CN114940491A - Low-cost and large-scale preparation method of wrinkle-free graphene - Google Patents
Low-cost and large-scale preparation method of wrinkle-free graphene Download PDFInfo
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- CN114940491A CN114940491A CN202210376336.2A CN202210376336A CN114940491A CN 114940491 A CN114940491 A CN 114940491A CN 202210376336 A CN202210376336 A CN 202210376336A CN 114940491 A CN114940491 A CN 114940491A
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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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
- C01B2204/22—Electronic 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
- C01B2204/24—Thermal properties
Abstract
The invention belongs to the technical field of graphene preparation, and particularly relates to a low-cost large-scale preparation method of wrinkle-free graphene. The preparation method comprises the following steps: 1) introducing protective atmosphere into the chemical vapor deposition reaction furnace until no impurity gas exists in the furnace; 2) heating the furnace to 700-900 ℃, introducing a carbon source into the furnace, and reacting for 10-20 min; 3) turning off the power supply, and cooling to room temperature; 4) and taking out the sample to obtain the wrinkle-free graphene. Compared with the conventional method for preparing the wrinkle-free graphene on the metal matrix such as the copper foil, the preparation method has the advantages of simple process, stable performance, independence on the metal growth matrix and the like, and is suitable for low-cost and large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to a low-cost large-scale preparation method of wrinkle-free graphene.
Background
Due to the two-dimensional hexagonal grid structure of the graphene, the graphene has excellent optical, electrical, magnetic and catalytic properties. The low-cost and large-scale preparation of the graphene is a key factor for promoting the industrial application of the graphene in the fields of electricity, magnetism, catalysis and the like. Compared with methods such as a mechanical stripping method and a chemical stripping method, the chemical vapor deposition method using the copper foil as the matrix has the advantages of high graphene growth quality, large growth area and the like, is the most promising process method for realizing low-cost and large-scale preparation of graphene, but the wrinkle defect is still a main problem faced by the graphene chemical vapor deposition method.
The wrinkles are caused by the different thermal expansion coefficients of graphene and copper foil. Graphene has a negative coefficient of thermal expansion, while copper has a positive coefficient of thermal expansion. Therefore, in the temperature reduction process of the chemical vapor deposition reaction, the volume deformation of the graphene and the volume deformation of the copper foil are different, and the wrinkle defect is formed on the surface of the graphene. Researches show that the wrinkle defects can reduce the electron mobility and the thermal conductivity of the graphene and influence the vibration of lattice phonons and the like. In a word, the fold defects have a great influence on optical, electrical, magnetic and other properties of the graphene. The method for regulating and controlling the crystal structure orientation of the copper foil and obtaining the low-crystal-plane-index growth matrix is a common way for eliminating the wrinkle defect of the graphene at present, but the method cannot solve the problem of the difference of the thermal expansion coefficients between the graphene and the copper foil and other metal growth matrixes.
Disclosure of Invention
The invention aims to provide a chemical vapor reaction method which does not adopt a metal growth matrix, thoroughly eliminates the difference of thermal expansion coefficients between graphene and the metal growth matrix and realizes the low-cost large-scale preparation of fold-free graphene. The wrinkle-free graphene is prepared by a chemical vapor phase method through a gas/liquid interface of the chemical vapor phase method under the condition of not using a growth substrate.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of wrinkle-free graphene, which comprises the following steps:
1) introducing protective atmosphere into the chemical vapor deposition reaction furnace until no impurity gas exists in the furnace;
2) raising the temperature of the furnace to 700-900 ℃, introducing a carbon source into the furnace, and reacting for 10-20 min;
3) turning off the power supply, and cooling to room temperature;
4) and taking out the sample to obtain the wrinkle-free graphene.
In the above technical solution, further, the protective atmosphere in step 1) is nitrogen or argon.
In the above technical solution, further, the carbon source in step 2) includes any one of ethanol, methane, or camphor.
In the above technical scheme, further, the temperature rise rate in the step 2) is 20-30 ℃/min.
In the above technical scheme, further, the cooling rate in the step 3) is 2-3 ℃/min.
The invention also provides graphene prepared by the preparation method.
According to the invention, by a chemical vapor phase method, factors such as a reaction precursor, a cooling speed, a reaction atmosphere and the like are regulated and controlled without using a growth matrix, a carbon source reacts to form a carbon atom six-membered ring, and the carbon atom six-membered ring is connected and grown to form a two-dimensional hexagonal grid structure of graphene.
The invention has the beneficial effects that:
compared with the conventional method for preparing the wrinkle-free graphene on the metal matrix such as the copper foil, the preparation method provided by the invention has the advantages of simple process, stable performance, independence on a metal growth matrix and the like, and is suitable for low-cost and large-scale industrial production.
The preparation method can realize low-cost and large-scale preparation of high-quality and large-area wrinkle-free graphene, and provides a high-quality graphene material for the fields of optics, electrics, magnetics, catalysis and the like.
Drawings
Fig. 1 is a macroscopic photograph of graphene prepared in example 1;
FIG. 2 is a transmission electron micrograph of graphene obtained in example 1, wherein a is an enlargement by 5 ten thousand times and b is an enlargement by 30 ten thousand times;
FIG. 3 is a transmission electron micrograph of graphene obtained in example 2, wherein a is magnified 3 ten thousand times and b is magnified 5 ten thousand times;
FIG. 4 is a transmission electron micrograph of graphene obtained in example 3, wherein a is magnified 3 ten thousand times and b is magnified 5 ten thousand times;
FIG. 5 is a comparison of the conductivity properties of graphene for the samples prepared in examples 1-3 with a reference sample;
FIG. 6 is a comparison of the thermal conductivity of graphene for the samples prepared in examples 1-3 and the reference sample.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
(1) Selecting ethanol as a carbon source;
(2) introducing argon protective gas into the chemical vapor deposition reaction furnace to complete cleaning of the cavity until no impurity gas exists in the furnace;
(3) heating the furnace to 750 ℃, introducing an ethanol carbon source into the furnace, and reacting for 15 min;
(4) turning off a power supply, and cooling the furnace temperature to room temperature at a cooling speed of 2 ℃/min under the argon protective atmosphere;
(5) and taking out the sample to obtain the wrinkle-free graphene.
