阅读说明：本技术 金属表面具有多相复合碳源的石墨烯制备方法及装置 (Method and device for preparing graphene with multiphase composite carbon source on metal surface ) 是由 刘悦 姚松松 杨昆明 范同祥 于 2021-08-31 设计创作，主要内容包括：本发明提供一种金属表面具有多相复合碳源的石墨烯制备方法及装置,所述制备方法包括如下步骤：提供固态有机碳源、液态有机碳源及气态有机碳源中的至少一种,形成碳源混合物；加热,使所述碳源混合物裂解为气态活性含碳基团；将所述气态活性含碳基团通入反应腔内,所述反应腔内放置有金属基底,在生长温度及生长压力下,所述气态活性含碳基团沉积在所述金属基底上,形成石墨烯层,以形成石墨烯金属复合结构。本发明制备方法先使碳源高温裂解,从而不需要金属基底对所述碳源进行催化,扩大了所述金属基底材料的可选范围,使得所述金属基底可为对碳源具有催化作用的材料也可为对碳源不具备催化作用的材料。(The invention provides a method and a device for preparing graphene with a multiphase composite carbon source on a metal surface, wherein the preparation method comprises the following steps: providing at least one of a solid organic carbon source, a liquid organic carbon source and a gaseous organic carbon source to form a carbon source mixture; heating to crack the carbon source mixture into gaseous active carbon-containing radicals; and introducing the gaseous active carbon-containing group into a reaction cavity, placing a metal substrate in the reaction cavity, and depositing the gaseous active carbon-containing group on the metal substrate at a growth temperature and a growth pressure to form a graphene layer so as to form a graphene metal composite structure. According to the preparation method, the carbon source is cracked at high temperature, so that the metal substrate is not required to catalyze the carbon source, the optional range of the metal substrate material is expanded, and the metal substrate can be a material with a catalytic effect on the carbon source and can also be a material without the catalytic effect on the carbon source.)

1. A preparation method of graphene with a multiphase composite carbon source on a metal surface is characterized by comprising the following steps:

providing at least one of a solid organic carbon source, a liquid organic carbon source and a gaseous organic carbon source to form a carbon source mixture;

heating to crack the carbon source mixture into gaseous active carbon-containing radicals;

and introducing the gaseous active carbon-containing group into a reaction cavity, placing a metal substrate in the reaction cavity, and depositing the gaseous active carbon-containing group on the metal substrate at a growth temperature and a growth pressure to form a graphene layer so as to form a graphene metal composite structure.

2. The method according to claim 1, wherein the step of providing at least one of a solid organic carbon source, a liquid organic carbon source and a gaseous organic carbon source to form a carbon source mixture comprises:

providing a solid organic carbon source and a liquid organic carbon source, and mixing the solid organic carbon source and the liquid organic carbon source according to a preset mass ratio to form a solid-liquid mixture;

and introducing a gaseous organic carbon source into the solid-liquid mixture to form the carbon source mixture.

3. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 2, wherein the preset mass ratio of the solid-liquid mixture is 0.01-30%.

4. The method of claim 2, wherein the solid-liquid mixture is passed into a vessel at a first flow rate and the gaseous organic carbon source is passed into the vessel at a second flow rate to form the carbon source mixture.

5. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 4, wherein the first flow rate is 0.0005 to 20ml/min, and the second flow rate is 0.1 to 500 sccm.

6. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein the solid organic carbon source, the liquid organic carbon source and the gaseous organic carbon source are hydrocarbons and derivatives thereof.

7. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein the solid organic carbon source is one or more selected from glucose, polycyclic aromatic hydrocarbon, PMMA, PEG, paraffin and stearic acid.

8. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein the liquid organic carbon source is selected from one or more of methanol, ethanol, anisole, benzene and chlorobenzene.

9. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein the gaseous organic carbon source is selected from CH₄、C₂H₆、C₂H₄、C₂H₂One or more of them.

