CN106587030A - Method for preparing graphene thin film by chemical vapor deposition at normal pressure and low temperature - Google Patents
Method for preparing graphene thin film by chemical vapor deposition at normal pressure and low temperature Download PDFInfo
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- CN106587030A CN106587030A CN201710018061.4A CN201710018061A CN106587030A CN 106587030 A CN106587030 A CN 106587030A CN 201710018061 A CN201710018061 A CN 201710018061A CN 106587030 A CN106587030 A CN 106587030A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a method for preparing a graphene thin film by chemical vapor deposition at normal pressure and low temperature. According to the method, a metal substrate is subjected to high-temperature annealing treatment firstly and then temperature-reduction annealing treatment; and next, the graphene thin film is obtained on the surface of the metal substrate through the chemical vapor deposition method. By virtue of the method, the catalysis activity of the metal substrate is improved, so that the growth temperature of graphene is lowered, and the energy consumption and cost of industrial production of the graphene thin film are lowered consequently; and compared with a conventional chemical vapor deposition method for synthesizing the graphene thin film, the method disclosed by the invention is simple in process, the carbon source is wide in source, the prepared graphene thin film is high in quality, and the number of layers is uniform and controllable.
Description
Technical field
The present invention relates to field of preparation of graphene, more particularly to one kind is made under atmospheric low-temperature using chemical vapour deposition technique
The method of standby graphene film.
Background technology
Graphene is to be based on sp by monolayer carbon atom2The hexagon cellular shape two dimensional crystal of hydridization composition, since quilt in 2004
Since Andre Geim and Konstantin Novoselov et al. have found, the extensive concern of scientific circles is attracted.Graphene exists
The excellent specific property that the aspects such as electricity, optics, calorifics, mechanics show so as in battery, flexible transparent electrode, energy storage material, electricity
There is huge potential application foreground in the fields such as catalyst, nano electron device and composite.
At present, the preparation method of graphene film mainly has：Mechanical stripping method, reduction-oxidation graphite method, chemical vapor deposition
Area method (CVD), epitaxial growth method etc..Wherein, though mechanical stripping method can be obtained the Graphene of excellent performance, less efficient and weight
Renaturation is poor；Reduction-oxidation graphite method can be prepared on a large scale Graphene, but its poor quality；Graphite prepared by SiC epitaxial growth methods
Alkene is with high costs.By contrast, chemical vapour deposition technique is simple to operate, and can prepare the uniform Graphene of large area, the number of plies,
Especially gaseous carbon sources can be the effective way for realizing Graphene serialization, industrialized production with without interruption.However, existing
CVD growth Graphene must carry out at high temperature（Usually above 1000 DEG C）, this greatly hinders the industry of Graphene
Metaplasia is produced.Therefore, find a kind of large-scale production of method that can prepare the controllable Graphene of the number of plies at low temperature to Graphene
With using most important.
The content of the invention
Present invention is generally directed to the problem that existing process for preparing graphenes by chemical vapour deposition must be carried out at high temperature, there is provided
A kind of method that utilization chemical vapour deposition technique prepares graphene film under atmospheric low-temperature.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of method that atmospheric cryochemistry vapour deposition prepares graphene film, comprises the steps：
（1）Metallic substrates are cleaned by ultrasonic 5 ~ 10min, and are removed metal substrate surface with hydrochloric acid, acetone, deionized water respectively
Then metallic substrates are carried out the high temperature anneal by moisture, and treatment conditions are：300 ~ 1000sccm of argon flow amount, hydrogen flowing quantity
10 ~ 100sccm, temperature are 850 ~ 1050 DEG C, 10 ~ 90min of process time；
（2）To step（1）The metallic substrates of middle Jing the high temperature anneals carry out cooling annealing, and treatment conditions are：In argon
200 ~ 800 DEG C are cooled under atmosphere at the uniform velocity, wherein argon flow amount is 300 ~ 1000sccm；
（3）Treat step（2）Middle metallic substrates are down to predetermined reaction temperature, are passed through gaseous carbon sources and argon, carry out chemical vapor deposition
Product, that is, obtain graphene film.