The graphene prepared in example 1 is subjected to electric conduction and heat conduction performance tests, and the result shows that the wrinkle-free graphene obtained in example 1 has the resistivity of 633 omega cm -2 Lower than 983 omega cm of graphene reported in literature -2 (ii) a The thermal conductivity of the wrinkle-free graphene obtained in example 1 is 1125 W.m -1 K -1 850 W.m higher than that of graphene reported in the literature -1 K -1 。
Example 2
(1) Selecting camphor as a carbon source;
(2) placing camphor in a quartz boat, placing the quartz boat in a chemical vapor reaction furnace, introducing argon protective gas into the chemical vapor deposition reaction furnace, and finishing cleaning a cavity until no impurity gas exists in the furnace;
(3) the temperature of the furnace is raised to 850 ℃ and the reaction lasts 20 min;
(4) turning off a power supply, and cooling the furnace temperature to room temperature at a cooling speed of 3 ℃/min under the argon protective atmosphere;
(5) and taking out the sample to obtain the wrinkle-free graphene.
The graphene prepared in example 2 is subjected to electric conduction and heat conduction performance tests, and the result shows that the wrinkle-free graphene obtained in example 2 has the resistivity of 618 omega cm -2 Lower than 983 omega cm reported in literature for graphene -2 (ii) a The thermal conductivity of the wrinkle-free graphene obtained in example 1 was 1086W · m -1 K -1 850 W.m higher than the graphene reported in the literature -1 K -1 。
Example 3
(1) Selecting methane as a carbon source;
(2) introducing nitrogen protective gas into the chemical vapor deposition reaction furnace to complete cleaning of the cavity until no impurity gas exists in the furnace;
(3) raising the furnace temperature to 800 ℃, introducing a methane carbon source into the furnace, and reacting for 15 min;
(4) turning off a power supply, and cooling the furnace temperature to room temperature at a cooling speed of 3 ℃/min under the nitrogen protective atmosphere;
(5) and taking out the sample to obtain the wrinkle-free graphene.
The graphene prepared in example 3 is subjected to electric conduction and heat conduction performance tests, and the result shows that the wrinkle-free graphene obtained in example 1 has the resistivity of 597 omega cm -2 Lower than 983 omega cm of graphene reported in literature -2 (ii) a The thermal conductivity of the wrinkle-free graphene obtained in example 1 was 1012 W.m -1 K -1 850 W.m higher than the graphene reported in the literature -1 K -1 。
The above examples are merely preferred embodiments of the present invention, and are not intended to limit the embodiments. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations and modifications may be made on the basis of the above description. Obvious variations or modifications of this invention are within the scope of the invention.
Claims (6)
1. A preparation method of wrinkle-free graphene is characterized by comprising the following steps: the preparation method comprises the following steps:
1) introducing protective atmosphere into the chemical vapor deposition reaction furnace until no impurity gas exists in the furnace;
2) heating the furnace to 700-900 ℃, introducing a carbon source into the furnace, and reacting for 10-20 min;
3) turning off the power supply, and cooling to room temperature;
4) and taking out the sample to obtain the wrinkle-free graphene.
2. The method of claim 1, wherein: the protective atmosphere in the step 1) is nitrogen or argon.
3. The method of claim 1, wherein: the carbon source in the step 2) comprises any one of ethanol, methane or camphor.
4. The method of claim 1, wherein: the temperature rise rate in the step 2) is 20-30 ℃/min.
5. The method of claim 1, wherein: and the cooling rate in the step 3) is 2-3 ℃/min.
6. Graphene prepared by the preparation method of any one of claims 1 to 5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100301212A1 (en) * | 2009-05-18 | 2010-12-02 | The Regents Of The University Of California | Substrate-free gas-phase synthesis of graphene sheets |
| CN105819429A (en) * | 2016-03-10 | 2016-08-03 | 北京大学 | Preparation method of wrinkle-free graphene |
| CN109437169A (en) * | 2018-12-04 | 2019-03-08 | 中国电子科技集团公司第十三研究所 | The method for preparing ultralow corrugation density grapheme material |
| CN110282617A (en) * | 2019-07-26 | 2019-09-27 | 北京石墨烯研究院 | A kind of graphene powder and preparation method thereof |
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- 2022-04-11 CN CN202210376336.2A patent/CN114940491A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100301212A1 (en) * | 2009-05-18 | 2010-12-02 | The Regents Of The University Of California | Substrate-free gas-phase synthesis of graphene sheets |
| CN105819429A (en) * | 2016-03-10 | 2016-08-03 | 北京大学 | Preparation method of wrinkle-free graphene |
| CN109437169A (en) * | 2018-12-04 | 2019-03-08 | 中国电子科技集团公司第十三研究所 | The method for preparing ultralow corrugation density grapheme material |
| CN110282617A (en) * | 2019-07-26 | 2019-09-27 | 北京石墨烯研究院 | A kind of graphene powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| DATO ALBERT WT AL. * |
| 石晓东;王伟;尹强;李春静;: "化学气相沉积制备大面积高质量石墨烯的研究进展" * |
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