology |
| CN111137879B (en) * | 2020-01-10 | 2023-06-06 | 南京工业大学 | Method for preparing graphene heat dissipation film by using self-propagating stripping technology |
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