CN107541709B - A kind of preparation method and graphene film of graphene film - Google Patents
A kind of preparation method and graphene film of graphene film Download PDFInfo
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Abstract
The present invention relates to carbon nanomaterial technical fields, and in particular to a kind of preparation method and graphene film of graphene film；After the preparation method of the graphene film is the following steps are included: (1) mix expanded graphite with water, it is put into liquid nitrogen, stands 5~60min, obtain graphene presoma；(2) graphene presoma, surfactant, reducing agent and metal salt are obtained into mixed system after mixing in a solvent, 10~30min is handled in microwave, obtains graphene suspension；(3) graphene suspension is coated in substrate using high speed ion injection method, obtains substrate A；(4) graphite ene coatings are deposited on substrate A using PVD method；(5) substrate is removed, graphene film presoma is obtained；(6) graphene film is compound with polyaniline, graphene film is obtained, there is good electric conductivity, consistency and flexibility by the graphene film that this method is prepared, have broad application prospects on electrode and display screen.
Description
Technical field
The present invention relates to carbon nanomaterial technical fields, and in particular to a kind of preparation method and graphene of graphene film
Film.
Background technique
Graphene (Graphene) be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in the flat of honeycomb lattice
Face film is a kind of two-dimensional material of only one carbon atom thickness.Graphene has transparency high (97.7%), electronics conduction
Fast (the 106S cm of rate-1), high mechanical strength (1.1TPa), good (the 5300W m of thermal conductivity-1K-1), stable structure and high ratio
Surface area (2600m2g-1) the features such as, make it in wearable electronic device just because of the unique structure of graphene and excellent property
Part, superpressure compression material, sensor, catalyst, carrier material, memory device (lithium ion battery, supercapacitor, fuel cell,
Solar battery etc.) etc. show potential application in numerous areas.It is shaped to by two-dimensional graphene material grapheme material group
Three-dimensional grapheme material have and porous, high light absorption, excellent photothermal conversion ability and tied in concentrated acid concentrated alkali solution
Structure keeps stable performance, has potential application grapheme material in terms of solar energy water cleaning.
Inorganic metal nanoparticle is evenly spread into graphene nanometer sheet surface, graphene-based inorganic metal nanometer is made
Composite material can not only account for the dual function property of tool graphene and inorganic metal nanoparticle, and there may be some new
The synergistic effect of grain husk.The compound performance that can be further improved material of inorganic metal nanoparticle and graphene is widened significantly
The application range of inorganic metal nanoparticle and graphene.Since the size and shape of nano material directly affects the physics of material
And chemical property, so an important trend tightens control engineering in terms of nanometer material preparation science and technical research
Research, the control including particle size, pattern, surface state and micro-structure.Have extensively due to nano metal in every field again
Application, so the control synthetic method of simple, effective graphene metal nanometer composite material is explored, for graphene inorganic
The research and application of nano metal composite material have important theory and realistic meaning.
Metal nanoparticle is grapheme modified, this can not only overcome huge Van der Waals force between graphene layer, prevents stone
The reunion of black alkene piece, enables the peculiar property of single-layer graphene to retain.Meanwhile obtained composite material many properties is than gold
Belong to inherently more superior, there is important application value in catalysis, the ceramic fields such as chemical industry and battery.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of preparation side of graphene film
Method has good electric conductivity, consistency and flexibility by the graphene film that this method is prepared.
The second purpose of invention is to provide a kind of graphene film.
To achieve the goals above, the present invention provides a kind of preparation method of graphene film, comprising the following steps:
(1) expansion process is carried out to graphite, obtains expanded graphite, after expanded graphite is mixed with water, is put into liquid nitrogen, it is quiet
5~60min is set, graphene presoma is obtained；
(2) graphene presoma, surfactant, reducing agent and metal salt are mixed after mixing in a solvent
System handles 10~30min in microwave, obtains graphene suspension；
(3) graphene suspension is coated in substrate using high speed ion injection method, obtains substrate A；
(4) graphite ene coatings are deposited on substrate A using ion sputtering process, obtains substrate B；
(5) substrate is removed, thin film precursor is obtained；
(6) thin film precursor is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, stand 5~30min
Afterwards, it is alternately washed with water and ethyl alcohol respectively, obtains graphene film.