Preferably, the metallic substrates are Copper Foil, cobalt paper tinsel, nickel foil, at least one in iron foil, or it is copper film, cobalt
At least one in film, nickel film, ferrum film.Metallic substrates used in the present invention can be by existing metallic film preparation method system
It is standby to obtain, the such as method such as magnetron sputtering, electrochemical deposition, vacuum evaporation.
Preferably, step（1）High temperature makes annealing treatment condition：Argon flow amount 800sccm, hydrogen flowing quantity 30sccm,
950 DEG C of temperature, process time 50min.
Preferably, the metallic substrates are Copper Foil.
Preferably, step（2）Middle rate of temperature fall is 1 ~ 30 DEG C/min.
Preferably, step（2）Middle metallic substrates are at the uniform velocity cooled to 300 ~ 700 DEG C.In the present invention, step（2）Dropped
During temperature annealing, it is also possible to by the metallic substrates of Jing the high temperature anneals, be first at the uniform velocity cooled to room temperature under an argon atmosphere, so
Rise to predetermined reaction temperature afterwards again.
Preferably, step（3）Described in gaseous carbon sources be methane, ethane, acetylene, ethylene, at least one in propane.
Preferably, step（3）Middle chemical vapor deposition conditions are：Carbon-source gas 1 ~ 10sccm of flow, argon flow amount 100
~ 1000sccm, 1 ~ 20min of response time.
Preferably, the gaseous carbon sources are methane.
Compared to existing technology, the present invention has the advantages that：
1. the present invention is by first carrying out the high temperature anneal to metallic substrates, then carries out cooling annealing, reduces gaseous carbon
Hydrogen compound improves the catalytic capability of metallic substrates itself, obtains in the energy of adsorption and dehydrogenation and cracking energy of metal substrate surface
Metallic substrates with high catalytic activity, so as to greatly reduce the growth temperature of Graphene, therefore reduce commercial production
The energy consumption and cost of graphene film, is conducive to the process of industrialization of Graphene.
2., present invention achieves preparing monolayer continuous graphite alkene thin film using chemical vapour deposition technique under atmospheric low-temperature, prepare
Graphene film Raman scattering have obvious 2D peaks, and IG/I2D＜ 0.5, light transmittance are 97.1 ~ 97.3%, compare traditional change
Learn vapour deposition process synthesizing graphite alkene thin film, the inventive method process is simple, carbon source wide material sources, the graphene film matter of preparation
Amount is high, the number of plies is homogeneous and controllable.
Description of the drawings
Fig. 1 is the experimental provision structural representation that the present invention prepares graphene film employing；
Fig. 2 is the optical microscope of graphene film prepared by embodiment 1；
Fig. 3 is the Raman spectrogram of graphene film prepared by embodiment 1；
Fig. 4 is the scanning electron microscope diagram of graphene film prepared by embodiment 1；
Fig. 5 is the optical microscope of graphene film prepared by embodiment 2；
Fig. 6 is the Raman spectrogram of graphene film prepared by embodiment 2；
Fig. 7 is the transmission electron microscope figure of graphene film prepared by embodiment 2.
Specific embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Fig. 1 is the experimental provision structural representation that the present invention prepares graphene film employing, as shown in figure 1, the device bag
Include argon source of the gas 1, hydrogen source gas 2, gaseous carbon sources 3, gas Flowrate Control System and mixed gas system 4, quartz ampoule 5 and CVD tubular types
Stove 6.When graphene film is prepared using the device, first metallic substrates 7 are positioned in quartz ampoule 5, and be in metallic substrates 7
The centre of tube furnace 6, after metallic substrates 7 Jing after twice annealing process, gaseous carbon sources 3 and argon are passed through in quartz ampoule 5 to be carried out
Chemical vapor deposition, you can obtain graphene film on 7 surface of metallic substrates.