10. The method according to claim 1, wherein the step of heating to crack the carbon source mixture into gaseous active carbon-containing groups is performed at a temperature of 25 to 1100 ℃ and a pressure of 0.005 to 780 Torr.

11. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein in the step of introducing the gaseous active carbon-containing groups into the reaction chamber, the flow rate of the gaseous active carbon-containing groups is 0.1-500 sccm.

12. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein before the step of introducing the gaseous active carbon-containing groups into the reaction chamber, a protective gas and a reducing gas are introduced into the reaction chamber to pretreat the metal substrate.

13. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 11, wherein the pretreatment temperature is 100-1000 ℃, the pressure is 0.05-500Torr, and the time is 1-100 min.

14. The method according to claim 11, wherein the temperature is adjusted to a growth temperature and a growth pressure after the pretreatment, the gaseous active carbon-containing groups are deposited on the metal substrate to form the graphene layer, and the graphene layer is formed on the metal surfaceGrowth ofThe temperature is 25-1100 ℃, and the growth pressure is 0.05780Torr, and the growth time is 1-100 min.

15. The method for preparing graphene with the multiphase composite carbon source on the metal surface according to claim 1, wherein the graphene metal composite structure is cooled after the step of depositing the gaseous active carbon-containing groups on the metal substrate at a growth temperature and a growth pressure to form a graphene layer so as to form the graphene metal composite structure, and the cooling rate is 5-40 ℃ per minute.

16. A graphene composite structure with a multiphase composite carbon source on a metal surface is characterized by comprising:

a metal substrate which does not have a catalytic effect on the cracking of a carbon source;

a graphene layer deposited on the metal substrate.

17. The graphene composite structure with the multiphase composite carbon source on the metal surface as claimed in claim 16, wherein the coverage rate of the graphene layer is greater than 98%.

18. The graphene composite structure with the multiphase composite carbon source on the metal surface as claimed in claim 16, wherein the thickness of the graphene layer is 1-200 nm.

19. An apparatus for the preparation of a graphene metal composite structure, the apparatus comprising: a carbon source mixing vessel for mixing at least one of a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source to form a carbon source mixture, and capable of being used for heating to crack the carbon source mixture into gaseous reactive carbon-containing radicals;

and the reaction cavity is communicated with the carbon source mixing container and is used for receiving the gaseous active carbon-containing groups, a metal substrate can be placed in the reaction cavity, and the gaseous active carbon-containing groups are deposited on the metal substrate at the growth temperature and the growth pressure to form a graphene layer so as to form a graphene metal composite structure.

20. The apparatus of claim 19, wherein the carbon source mixing vessel further comprises:

a solid-liquid mixing device for mixing the solid organic carbon source and the liquid organic carbon source to form a solid-liquid mixture;

a gaseous organic carbon source supply device for supplying a gaseous organic carbon source;

and one end of the multiphase carbon source mixing tank is communicated with the solid-liquid mixing device and the gaseous organic carbon source supply device and is used for receiving the solid-liquid mixture and the gaseous organic carbon source to form a carbon source mixture, and the other end of the multiphase carbon source mixing tank is communicated with the reaction cavity and is used for providing gaseous active carbon-containing radicals into the reaction cavity, and the multiphase carbon source mixing tank can be heated so as to crack the carbon source mixture into the gaseous active carbon-containing radicals.

21. The apparatus of claim 20, wherein the multi-phase carbon source mixing tank comprises a heating chamber and a pyrolysis chamber disposed in the heating chamber, wherein the inner wall of the pyrolysis chamber has a spiral configuration, and the pyrolysis chamber is communicated with the solid-liquid mixing device and the gaseous organic carbon source supply device, and the other end of the pyrolysis chamber is communicated with the reaction chamber.

Technical Field

The invention relates to the field of composite material preparation, in particular to a method and a device for preparing graphene with a multiphase composite carbon source on a metal surface.