In the present invention, by mixing expanded graphite according to a certain percentage with water, it is tuned into slurry, hydrone is made to penetrate into stone
In the lamellar spacing of ink, then slurry is placed in liquid nitrogen, liquid water is expanded into solid ice under ultralow temperature, so that graphite is into one
Step removing generates graphene, and the content of water and graphene is hypovolia an important factor for influencing its peeling effect, then without
Method plays the role of removing graphene, and water content is higher, then reduces charge stripping efficiency again, it is preferred that the expanded graphite and water
Weight ratio be 1:(0.6~2.3).
In the present invention, expanded graphite is mixed in the solution with metal salt, can in expanded graphite intercalation metal ion,
On the one hand it can reunite to avoid the graphene of removing, on the other hand, metal ion is imported in graphite linings, it can be to graphite
Alkene is modified, so that graphene not only has good transmitance, but also has excellent electric conductivity.Preferably, described
Metal salt is at least one of cobalt salt, nickel salt, manganese salt, silver salt, mantoquita, zinc salt, magnesium salts；The concentration of metal ion influences graphite
The electric conductivity of alkene, it is further preferred that the concentration of the metal ion is 1~5mol/L.
Graphite oxide can be reduced into redox graphene by reducing agent, so that the electric conductivity of graphene film is improved,
Preferably, the reducing agent is at least one of ascorbic acid, hydrazine hydrate, sodium borohydride and sodium citrate, further, institute
The concentration for stating reducing agent is 2~10mol/L.
In step (2), acid solution not only contributes to the removing of graphene, also helps metal ion in the solution
Stability, it is preferred that pH≤3 of the mixed system are adjusted by least one of addition sulfuric acid, hydrochloric acid, nitric acid, perchloric acid etc.
Save the pH value of mixed system.
In order to improve the stability of graphene suspension, surfactant, surface are also contained in the graphene suspension
Activating agent can be improved the stability of graphene suspension, it is preferred that the surfactant is N- methyl-pyrrolidon, ten
Dialkyl benzene sulfonic acids sodium, polyvinylpyrrolidone, sodium lignin sulfonate, cetyl trimethylammonium bromide, polyoxyethylene laural
Ether, dibutyltin oxide, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethylacrylic acid, in polyethylene glycol oxide at least
It is a kind of.
The concentration of graphene presoma is also to influence one of the factor of graphene film stability in the present invention, before graphene
It is excessively high to drive bulk concentration, then can cause the reunion of graphene, graphene precursor concentration is too low, then will lead to the graphite of subsequent preparation
Alkene film consistency reduces, it is preferred that the concentration of the graphene is 3~15mg/mL.
Organic solvent is the medium of dispersed graphite alkene, and the present invention does not have special requirement to it, can be the field skill
Organic solvent well known to art personnel, in order to reduce the time of later period drying, the preferably low-boiling organic solvent of the present invention, such as
It can be at least one of ethyl alcohol, acetone, methylene chloride and ether.
The present invention forms base's graphene film in substrate surface by high speed ion injection method, wherein the work of ion injection
Skill parameter is an important factor for influencing graphene film performance, in order to obtain base relatively thin and in homogeneous thickness graphene film, preferably
, the influx of the high speed ion injection method is 1~5 × 10-6g/cm2；It is further preferred that the injection time be 3~
10min；It is furthermore preferred that the Implantation Energy is 60~120eV.
In order to enable subsequent coating to go on smoothly, the quality of graphene film is improved, is prolonged its service life, at this
In the preparation method of invention, also substrate is pre-processed, to reach the mesh for removing substrate surface greasy dirt, rusty stain and dust
's.The present invention pre-processes substrate using conventional use of method in the art, specifically, the pretreated step
Are as follows: substrate is cleaned by ultrasonic with organic solvent, then removes the solvent of substrate surface, is dried.