Embodiment 1
The present embodiment prepares graphene film using chemical deposition under atmospheric low-temperature, comprises the steps：
（1）Copper Foil is cleaned by ultrasonic into 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, the moisture of copper foil surface is then removed,
Again Copper Foil is put in quartz ampoule, and Copper Foil is located in the middle of tube furnace, regulations argon flow amount is 800sccm, and hydrogen flowing quantity is
Copper Foil is heated to 950 DEG C under this atmosphere by 30sccm, and re-annealing processes 50min；
（2）By step（1）The Copper Foil of annealed process, is at the uniform velocity cooled to 700 DEG C under an argon atmosphere, and wherein argon flow amount is
300sccm, rate of temperature fall are 28 DEG C/min；
（3）Treat step（2）When middle Copper Foil temperature is down to 700 DEG C, methane and argon growth Graphene are passed through, wherein methane flow is
2sccm, argon flow amount are 500sccm, and the response time is 5min；
（4）After reaction 5min, stopping is passed through methane, and Copper Foil is quickly down to room temperature, you can obtain Graphene in copper foil surface
Thin film.
Fig. 2 is transferred to SiO for graphene film obtained in the present embodiment2Optical microscope picture in/Si substrates, by scheming
2 as can be seen that graphene film thickness manufactured in the present embodiment is uniform.
Fig. 3 is the Raman collection of illustrative plates of graphene film manufactured in the present embodiment, as shown in figure 3, graphite manufactured in the present embodiment
Clearly, and the ratio at 2D peaks and G peaks is more than 2, while also there is obvious defect peak D peaks, demonstrate,proves at the characteristic peak 2D peaks of alkene thin film
Bright the present embodiment has prepared the single-layer graphene of better quality.
Fig. 4 is transferred to SiO for graphene film manufactured in the present embodiment2Scanning electron microscope diagram piece in/Si substrates,
The border of Graphene be can clearly be seen that on the picture left side, and in figure, do not see crackle, it was demonstrated that Graphene manufactured in the present embodiment
It is continuous.
Embodiment 2
The present embodiment prepares graphene film using chemical deposition under atmospheric low-temperature, comprises the steps：
（1）Copper Foil is cleaned by ultrasonic into 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, the moisture of copper foil surface is then removed,
Again Copper Foil is put in quartz ampoule, and Copper Foil is located in the middle of tube furnace, regulations argon flow amount is 800sccm, and hydrogen flowing quantity is
Copper Foil is heated to 950 DEG C under this atmosphere by 30sccm, and re-annealing processes 50min；
（2）By step（1）The Copper Foil of annealed process, is at the uniform velocity cooled to 400 DEG C under an argon atmosphere, and wherein argon flow amount is
300sccm, rate of temperature fall are 30 DEG C/min；
（3）Treat step（2）When middle Copper Foil temperature is down to 400 DEG C, methane and argon growth Graphene are passed through, wherein methane flow is
10sccm, argon flow amount are 500sccm, and the response time is 10min；
（4）After reaction 10min, stopping is passed through methane, and Copper Foil is quickly down to room temperature, you can obtain Graphene in copper foil surface
Thin film.
Fig. 5 is transferred to SiO for graphene film obtained in the present embodiment2Optical microscope picture in/Si substrates, by scheming
2 as can be seen that graphene film thickness manufactured in the present embodiment uniformly, can be clearly seen that SiO from rent2/ Si substrates
With the border of Graphene.
Fig. 6 is the Raman collection of illustrative plates of graphene film manufactured in the present embodiment, as shown in figure 3, graphite manufactured in the present embodiment
Clearly, and the ratio at 2D peaks and G peaks is close to 2 at the characteristic peak 2D peaks of alkene thin film, and compared to embodiment 1, prepared by the present embodiment
The defect peak D peaks of graphene film reduced, show that Graphene quality manufactured in the present embodiment is more slightly higher than embodiment.