Background

Graphene (Gr) has been the focus of research in various fields due to its excellent mechanical and electrical conductivity properties. However, graphene layers are thick at the nanometer size, making their preparation difficult, which greatly limits the applications of graphene. At present, the methods for industrially preparing graphene mainly comprise: (1) a mechanical peeling method; (2) epitaxial growth method; (3) a redox process; (4) chemical vapor deposition, and the like. The chemical vapor deposition method is the most suitable scheme for mass industrial application at present by virtue of the characteristics of high film-forming quality, controllable thickness, simple process, large-scale production and the like. However, the current chemical vapor deposition methods also have problems that limit the industrial large-scale application of the methods.

The traditional chemical vapor deposition method for preparing graphene usually adopts gas as a carbon source, heats a substrate material to 800-.

The traditional chemical vapor deposition method for preparing graphene mainly has the following problems: (1) graphene preparation is slow. The process generally needs 30-60 minutes to prepare the graphene film with the coverage rate of more than 98%; (2) the preparation temperature of the graphene is high. The preparation temperature is generally 800-; (3) graphene can only be prepared on the surface of a substrate material having a catalytic effect on the decomposition of a carbon source. The existing method for preparing graphene cannot meet the requirements of users.

Therefore, a new method for preparing a graphene-metal composite structure is needed to meet the user requirements.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method and a device for preparing graphene with a multiphase composite carbon source on a metal surface, which can expand the range of a metal substrate and improve the performance of a composite structure.

In order to solve the above problems, the present invention provides a method for preparing a graphene metal composite structure, which comprises the following steps: providing at least one of a solid organic carbon source, a liquid organic carbon source and a gaseous organic carbon source to form a carbon source mixture; heating to crack the carbon source mixture into gaseous active carbon-containing radicals; and introducing the gaseous active carbon-containing group into a reaction cavity, placing a metal substrate in the reaction cavity, and depositing the gaseous active carbon-containing group on the metal substrate to form a graphene layer under the growth temperature and growth pressure to form a graphene metal composite structure.

Further, providing at least one of a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source, and forming a carbon source mixture comprises: providing a solid organic carbon source and a liquid organic carbon source, and mixing the solid organic carbon source and the liquid organic carbon source according to a preset mass ratio to form a solid-liquid mixture; and introducing a gaseous organic carbon source into the solid-liquid mixture to form the carbon source mixture.

Further, the preset mass ratio of the solid-liquid mixture is 0.01-30%.

Further, the solid-liquid mixture is passed into a vessel at a first flow rate, and the gaseous organic carbon source is passed into the vessel at a second flow rate to form the carbon source mixture.

Further, the first flow rate is 0.0005 to 20ml/min, and the second flow rate is 0.1 to 500 sccm.

Further, the solid organic carbon source, the liquid organic carbon source and the gaseous organic carbon source are hydrocarbons and derivatives thereof.

Further, the solid organic carbon source is selected from one or more of glucose, polycyclic aromatic hydrocarbon, PMMA, PEG, paraffin and stearic acid.

Further, the liquid organic carbon source is selected from one or more of methanol, ethanol, anisole, benzene and chlorobenzene.

Further, the gaseous organic carbon source is selected from CH₄、C₂H₆、C₂H₄、C₂H₂One or more of them.

Further, in the step of heating to crack the carbon source mixture into gaseous active carbon-containing groups, the heating temperature is 25 to 1100 ℃ and the pressure is 0.005 to 780 Torr.

Further, in the step of introducing the gaseous active carbon-containing groups into the reaction chamber, the flow rate of the gaseous active carbon-containing groups is 0.1-500 sccm.

Further, before the step of introducing the gaseous activated carbon-containing group into the reaction chamber, introducing a protective gas and a reducing gas into the reaction chamber to pretreat the metal substrate.

Further, the temperature of the pretreatment is 100-1000 ℃, the pressure is 0.05-500Torr, and the time is 1-100 min.