By the spin coating PMMA on graphene film, convenient for the not damaged transfer of later period graphene film.In order to improve stone
The electric conductivity of black alkene film in the present invention, carries out the metal-doped graphene film of sputtering sedimentation on substrate graphene film, should
Graphene film not only has complete lattice structure, also has excellent electric conductivity.
The present invention continues to deposit graphene film on substrate film by sputtering method.The wherein technique of sputtering sedimentation
Are as follows: it is passed through carbon-source gas and inert gas into settling chamber, opens grid bias power supply, the sputtering sedimentation graphene film on substrate A,
More specifically: substrate A being placed in magnetron sputtering plating settling chamber, it is 1 × 10 that coated film deposition room, which is evacuated to pressure,-3Pa,
Then it is passed through argon gas and carbon-source gas into settling chamber, opens grid bias power supply, graphene film is deposited on substrate A, sputters item
Part is that the back bias voltage applied to substrate is -100V, and bias duty ratio is 50%.
Preferably, the flow-rate ratio of the carbon-source gas and the inert gas is 1:(2~10).
The sputtering sedimentation time be determine film thickness key factor, it is preferred that the time of the sputtering sedimentation be 2~
12min。
The present invention improves the electric conductivity of the film of graphene by loading conducting high polymers on graphene film,
In addition, conducting polymer also has good flexibility, it is able to maintain the flexibility of graphene film.
The present invention also provides a kind of graphene films, are prepared according to above-mentioned preparation method.
Preferably, the graphene film with a thickness of 50~200nm.
Through the above technical solutions, the present invention has following technical effect that
1, on the one hand the intercalation metal ion in expanded graphite can reunite to avoid the graphene of removing, another party
Metal ion is imported in graphite linings, can be modified to graphene, so that graphene not only has good transmission by face
Rate, but also there is excellent electric conductivity.
2, the graphene as made from the graphene and physical vapour deposition (PVD) for preparing high speed ion injection method is compound, so that
Graphene film has good flexible, electric conductivity and consistency.
3, by loading conducting high polymers on graphene film, the electric conductivity and flexibility of graphene film are improved.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) prepared by expanded graphite: 98% concentrated sulfuric acid of 55mL and 1g sodium nitrate, condition of ice bath first is added in dry beaker
Lower cooling is added 4g crystalline flake graphite in stirring and is slowly added to 5g permanganic acid after mixing when system temperature is lower than 5 DEG C
Potassium, control reacting liquid temperature are no more than 20 DEG C, react 2h, then place the beaker in 35 DEG C or so of water bath with thermostatic control, uniformly stir
It mixes, liquid temperature to be mixed rises to 35 DEG C, reacts 30min, and 92mL deionized water is added, control reacting liquid temperature at 98 DEG C or so,
Continue to stir 15min, 280mL deionized water is then added by reaction terminating, while 30% hydrogen peroxide of 20mL is added, it is at this moment molten
Liquid becomes vivid yellow from brownish black, filters while hot, and is washed with 5% dilute hydrochloric acid of 2L to product, is filled with deionized water
Divide washing until pH value is neutrality.Then dry in 60 DEG C of baking ovens, the graphite oxide of acquisition is placed in drier and protects by grinding
It deposits, 2g graphite oxide powder is taken to be placed in 100mL ceramic crucible, lid is tied up into fixation with thin wire, the crucible tied up is put
Enter in 1050 DEG C of Muffle furnaces, is taken out after 30s, obtain expanded graphite；
After expanded graphite and water are mixed according to the ratio of 1:1.5, it is put into liquid nitrogen, 30min is stood, then at 60 DEG C
10min is placed, graphene presoma is obtained；
(2) by 1g graphene presoma, 2g cetyl trimethylammonium bromide, 0.8mol ascorbic acid and 0.3mol chlorination
