CN114506843B - Method for rapidly preparing graphene film on nonmetallic substrate - Google Patents
Method for rapidly preparing graphene film on nonmetallic substrate Download PDFInfo
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- CN114506843B CN114506843B CN202210175355.9A CN202210175355A CN114506843B CN 114506843 B CN114506843 B CN 114506843B CN 202210175355 A CN202210175355 A CN 202210175355A CN 114506843 B CN114506843 B CN 114506843B
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for rapidly preparing a graphene film on a nonmetallic substrate, which comprises the following steps: step (1): covering a nonmetallic substrate on two sides of a conductive material with the surface coated with a carbon source organic reagent to form a nonmetallic substrate/carbon source organic reagent/conductive material/carbon source organic reagent/nonmetallic substrate interlayer; step (2): and (3) placing the interlayer obtained in the step (1) in an electrode discharge chamber, and performing discharge treatment on the interlayer in a vacuum state. According to the invention, the graphene film can be grown on the nonmetallic substrate in a short time by utilizing the fact that high current is instantaneously passed through the graphene paper to generate high temperature (2000 ℃), so that the problems of long time, high cost and the like in the existing graphene film preparation process are effectively solved.
Description
Technical Field
The invention relates to the technical field of graphene film preparation, in particular to a method for rapidly preparing a graphene film on a nonmetallic substrate.
Background
Graphene is a material composed of carbon atoms and sp 2 The two-dimensional carbon nanomaterial with the hexagonal lattice formed by the hybridized orbits has excellent performances such as extremely high mechanical strength and ultra-high carrier mobility, and is considered to have wide application prospects in various fields.
The existing large-area graphene film is mainly prepared on a copper substrate by a chemical vapor deposition method, and is generally required to be transferred to a target substrate (generally a non-metal substrate such as a silicon wafer, glass, an acrylic plate and the like) during application, so that the transfer process not only increases the preparation cost, but also is easy to damage the graphene film and introduces impurities. Another approach is to grow directly on nonmetallic substrates, typically also by chemical vapor deposition, but typically requires higher temperatures (> 1000 degrees celsius), long growth times (tens of minutes to hours), and higher defects.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a method for rapidly preparing a graphene film on a nonmetallic substrate, which utilizes high current to instantaneously pass through graphene paper to generate high temperature (2000 ℃), can grow the graphene film on the nonmetallic substrate in a short time, and effectively solves the problems of long time, high cost and the like in the existing graphene film preparation process.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a method for rapidly preparing a graphene film on a nonmetallic substrate, which comprises the following steps:
step (1): covering a nonmetallic substrate on two sides of a conductive material with the surface coated with a carbon source organic reagent to form a nonmetallic substrate/carbon source organic reagent/conductive material/carbon source organic reagent/nonmetallic substrate interlayer;
step (2): and (3) placing the interlayer obtained in the step (1) in an electrode discharge chamber, and performing discharge treatment on the interlayer in a vacuum state.
The principle of the method for preparing the graphene film on the nonmetallic substrate is as follows: coating an organic reagent serving as a carbon source on two sides of a conductive material, and then covering the two sides of the conductive material coated with the organic reagent with a nonmetallic substrate to form a sandwich structure (nonmetallic substrate/carbon source organic reagent/conductive material/carbon source organic reagent/nonmetallic substrate sandwich); and then placing the sandwich structure (nonmetallic substrate/carbon source organic reagent/conductive material/carbon source organic reagent/nonmetallic substrate sandwich) in an electrode discharge chamber, performing discharge treatment on the sandwich in a vacuum state, and in the short-time high-voltage discharge treatment process, generating a large amount of Joule heat which can thermally crack the carbon source into carbon active species, and rapidly completing recombination on the nonmetallic substrates on the two sides to obtain graphene. For example, two ends of a conductive material such as graphite paper are connected with electrodes, organic reagents such as n-hexane (or ethanol, acetone, etc.) are coated on two sides of the graphite paper, then the two sides are clamped by a non-metal substrate (such as quartz plate, glass, etc.), then the graphite paper is heated by current, the temperature is regulated by the current, and the reaction time is regulated by the current-on time, so that the graphene film is rapidly prepared on the non-metal substrate.
Further, the carbon source organic reagent is any liquid organic reagent containing carbon; the graphene may be doped by a liquid organic reagent containing no sulfur or nitrogen, such as N-hexane, ethanol, or acetone, or a liquid organic reagent containing sulfur or nitrogen, such as acetonitrile, N-dimethylformamide, dimethylsulfoxide, pyridine, or carbon disulfide, or a polymer such as polyethylene glycol.
Further, nonmetallic substrates include, but are not limited to, silicon wafers, quartz wafers, boron nitride, glass, aluminum oxide, silicon wafers with silica coatings, mica wafers, sapphire, and the like.
Further, the conductive material includes, but is not limited to, graphene felt, carbon fiber cloth, metal foil such as gold, silver, copper, platinum, tungsten, iron, chromium, cobalt, nickel, and the like.