Further, after the pretreatment is finished, the temperature is adjusted to the growth temperature and the growth pressure, the gaseous active carbon-containing groups are deposited on the metal substrate to form a graphene layer, the growth temperature is 25-1100 ℃, the growth pressure is 0.05-780Torr, and the growth time is 1-100 min.

Further, under the growth temperature and the growth pressure, the gaseous active carbon-containing groups are deposited on the metal substrate to form a graphene layer, and after the step of forming the graphene metal composite structure, the graphene metal composite structure is cooled at a cooling rate of 5-40 ℃ per minute.

The invention also provides a graphene composite structure with a multiphase composite carbon source on the metal surface, which comprises the following components: a metal substrate which does not have a catalytic effect on the cracking of a carbon source; a graphene layer deposited on the metal substrate.

Further, the coverage rate of the graphene layer is greater than 98%.

Further, the thickness of the graphene layer is 1-200 nm.

The invention also provides a device for preparing the graphene-metal composite structure, which comprises the following components:

a carbon source mixing vessel for mixing at least one of a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source to form a carbon source mixture, and capable of being used for heating to crack the carbon source mixture into gaseous reactive carbon-containing radicals;

and the reaction cavity is communicated with the carbon source mixing container and is used for receiving the gaseous active carbon-containing groups, a metal substrate can be placed in the reaction cavity, and the gaseous active carbon-containing groups are deposited on the metal substrate at the growth temperature and the growth pressure to form a graphene layer so as to form a graphene metal composite structure.

Further, the carbon source mixing container further comprises:

a solid-liquid mixing device for mixing the solid organic carbon source and the liquid organic carbon source to form a solid-liquid mixture;

a gaseous organic carbon source supply device for supplying a gaseous organic carbon source;

and one end of the multiphase carbon source mixing tank is communicated with the solid-liquid mixing device and the gaseous organic carbon source supply device and is used for receiving the solid-liquid mixture and the gaseous organic carbon source to form a carbon source mixture, and the other end of the multiphase carbon source mixing tank is communicated with the reaction cavity and is used for providing gaseous active carbon-containing radicals into the reaction cavity, and the multiphase carbon source mixing tank can be heated so as to crack the carbon source mixture into the gaseous active carbon-containing radicals.

Further, heterogeneous carbon source blending tank includes the heating chamber and arranges in the schizolysis chamber in the heating chamber, schizolysis intracavity wall is the spiral configuration, the schizolysis chamber with solid-liquid mixing arrangement reaches gaseous state organic carbon source supply device intercommunication, the other end with the reaction chamber intercommunication.

The method has the advantages that a solid-liquid-gas multiphase carbon source mixture is adopted, the multiphase carbon source mixture is subjected to pyrolysis before entering a reaction cavity to form gaseous active carbon-containing groups, and the gaseous active carbon-containing groups are deposited on the surface of the metal substrate to form a graphene metal composite structure. According to the preparation method of the graphene metal composite structure, the carbon source is cracked at high temperature, so that the metal substrate is not required to catalyze the carbon source, the optional range of the metal substrate material is expanded, and the metal substrate can be a material with a catalytic effect on the carbon source and can also be a material without a catalytic effect on the carbon source.

Drawings

Fig. 1 is a schematic step diagram of a method for preparing graphene with a multiphase composite carbon source on a metal surface according to an embodiment of the present invention;

fig. 2 is a scanning electron microscope image of the surface of the graphene-metal wire composite structure prepared by the preparation method provided by the embodiment of the invention;

fig. 3 is a scanning electron microscope image of the surface of the graphene metal foil composite structure prepared by the preparation method provided by an embodiment of the invention;

fig. 4 is a transmission electron microscope image of a graphene-metal wire composite structure prepared by the preparation method provided by an embodiment of the invention;

FIG. 5 is a schematic structural diagram of an apparatus for preparing a composite structure with a multiphase composite carbon source on a metal surface according to an embodiment of the present invention.