Iron obtains mixed system after mixing in 200mL ethyl alcohol, and it is 1.5 that hydrochloric acid conditioning solution pH value, which is added, then in microwave
15min is handled, then ultrasonic disperse 10min, is centrifuged under the rate of 2000r/min, takes supernatant, and obtaining concentration is 12mg/
The graphene suspension of mL；
(3) copper sheet dehydrated alcohol and acetone are cleaned by ultrasonic stainless steel substrates 30min respectively, then dried, using high speed
Graphene suspension is coated in substrate by ion injection method, base's graphene film that coating thickness is about 20nm on copper sheet,
Substrate A is obtained, wherein the influx of high speed ion injection method is 1 × 10-6g/cm2；Injection time is 5min；Implantation Energy is
80eV；
(4) substrate A is placed in magnetron sputtering plating settling chamber, it is 1 × 10 that coated film deposition room, which is evacuated to pressure,- 3Pa is passed through argon gas and acetylene in backward settling chamber, and wherein the flow of argon gas is 40sccm, and the flow of acetylene is 100sccm, opens
Grid bias power supply is opened, the second graphene film that deposition thickness is about 10nm on substrate A obtains substrate B, and sputtering condition is to base
The back bias voltage that piece applies is -100V, and bias duty ratio is 50%, sedimentation time 2min；
(5) copper sheet of above-mentioned load graphene film is placed in the ferric chloride solution of 0.5moL/L, until copper sheet quilt completely
Corrosion, then film is washed with water 3 times, after drying, obtain thin film precursor；
(6) graphene film is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, after standing 5min,
The polyaniline with a thickness of 20nm is formed on thin film precursor, is alternately washed with water and ethyl alcohol respectively, is obtained graphene film.
The graphene film being prepared according to the above method is by base's graphene film, middle layer graphene film and polyaniline group
At.
Embodiment 2
(1) the preparation method is the same as that of Example 1 for expanded graphite preparation；
After expanded graphite and water are mixed according to the ratio of 1:1.2, it is put into liquid nitrogen, 15min is stood, then at 50 DEG C
10min is placed, graphene presoma is obtained；
(2) by 1g graphene presoma, 1.5g polyacrylamide, 0.4mol sodium borohydride and 0.6 chloroplatinic acid in 200mL third
Mixed system is obtained in ketone after mixing, it is 2 that sulfuric acid regulation solution pH value, which is added, 20min is then handled in microwave, then
Ultrasonic disperse 5min is centrifuged under the rate of 2500r/min, takes supernatant, obtains the graphene suspension that concentration is 8mg/mL；
(3) copper sheet dehydrated alcohol and acetone are cleaned by ultrasonic stainless steel substrates 30min respectively, then dried, using high speed
Graphene suspension is coated in substrate by ion injection method, base's graphene film that coating thickness is about 20nm on copper sheet,
Substrate A is obtained, wherein the influx of high speed ion injection method is 2 × 10-6g/cm2；Injection time is 7min；Implantation Energy is
100eV；
(4) substrate A is placed in magnetron sputtering plating settling chamber, it is 1 × 10 that coated film deposition room, which is evacuated to pressure,- 3Then Pa is passed through argon gas and acetylene into settling chamber, wherein the flow of argon gas is 25sccm, and the flow of acetylene is 100sccm,
Grid bias power supply is opened, the second graphene film that deposition thickness is about 50nm on substrate A obtains substrate B, and sputtering condition is pair
The back bias voltage that substrate applies is -100V, and bias duty ratio is 50%, sedimentation time 10min；
(5) copper sheet of above-mentioned load graphene film is placed in the ferric chloride solution of 0.5moL/L, until copper sheet quilt completely
Corrosion, then film is washed with water 3 times, after drying, obtain thin film precursor；
(6) thin film precursor is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, after standing 10min,
The polyaniline with a thickness of 30nm is formed on thin film precursor, is alternately washed with water and ethyl alcohol respectively, is obtained graphene film.