Further, the working parameters of the electrode discharge chamber are as follows: the voltage is 180-250V, preferably 200-220V; the discharge duration is 300-1000ms, preferably 300-600ms.
In the invention, the reaction temperature is regulated by the voltage and the discharge time together, the higher the voltage is, the shorter the discharge time is, the larger the heat obtained by the reaction system is, and the higher the quality of the graphene obtained on the nonmetallic substrate is; the reaction time is regulated by the power-on time.
Further, the electrode discharge chamber is at least connected with a power supply anode, a power supply cathode, a vacuum device and a controller, and the power supply anode and the power supply cathode are connected with two ends of the graphite paper to realize the current heating of the graphite paper; the vacuum device can be a device such as a vacuum pump and the like for vacuumizing the electrode discharge chamber; the controller can adopt a relay matched controller, thereby realizing the control of discharge working parameters. For example, the electrode discharge chamber can be modified by a plastic vacuum drying oven (three holes are formed for connecting the positive electrode, the negative electrode and a vacuum pump of a power supply respectively; a vacuum meter is arranged at the top of the cover, and vacuumizing treatment is carried out before each reaction).
Further, before the interlayer in the step (2) is subjected to discharge treatment, the method further comprises: the reaction chamber is vacuumized, and the sample is pretreated in 300-1000ms under 130-150V voltage.
The pretreatment step is mainly used for carbon source reagents with weak volatility such as esters (e.g. methyl benzoate and the like).
In summary, the invention has the following advantages:
1) The invention provides a method for rapidly preparing a graphene film on a nonmetallic substrate, which utilizes high current to instantaneously pass through graphene paper to generate high temperature (2000 ℃), can grow the graphene film on the nonmetallic substrate in a short time, and effectively solves the problems of long time, high cost and the like in the existing graphene film preparation process.
2) Compared with the method for preparing the graphene film by adopting the conventional chemical vapor deposition reaction chamber, the method has the following advantages: 1. the device is simple and has low cost; 2. the reaction position is directly heated, so that the energy utilization rate is high; 3. the temperature is high (> 2000 ℃) and the high-quality graphene film can be obtained.
Drawings
FIG. 1 is a schematic diagram of a sandwich structure according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
Thus, the following detailed description of the embodiments of the invention, as provided, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
Example 1
The example provides a method for rapidly preparing a graphene film on a nonmetallic substrate, as shown in fig. 1, comprising the following steps:
(1) Preparation of a reaction system: taking graphite paper with the length of 10cm and the width of 6cm, and respectively spin-coating 10ml of n-hexane on two sides of the graphite paper; then, respectively covering the two sides by using quartz plates (length 5cm and width 2 cm), and clamping the quartz plates on the two sides by using crocodile clips for fixing to obtain an interlayer of a nonmetallic substrate/a carbon source organic reagent/a conductive material/a carbon source organic reagent/a nonmetallic substrate, a quartz plate/n-hexane/graphite paper/n-hexane/a quartz plate;
(2) Preparation of graphene film: placing the interlayer of the quartz plate/n-hexane/graphite paper/n-hexane/quartz plate in a reaction chamber, and closing the reaction chamber after the two ends of the graphite paper are respectively connected with the positive and negative poles of a power supply; after the reaction chamber is vacuumized, the interlayer is subjected to discharge treatment under the discharge condition of 220V and 300ms through a controller; and when the voltage of the reaction chamber is 0V, opening the reaction chamber, and taking out the quartz plate substrate, so that the graphene can be obtained on the quartz plate substrate.
The graphene film obtained by the method has the characteristics of no defect structure, good appearance and excellent electrical property.
It should be noted that, the present embodiment is only used for illustrating and explaining the technical scheme and technical concept of the present invention, and is not used for limiting the present invention; of particular note, the carbon source organic reagent in this example is any liquid organic reagent; if N-hexane is replaced by a liquid organic reagent containing no sulfur or no nitrogen such as ethanol, acetone and the like or a polymer such as polyethylene glycol and the like, the liquid organic reagent containing sulfur or nitrogen such as acetonitrile, N-dimethylformamide, dimethyl sulfoxide, pyridine, carbon disulfide and the like can be replaced by a liquid organic reagent containing sulfur or nitrogen and the like, so that the graphene is doped; the quartz plate in this example can be replaced by other conventional nonmetallic substrates such as silicon wafers, boron nitride, glass, alumina, silicon wafers with silicon dioxide coatings, mica plates, sapphire, and the like. In the embodiment, the graphite paper can be replaced by other conductive materials such as graphene felt, carbon fiber cloth, metal foils such as gold, silver, copper, platinum, tungsten, iron, chromium, cobalt, nickel and the like; the graphene film with a defect-free structure and excellent morphology and electrical properties can be successfully prepared, and the invention is not repeated.
Example 2
The present example provides a method for rapidly preparing graphene thin films on a nonmetallic substrate, which differs from example 1 only in that: the working parameters of the electrode discharge chamber are as follows: the voltage is 180V, and the discharge time is 900ms; the rest steps and parameters are the same.