Detailed Description

The following describes in detail specific embodiments of the method and apparatus for preparing graphene with a multiphase composite carbon source on a metal surface according to the present invention with reference to the accompanying drawings.

Fig. 1 is a schematic step diagram of a method for preparing graphene with a multiphase composite carbon source on a metal surface according to an embodiment of the present invention, and referring to fig. 1, the method for preparing a graphene-metal composite structure according to the present invention includes the following steps:

in step S10, at least one of a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source is provided to form a carbon source mixture.

In this embodiment, three carbon sources, a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source, are provided to form a multi-phase carbon source mixture, while in other embodiments of the invention, one or both of a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source may be provided to form a carbon source mixture.

Wherein the solid organic carbon source, the liquid organic carbon source and the gaseous organic carbon source are hydrocarbons and derivatives thereof. In the present embodiment, the solid organic carbon source is selected from one or more of glucose, polycyclic aromatic hydrocarbon, PMMA, PEG, paraffin, and stearic acid; the liquid organic carbon source is selected from one or more of methanol, ethanol, anisole, benzene and chlorobenzene; the gaseous organic carbon source is selected from CH₄、C₂H₆、C₂H₄、C₂H₂One or more of them.

Further, in the present embodiment, the solid organic carbon source and the liquid organic carbon source are mixed in a predetermined mass ratio to form a solid-liquid mixture; and then introducing a gaseous organic carbon source into the solid-liquid mixture to form the multiphase carbon source mixture. The method can accurately control the addition amount of the solid organic carbon source and the introduction ratio of the solid-liquid mixture to the gaseous organic carbon source. Wherein the preset mass ratio is the mass ratio of the solid organic carbon source to the liquid organic carbon source, and the value is 0.01-30%. In other embodiments of the present invention, the solid organic carbon source, the liquid organic carbon source, and the gaseous organic carbon source may be mixed simultaneously.

Further, in this embodiment, after forming the solid-liquid mixture, the solid-liquid mixture is passed into a vessel at a first flow rate while simultaneously passing the gaseous organic carbon source into the vessel at a second flow rate to form the multi-phase carbon source mixture. Wherein the first flow rate is 0.0005 to 20ml/min and the second flow rate is 0.1 to 500sccm, so that the gaseous organic carbon source can be sufficiently mixed with the solid-liquid mixture. For example, in this embodiment, the vessel may be a multiphase carbon source mixing tank.

Referring to step S11, the carbon source mixture is heated to crack into gaseous activated carbon-containing radicals.

In this step, the carbon source mixture is heated at a temperature of 25 to 1100 ℃ and a pressure of 0.005 to 780 Torr. And carrying out pyrolysis on the carbon source mixture to form gaseous active carbon-containing groups.

Specifically, in the present embodiment, the temperature of the carbon source mixing tank is raised to 25 to 1100 ℃, the pressure in the multi-phase carbon source mixing tank is maintained at 0.005 to 780Torr, and the multi-phase carbon source mixture is pyrolyzed to form gaseous active carbon-containing radicals. The temperature and the pressure in the multiphase carbon source mixing tank are specifically set according to the difference of multiphase carbon sources, and the cracking of the carbon sources can be realized.

Referring to step S12, the gaseous active carbon-containing group is introduced into a reaction chamber, a metal substrate is placed in the reaction chamber, and the gaseous active carbon-containing group is deposited on the metal substrate at a growth temperature and a growth pressure to form a graphene layer, so as to form a graphene metal composite structure.

The metal substrate is a metal wire or a metal foil, the diameter of the metal wire is 10-500 micrometers, and the thickness of the metal foil is 10-500 micrometers.