The graphene film being prepared according to the above method is by base's graphene film, middle layer graphene film and polyaniline group
At.
Embodiment 3
(1) the preparation method is the same as that of Example 1 for expanded graphite preparation；
After expanded graphite and water are mixed according to the ratio of 1:1.8, it is put into liquid nitrogen, 5min is stood, then at 60 DEG C
5min is placed, graphene presoma is obtained；
(2) by 1g graphene presoma, 0.8g polyvinyl alcohol, 1.2mol sodium borohydride and 0.5mol gold chloride in 200mL
Mixed system is obtained in acetone after mixing, it is 3 that nitric acid, which is added, and adjusts solution ph, 25min is then handled in microwave, so
Ultrasonic disperse 8min afterwards is centrifuged under the rate of 2000r/min, takes supernatant, obtains the graphene that concentration is 5mg/mL and suspends
Liquid；
(3) copper sheet dehydrated alcohol and acetone are cleaned by ultrasonic stainless steel substrates 30min respectively, then dried, using high speed
Graphene suspension is coated in substrate by ion injection method, base's graphene film that coating thickness is about 20nm on copper sheet,
Substrate A is obtained, wherein the influx of high speed ion injection method is 3 × 10-6g/cm2；Injection time is 5min；Implantation Energy is
120eV；
(4) substrate A is placed in magnetron sputtering plating settling chamber, it is 1 × 10 that coated film deposition room, which is evacuated to pressure,- 3Then Pa is passed through argon gas and acetylene into settling chamber, wherein the flow of argon gas is 30sccm, and the flow of acetylene is 150sccm,
Grid bias power supply is opened, the second graphene film that deposition thickness is about 50nm on substrate A obtains substrate B, and sputtering condition is pair
The back bias voltage that substrate applies is -100V, and bias duty ratio is 50%, sedimentation time 3min；
(5) copper sheet of above-mentioned load graphene film is placed in the ferric chloride solution of 0.5moL/L, until copper sheet quilt completely
Corrosion, then film is washed with water 3 times, after drying, obtain thin film precursor；
(6) thin film precursor is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, after standing 20min,
The polyaniline with a thickness of 30nm is formed on thin film precursor, is alternately washed with water and ethyl alcohol respectively, is obtained graphene film.
The graphene film being prepared according to the above method is by base's graphene film, middle layer graphene film and polyaniline group
At.
Embodiment 4
(1) the preparation method is the same as that of Example 1 for expanded graphite preparation；
After expanded graphite and water are mixed according to the ratio of 1:2.3, it is put into liquid nitrogen, 10min is stood, then at 55 DEG C
7min is placed, graphene presoma is obtained；
(2) by 1g graphene presoma, 3.2g polymethylacrylic acid, 1mol sodium citrate and 1mol manganese nitrate in 200mL
Mixed system is obtained in ether after mixing, it is 1 that hydrochloric acid conditioning solution pH value, which is added, 30min is then handled in microwave, so
Ultrasonic disperse 5min afterwards is centrifuged under the rate of 3000r/min, takes supernatant, obtains the graphene that concentration is 3mg/mL and suspends
Liquid；
(3) copper sheet dehydrated alcohol and acetone are cleaned by ultrasonic stainless steel substrates 30min respectively, then dried, using high speed
Graphene suspension is coated in substrate by ion injection method, base's graphene film that coating thickness is about 30nm on copper sheet,
Substrate A is obtained, wherein the influx of high speed ion injection method is 4 × 10-6g/cm2；Injection time is 12min；Implantation Energy is
100eV；
(4) substrate A is placed in magnetron sputtering plating settling chamber, it is 1 × 10 that coated film deposition room, which is evacuated to pressure,- 3Then Pa is passed through argon gas and acetylene into settling chamber, wherein the flow of argon gas is 40sccm, and the flow of acetylene is 80sccm, opens
Grid bias power supply is opened, the second graphene film that deposition thickness is about 60nm on substrate A obtains substrate B, and sputtering condition is to base
The back bias voltage that piece applies is -100V, and bias duty ratio is 50%, sedimentation time 10min；
(5) copper sheet of above-mentioned load graphene film is placed in the ferric chloride solution of 0.5moL/L, until copper sheet quilt completely
Corrosion, then film is washed with water 3 times, after drying, obtain thin film precursor；
(6) thin film precursor is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, after standing 30min,
The polyaniline with a thickness of 50nm is formed on thin film precursor, is alternately washed with water and ethyl alcohol respectively, is obtained graphene film.