Fig. 7 is the transmission electron micrograph that graphene film manufactured in the present embodiment is transferred on copper mesh, can by Fig. 7
Will become apparent from Graphene manufactured in the present embodiment as single-layer graphene.
Embodiment 3
The present embodiment prepares graphene film using chemical deposition under atmospheric low-temperature, comprises the steps：
（1）Using magnetron sputtering method in SiO2Corronil thin film is prepared on/Si pieces, corronil thin film is put into into quartz then
Guan Zhong, and corronil thin film is located in the middle of tube furnace, regulation argon flow amount is 900sccm, and hydrogen flowing quantity is 30sccm,
By corronil film heating to 900 DEG C under this atmosphere, re-annealing processes 65min；
（2）By step（1）The corronil thin film of annealed process, is at the uniform velocity cooled to 400 DEG C, wherein argon under an argon atmosphere
Flow is 400sccm, and rate of temperature fall is 25 DEG C/min；
（3）Treat step（2）When middle corronil film temperature is down to 400 DEG C, ethane acetylene gaseous mixture and argon growth stone are passed through
Black alkene, wherein mixed gas flow are 10sccm, and in gaseous mixture, ethane acetylene volume ratio is 1:2, argon flow amount is 600sccm, instead
It is 15min between seasonable；
（4）After reaction 15min, stopping is passed through gaseous mixture, and corronil thin film is quickly down to room temperature, you can in corronil
Film surface obtains graphene film.
Embodiment 4
The present embodiment prepares graphene film using chemical deposition under atmospheric low-temperature, comprises the steps：
（1）Copper-iron alloy paper tinsel is cleaned by ultrasonic into 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, copper-iron alloy is then removed
The moisture on paper tinsel surface, then copper-iron alloy paper tinsel is put in quartz ampoule, and copper-iron alloy paper tinsel is located in the middle of tube furnace, adjust argon
Flow is 300sccm, and hydrogen flowing quantity is 15sccm, and Copper Foil is heated to 850 DEG C under this atmosphere, re-annealing process
10min；
（2）By step（1）The copper-iron alloy paper tinsel of annealed process, is at the uniform velocity cooled to 300 DEG C, wherein argon stream under an argon atmosphere
Measure as 600sccm, rate of temperature fall is 3 DEG C/min；
（3）Treat step（2）When middle Copper Foil temperature is down to 300 DEG C, acetylene and argon growth Graphene are passed through, wherein acetylene flow is
5sccm, argon flow amount are 1000sccm, and the response time is 20min；
（4）After reaction 20min, stopping is passed through methane, and copper-iron alloy paper tinsel is quickly down to room temperature, you can in copper-iron alloy paper tinsel table
Face obtains graphene film.
Embodiment 5
The present embodiment prepares graphene film using chemical deposition under atmospheric low-temperature, comprises the steps：
（1）Copper film is cleaned by ultrasonic into 5 ~ 10min with hydrochloric acid, acetone and deionized water respectively, the moisture on copper film surface is then removed,
Again copper film is put in quartz ampoule, and copper film is located in the middle of tube furnace, regulations argon flow amount is 500sccm, and hydrogen flowing quantity is
Copper Foil is heated to 1050 DEG C under this atmosphere by 90sccm, and re-annealing processes 90min；
（2）By step（1）The copper film of annealed process, is at the uniform velocity cooled to 800 DEG C under an argon atmosphere, and wherein argon flow amount is
1000sccm, rate of temperature fall are 15 DEG C/min；
（3）Treat step（2）When middle Copper Foil temperature is down to 800 DEG C, ethylene and argon growth Graphene are passed through, wherein ethene flow is
8sccm, argon flow amount are 100sccm, and the response time is 1min；
（4）After reaction 1min, stopping is passed through methane, and copper film is quickly down to room temperature, you can obtain Graphene on copper film surface
Thin film.