Example 3
The present example provides a method for rapidly preparing graphene thin films on a nonmetallic substrate, which differs from example 1 only in that: the working parameters of the electrode discharge chamber are as follows: the voltage is 200V, and the discharge time is 400ms; the rest steps and parameters are the same.
Example 4
The present example provides a method for rapidly preparing graphene thin films on a nonmetallic substrate, which differs from example 1 only in that: the carbon source reagent is regulated to be methyl benzoate; before the sandwich structure is subjected to discharge treatment, the method further comprises the following steps: the reaction chamber is vacuumized, and the sample is preprocessed in 500ms under 140V voltage; the rest steps and parameters are the same.
The foregoing is merely illustrative and explanatory of the invention as it is claimed, as modifications and additions may be made to, or similar to, the particular embodiments described, without the benefit of the inventors' inventive effort, and as alternatives to those of skill in the art, which remain within the scope of this patent.
Claims (4)
1. The method for rapidly preparing the graphene film on the nonmetallic substrate is characterized by comprising the following steps of:
step (1): covering a nonmetallic substrate on two sides of a conductive material with the surface coated with a carbon source organic reagent to form a nonmetallic substrate/carbon source organic reagent/conductive material/carbon source organic reagent/nonmetallic substrate interlayer; the conductive material comprises at least one of graphene felt and carbon fiber cloth;
step (2): placing the interlayer obtained in the step (1) in an electrode discharge chamber, and performing discharge treatment on the interlayer in a vacuum state; the working parameters of the electrode discharge chamber are as follows: the voltage is 180-250V, and the discharge time is 300-1000ms.
2. The method for rapidly preparing graphene thin films on a nonmetallic substrate according to claim 1, wherein the carbon source organic reagent is a carbon-containing liquid organic reagent.
3. The method for rapidly preparing a graphene film on a non-metallic substrate according to claim 1, wherein the non-metallic substrate comprises at least one of a silicon wafer, a quartz plate, boron nitride, glass, alumina, a silicon wafer with a silicon dioxide coating, a mica plate, and sapphire.
4. The method for rapidly preparing graphene film on a nonmetallic substrate according to claim 1, wherein before the interlayer is subjected to discharge treatment in the step (2), the method further comprises: the reaction chamber is vacuumized, and the sample is pretreated in 300-1000ms under 130-150V voltage.
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| WO2015149116A1 (en) * | 2014-04-04 | 2015-10-08 | Commonwealth Scientific And Industrial Research Organisation | Graphene process and product |
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| WO2012148439A1 (en) * | 2011-04-25 | 2012-11-01 | William Marsh Rice University | Direct growth of graphene films on non-catalyst surfaces |
| CN102719877B (en) * | 2011-06-09 | 2014-09-03 | 中国科学院金属研究所 | Low-cost lossless transfer method of graphene |
| CN102306781A (en) * | 2011-09-05 | 2012-01-04 | 中国科学院金属研究所 | Doped graphene electrode material, macro preparation method and application of doped graphene electrode material |
| GB2498944B (en) * | 2012-01-31 | 2016-01-06 | Univ Leiden | Thin film formation |
| JP2013177659A (en) * | 2012-02-29 | 2013-09-09 | Nagoya Institute Of Technology | Method for manufacturing graphene structure |
| JP6097908B2 (en) * | 2012-05-25 | 2017-03-22 | 国立研究開発法人物質・材料研究機構 | Process for producing exfoliated graphene film |
| CN103449423B (en) * | 2013-08-27 | 2016-03-16 | 常州第六元素材料科技股份有限公司 | A kind of Graphene heat conducting film and preparation method thereof |
| CN103663437B (en) * | 2014-01-10 | 2016-01-06 | 青岛华高能源科技有限公司 | Magnetron sputtering technique is utilized to prepare graphene quantum dot |
| US20150221408A1 (en) * | 2014-02-04 | 2015-08-06 | Samsung Sdi Co., Ltd. | Graphene based hybrid thin films and their applications |
| CN106132872A (en) * | 2014-03-28 | 2016-11-16 | 曼彻斯特大学 | The graphene oxide barrier material of reduction |
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| CN111170317B (en) * | 2018-11-12 | 2022-02-22 | 有研工程技术研究院有限公司 | Preparation method of graphene modified diamond/copper composite material |
| CN112267040A (en) * | 2020-10-20 | 2021-01-26 | 南昌航空大学 | Preparation method of graphene-carbon nanotube/copper-based composite material |
| CN112725660A (en) * | 2020-12-21 | 2021-04-30 | 上海交通大学 | Powder metallurgy preparation method of graphene reinforced aluminum-based composite material |
| CN112875754B (en) * | 2021-01-19 | 2021-12-03 | 北京科技大学 | Preparation and application method of graphene intercalation molybdenum disulfide composite material |
| CN112838201A (en) * | 2021-04-06 | 2021-05-25 | 湖南镕锂新材料科技有限公司 | Cu2MoS4Composite negative electrode material, preparation method thereof and sodium ion battery |
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