The graphene film being prepared according to the above method is by base's graphene film, middle layer graphene film and polyaniline group
At.
Embodiment 5
(1) the preparation method is the same as that of Example 1 for expanded graphite preparation；
After expanded graphite and water are mixed according to the ratio of 1:0.6, it is put into liquid nitrogen, 60min is stood, then at 60 DEG C
5min is placed, graphene presoma is obtained；
(2) 1g graphene presoma, 1.2g polyvinylpyrrolidone, 2mol reducing agent and 0.2mol ferric nitrate are existed
Mixed system is obtained in 200mL methylene chloride after mixing, it is 1.2 that hydrochloric acid conditioning solution pH value, which is added, then in microwave
10min is handled, then ultrasonic disperse 10min, is centrifuged under the rate of 3000r/min, takes supernatant, and obtaining concentration is 15mg/
The graphene suspension of mL；
(3) copper sheet dehydrated alcohol and acetone are cleaned by ultrasonic stainless steel substrates 30min respectively, then dried, using high speed
Graphene suspension is coated in substrate by ion injection method, base's graphene film that coating thickness is about 40nm on copper sheet,
Substrate A is obtained, wherein the influx of high speed ion injection method is 5 × 10-6g/cm2；Injection time is 3min；Implantation Energy is
120eV；
(4) substrate A is placed in coated film deposition room, it is 1 × 10 that coated film deposition room, which is evacuated to pressure,-3Pa, then to
Argon gas and acetylene are passed through in settling chamber, wherein the flow of argon gas is 20sccm, and the flow of acetylene is 200sccm, opens bias plasma
Source, the second graphene film that deposition thickness is about 60nm on substrate A obtain substrate B, and sputtering condition is to apply to substrate
Back bias voltage is -100V, and bias duty ratio is 50%, sedimentation time 5min；
(5) copper sheet of above-mentioned load graphene film is placed in the ferric chloride solution of 0.5moL/L, until copper sheet quilt completely
Corrosion, then film is washed with water 3 times, after drying, obtain thin film precursor；
(6) thin film precursor is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, after standing 15min,
The polyaniline with a thickness of 100nm is formed on thin film precursor, is alternately washed with water and ethyl alcohol respectively, is obtained graphene film.
The graphene film being prepared according to the above method is by base's graphene film, middle layer graphene film and polyaniline group
At.
Comparative example 1
Using the method for embodiment 1, the difference is that, do not use liquid nitrogen frozen.
Comparative example 2
Using the method for embodiment 1, the difference is that, in step (2), do not use reducing agent to go back graphite oxide
It is former.
Comparative example 3
Using the method for embodiment 1, the difference is that, in step (2), do not use metal ion to carry out expanded graphite slotting
Layer processing.
Comparative example 4
Using the method for embodiment 1, the difference is that, it does not contain step (3), graphene film is directly deposited on copper sheet.
Comparative example 5
Using the method for embodiment 1, the difference is that, it does not contain step (4), injection coating base's graphite directly on copper sheet
Alkene.
Comparative example 6
Using the method for embodiment 1, the difference is that, it does not contain step (5), injection coating base's graphene.
Performance test
Surface resistance test: it is tested using surface resistance of the Keithley2700 to film, experimental result such as table 1.