Finally illustrate, above example is only unrestricted to illustrate technical scheme, although with reference to compared with
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, and without deviating from the objective and scope of technical solution of the present invention, which all should be covered at this
In the middle of the right of invention.
Claims (9)
1. a kind of method that atmospheric cryochemistry vapour deposition prepares graphene film, it is characterised in that comprise the steps：
（1）Metallic substrates are cleaned by ultrasonic 5 ~ 10min, and are removed metal substrate surface with hydrochloric acid, acetone, deionized water respectively
Then metallic substrates are carried out the high temperature anneal by moisture, and treatment conditions are：300 ~ 1000sccm of argon flow amount, hydrogen flowing quantity
10 ~ 100sccm, temperature are 850 ~ 1050 DEG C, 10 ~ 90min of process time；
（2）To step（1）The metallic substrates of middle Jing the high temperature anneals carry out cooling annealing, and treatment conditions are：In argon
200 ~ 800 DEG C are cooled under atmosphere at the uniform velocity, wherein argon flow amount is 300 ~ 1000sccm；
（3）Treat step（2）Middle metallic substrates are down to predetermined reaction temperature, are passed through gaseous carbon sources and argon, carry out chemical vapor deposition
Product, that is, obtain graphene film.
2. the method that atmospheric cryochemistry vapour deposition according to claim 1 prepares graphene film, it is characterised in that
The metallic substrates are Copper Foil, cobalt paper tinsel, nickel foil, at least one in iron foil, or in copper film, cobalt film, nickel film, ferrum film extremely
Few one kind.
3. the method that atmospheric cryochemistry vapour deposition according to claim 1 prepares graphene film, it is characterised in that
Step（1）High temperature makes annealing treatment condition：Argon flow amount 800sccm, hydrogen flowing quantity 30sccm, 950 DEG C of temperature, process time
50min。
4. the method that atmospheric cryochemistry vapour deposition according to claim 2 prepares graphene film, it is characterised in that
The metallic substrates are Copper Foil.
5. the method that atmospheric cryochemistry vapour deposition according to claim 1 prepares graphene film, it is characterised in that
Step（2）Middle rate of temperature fall is 1 ~ 30 DEG C/min.
6. the method that atmospheric cryochemistry vapour deposition according to claim 1 prepares graphene film, it is characterised in that
Step（2）Middle metallic substrates are at the uniform velocity cooled to 300 ~ 700 DEG C.
7. the method that atmospheric cryochemistry vapour deposition according to claim 1 prepares graphene film, it is characterised in that
Step（3）Described in gaseous carbon sources be methane, ethane, acetylene, ethylene, at least one in propane.
8. the method that atmospheric cryochemistry vapour deposition according to claim 1 prepares graphene film, it is characterised in that
Step（3）Middle chemical vapor deposition conditions are：Carbon-source gas 1 ~ 10sccm of flow, 100 ~ 1000sccm of argon flow amount, during reaction
Between 1 ~ 20min.
9. the method that atmospheric cryochemistry vapour deposition according to claim 7 prepares graphene film, it is characterised in that
The gaseous carbon sources are methane.