In the embodiment of the invention, a metal substrate is transported between a roll-to-roll input end and a roll-to-roll output end by using a roll-to-roll (R2R) deposition mode, and during the transport process of the metal substrate, the gaseous active carbon-containing groups are deposited on the surface of the metal substrate to form a graphene layer. The roll-to-roll deposition mode can be used for continuously preparing the graphene metal composite structure.

The roll-to-roll vapor deposition equipment comprises a tube furnace, a roll input end and a roll output end, wherein the roll input end and the roll output end are respectively positioned on two sides of the tube furnace. The opposite-rolling input end and the opposite-rolling output end respectively comprise cylindrical rollers, a continuous metal substrate is rolled on the rollers of the opposite-rolling input end, the metal substrate is conveyed into the tubular furnace through the conveying belt and the rollers rotate, gaseous active carbon-containing groups are deposited to form a graphene metal composite structure, the graphene metal composite structure is output from the other end of the tubular furnace, and the graphene metal composite structure is rolled on the rollers of the opposite-rolling output end, so that continuous preparation can be realized.

In this embodiment, the flow rate of the gaseous activated carbon-containing radicals introduced into the reaction chamber is 0.1 to 500 sccm. Further, in this embodiment, before the step of introducing the gaseous activated carbon-containing group into the reaction chamber (i.e. before step S12), the following steps are further included: and introducing protective gas and reducing gas into the reaction cavity to pretreat the metal substrate, and removing an oxide layer and impurities on the surface of the metal substrate to facilitate the deposition of subsequent gaseous active carbon-containing groups. Wherein the protective gas is selected from at least one of nitrogen, argon and helium, and the reducing gas is selected from at least one of hydrogen and carbon monoxide.

Further, in the pretreatment process, in order to improve the pretreatment efficiency, the pretreatment temperature is 100-1000 ℃, the pressure in the reaction chamber is 0.05-500Torr, and the treatment time is 1-100 min. Further, the flow rate of the protective gas is 1-500sccm, and the flow rate of the reducing gas is 1-500 sccm.

Further, in the reaction cavity, the growth temperature is 25-1100 ℃, the growth pressure is 0.05-780Torr, and the growth time is 1-100min, so as to finish the deposition of the gaseous active carbon-containing radicals. The preset temperature and the preset pressure can be specifically set according to different types of the gaseous active carbon-containing groups.

Further, after the step of forming the graphene-metal composite structure, the method further comprises the following steps: and cooling the graphene metal composite structure. That is, the graphene metal composite structure on which the graphene has grown is rapidly cooled from a high temperature to a room temperature. In this embodiment, cooling may be performed by means of circulating water cooling, and in other embodiments of the present invention, other cooling means, such as air cooling, may be used.

Further, the cooling rate is 5-40 ℃ per minute, so that rapid cooling is realized.

According to the invention, a carbon source mixture is pyrolyzed before entering a reaction cavity to form gaseous active carbon-containing groups, and the gaseous active carbon-containing groups are deposited on the surface of a metal substrate to form a graphene metal composite structure. According to the preparation method of the graphene metal composite structure, the carbon source is subjected to pyrolysis at first, so that the carbon source is not required to be catalyzed by a metal substrate, and the optional range of the metal substrate material is expanded. The metal substrate may be a material having a catalytic effect on a carbon source or a material having no catalytic effect on a carbon source. In addition, the metal substrate may be not only a pure metal but also a metal alloy. For example, the metal substrate may be a wire or foil of a metal such as Fe, Ag, Au, Cu, Ru, Ta, Al, Mg, Ni, Co, Cr, Zr, Sn, Ti, Mo, Zn, or an alloy thereof such as Cu-Cr system, Cu-Mg system, Cu-Fe system, Cu-Ni system, Cu-Ag system, or the like.