Flexible test: the film in Examples 1 to 5 and comparative example 1~6 is adhered in glass fiber filter paper, is carried out curved
Folding, bending angle are 150 °, the maximum bending number of recording paper.
Table 1
| Embodiment number | Surface resistance (m Ω/sq) | Bend number |
| Embodiment 1 | 321 | 50000 |
| Embodiment 2 | 345 | 50000 |
| Embodiment 3 | 336 | 45000 |
| Embodiment 4 | 389 | 48000 |
| Embodiment 5 | 397 | 48000 |
| Comparative example 1 | 425 | 35000 |
| Comparative example 2 | 436 | 32000 |
| Comparative example 3 | 418 | 40000 |
| Comparative example 4 | 441 | 15000 |
| Comparative example 5 | 457 | 8000 |
| Comparative example 6 | 469 | 5000 |
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction.In order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (7)
1. a kind of preparation method of graphene film, which comprises the following steps:
(1) expansion process is carried out to graphite, obtains expanded graphite, after expanded graphite is mixed with water, is put into liquid nitrogen, stand 5
~60min obtains graphene presoma；
(2) graphene presoma, surfactant, reducing agent and metal salt are obtained into mixture after mixing in a solvent
System handles 10~30min in microwave, obtains graphene suspension；
(3) graphene suspension is coated in substrate using high speed ion injection method, obtains substrate A；
(4) graphite ene coatings are deposited on substrate A using PVD method；
(5) substrate is removed, thin film precursor is obtained；
(6) thin film precursor is added in the sulfuric acid solution dissolved with aniline monomer, forms reaction solution, after standing 5~30min,
It is alternately washed with water and ethyl alcohol respectively, obtains graphene film.
2. the preparation method of graphene film according to claim 1, which is characterized in that in step (1), the expansion
The weight ratio of graphite and water is 1:(0.6~2.3).
3. the preparation method of graphene film according to claim 1 or 2, which is characterized in that described in step (2)
Metal salt is at least one of cobalt salt, nickel salt, manganese salt, silver salt, mantoquita, zinc salt, magnesium salts；And/or
The reducing agent is at least one of ascorbic acid, hydrazine hydrate, sodium borohydride, sodium citrate；And/or
The surfactant is N- methyl-pyrrolidon, neopelex, polyvinylpyrrolidone, sulfomethylated lignin
Sour sodium, polyoxyethylene laurel ether, dibutyltin oxide, polyvinyl alcohol, polyacrylamide, gathers cetyl trimethylammonium bromide
At least one of acrylic acid, polymethylacrylic acid, polyethylene glycol oxide.
4. the preparation method of graphene film according to claim 3, which is characterized in that in step (2), the mixing
In system, the concentration of the graphene presoma is 3~15mg/mL；And/or
The concentration of the reducing agent is 2~10mol/L；And/or
The concentration of the metal salt is 1~5mol/L.
5. the preparation method of graphene film according to claim 3, which is characterized in that in step (3), the high speed
The influx of ion injection method is 1~5 × 10-6g/cm2；And/or
Injection time is 3~10min；And/or
Implantation Energy is 60~120eV.
6. a kind of graphene film, which is characterized in that the preparation of preparation method described according to claim 1~any one of 5
It obtains.
7. graphene film according to claim 6, which is characterized in that the graphene film with a thickness of 50~
200nm。
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| CN109665515A (en) * | 2018-12-18 | 2019-04-23 | 武汉华星光电半导体显示技术有限公司 | Grapheme material preparation method, OLED luminescent device and display device |
| CN113593769B (en) * | 2021-07-07 | 2023-07-28 | 宁波石墨烯创新中心有限公司 | Graphene composite film and preparation method thereof |
| CN114230898B (en) * | 2021-12-31 | 2024-01-12 | 河北科技大学 | Graphene transparent conductive film and preparation method and application thereof |
| CN115893384B (en) * | 2022-11-28 | 2024-03-08 | 南开大学 | Synthesis method of porous graphene-like nanosheets with biomass as raw material |
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