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Cited By (14)
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| CN107217239A (en) * | 2017-06-14 | 2017-09-29 | 华南理工大学 | It is a kind of to improve the method for graphene film electric conductivity prepared by aumospheric pressure cvd method |
| CN108220912A (en) * | 2018-01-17 | 2018-06-29 | 南昌航空大学 | It is a kind of it is Ni-based on prepare the method for hydrophilic graphene film |
| CN108502873A (en) * | 2018-06-26 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of high quality, less defect, the preparation method of the uniform graphene of structure |
| CN108614313A (en) * | 2018-05-09 | 2018-10-02 | 中国科学院长春光学精密机械与物理研究所 | The adjustable method for reducing optical surface reflectivity |
| CN109023291A (en) * | 2018-08-14 | 2018-12-18 | 北京镭硼科技有限责任公司 | A kind of graphene film and the preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586868A (en) * | 2012-02-06 | 2012-07-18 | 中国科学院金属研究所 | Preparation method of large-size single-crystal graphene and continuous thin film thereof |
| CN103303910A (en) * | 2013-06-06 | 2013-09-18 | 中国科学技术大学 | Method for preparing graphene and graphene prepared thereby |
-
2017
- 2017-01-11 CN CN201710018061.4A patent/CN106587030B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586868A (en) * | 2012-02-06 | 2012-07-18 | 中国科学院金属研究所 | Preparation method of large-size single-crystal graphene and continuous thin film thereof |
| CN103303910A (en) * | 2013-06-06 | 2013-09-18 | 中国科学技术大学 | Method for preparing graphene and graphene prepared thereby |
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| CN107217239A (en) * | 2017-06-14 | 2017-09-29 | 华南理工大学 | It is a kind of to improve the method for graphene film electric conductivity prepared by aumospheric pressure cvd method |
| CN108220912A (en) * | 2018-01-17 | 2018-06-29 | 南昌航空大学 | It is a kind of it is Ni-based on prepare the method for hydrophilic graphene film |
| CN108614313A (en) * | 2018-05-09 | 2018-10-02 | 中国科学院长春光学精密机械与物理研究所 | The adjustable method for reducing optical surface reflectivity |
| CN108502873A (en) * | 2018-06-26 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of high quality, less defect, the preparation method of the uniform graphene of structure |
| CN108502873B (en) * | 2018-06-26 | 2021-06-29 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Preparation method of high-quality graphene with few defects and uniform structure |
| CN110745815A (en) * | 2018-07-24 | 2020-02-04 | 南开大学 | Method for preparing graphene-metal composite wire |
| CN110745815B (en) * | 2018-07-24 | 2022-08-16 | 南开大学 | Method for preparing graphene-metal composite wire |
| CN109023291A (en) * | 2018-08-14 | 2018-12-18 | 北京镭硼科技有限责任公司 | A kind of graphene film and the preparation method and application thereof |
| CN109378443A (en) * | 2018-10-01 | 2019-02-22 | 河北工程大学 | A kind of manufacturing method of composite graphite alkene lithium ion battery and composite graphite alkene electrode |
| CN113365726A (en) * | 2019-02-01 | 2021-09-07 | 比勒陀利亚大学 | Graphene cotton and its manufacture |
| CN113365726B (en) * | 2019-02-01 | 2024-01-05 | 比勒陀利亚大学 | Graphene cotton and its production |
| CN109850878A (en) * | 2019-04-02 | 2019-06-07 | 华南理工大学 | A kind of graphene and preparation method thereof |
| CN110203912A (en) * | 2019-07-17 | 2019-09-06 | 西北有色金属研究院 | A kind of method that low molten carbon material surface ties up preparation two-dimensional graphene film layer surely |
| CN110775965A (en) * | 2019-12-02 | 2020-02-11 | 江苏龙汇纳米科技有限公司 | Chemical vapor deposition process for preparing high-molecular nano composite material |
| CN112126928A (en) * | 2020-09-10 | 2020-12-25 | 安徽德诠新材料科技有限公司 | Method for preparing heat pipe by vapor deposition |
| CN112126928B (en) * | 2020-09-10 | 2023-06-02 | 安徽德诠新材料科技有限公司 | Method for preparing heat pipe by vapor deposition |
| CN112919455A (en) * | 2021-02-07 | 2021-06-08 | 正大能源材料(大连)有限公司 | Method for preparing graphene film by carbon dioxide combined with low-pressure chemical vapor deposition |
| CN112919455B (en) * | 2021-02-07 | 2022-11-01 | 正大能源材料(大连)有限公司 | Method for preparing graphene film by carbon dioxide combined low-pressure chemical vapor deposition |
| CN114539974A (en) * | 2022-02-21 | 2022-05-27 | 厦门大学 | Method for preparing magnetic metal @ graphene wave-absorbing material based on chemical vapor deposition method |
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