In addition, in the traditional graphene preparation method, a carbon source is decomposed into active groups by virtue of the catalytic action of a metal substrate on the decomposition of the carbon source, graphene is gradually deposited on the surface of a metal material, and after the surface of the metal material is covered by the graphene, the metal material loses the decomposition action on the carbon source, so that the thickness of the prepared graphene is usually thin (less than 5nm), and the growth mode is called self-limiting growth. The method avoids the dependence of the graphene preparation process on the surface catalysis of the metal material, so that thicker graphene can be prepared, and the thicker graphene preparation process is also favorable for forming higher coverage rate. Specifically, in the preparation method, the thickness of the deposited graphene layer can reach 1-200nm, and the coverage rate of the deposited graphene layer can reach more than 98%.

The invention further provides a graphene metal composite structure formed by the preparation method, which comprises a metal substrate and a graphene layer. The metal substrate has no catalytic effect on the cracking of the carbon source. The graphene layer is deposited on the metal substrate.

In the graphene metal composite structure, a metal substrate is not required to be adopted for catalysis during graphene deposition, so that the metal substrate can be made of a material which does not have a catalytic effect on carbon source cracking, and can also be made of a material which has a catalytic effect on the carbon source cracking, and the material selection range of the metal substrate is greatly expanded. Further, the metal substrate may be a pure metal or an alloy. In addition, the method avoids the dependence of the graphene preparation process on the surface catalysis of the metal material, so that thicker graphene can be prepared, and the thicker graphene preparation process is also favorable for forming higher coverage rate. For example, in one embodiment of the present invention, the coverage of the graphene layer is greater than 98%. The thickness of the graphene layer is 1-200 nm.

The invention also provides an embodiment of a preparation method of the graphene metal composite structure. The concrete description is as follows:

(1) dissolving one or more of organic substances such as glucose, polycyclic aromatic hydrocarbon, PMMA, PEG, paraffin, stearic acid and the like in one or more organic solvents such as methanol, ethanol, anisole, benzene, chlorobenzene and the like in a mass ratio of 0.01-30% to form a solid-liquid carbon source mixture.

(2) The mixture was pumped into a multiphase carbon source mixing tank at a rate of 0.0005-20mL/min using a peristaltic pump.

(3) Introducing CH into the multiphase carbon source mixing tank at a flow rate of 0.1-500 sccm₄、C₂H₆、C₂H₄、C₂H₂Etc. with one or more of the carbon-containing gases.

(4) And heating the multi-phase carbon source mixing tank to 25-1100 ℃, and keeping the pressure in the mixing tank at 0.005-780Torr, so that the multi-phase carbon source is cracked into gaseous active carbon-containing radicals in the mixing tank.

(5) The metal wire (foil) with the length of 1-5000m and the diameter of 10-500 μm or the metal foil with the thickness of 10-500 μm is placed in a tube furnace, and protective gas and reducing gas are introduced into the tube furnace to pretreat the metal wire (foil). Wherein the protective gas is N₂Ar, He and the like, and the reducing gas is H₂And CO, and the like. The flow rates of the protective gas and the reducing gas are respectively 1-500sccm and 1-500sccm, the pressure in the tubular furnace is 0.05-500Torr, the treatment temperature is 100-.

(6) After the pretreatment process is finished, adjusting the temperature in the tubular furnace to be 25-1100 ℃, introducing the gaseous active carbon-containing radicals into the tubular furnace at the flow rate of 0.1-500 sccm, adjusting the pressure in the tubular furnace to be 0.05-780Torr by using a vacuum pump, and adjusting the rolling speed to ensure that the growth time of the graphene in a constant-temperature region of the tubular furnace is 1-100 min.

(6) And rapidly cooling the Gr grown metal wire (foil) to room temperature from high temperature by using a circulating cooling water system (the cooling speed is controlled to be 5-40 ℃/min), and further obtaining graphene/metal wire (foil) at the output end of the involution, wherein the coverage rate of the graphene can reach more than 98 percent, and the thickness range of the graphene is 1-200 nm.

Fig. 2 is a scanning electron microscope image of the surface of the graphene-metal wire composite structure prepared by the preparation method according to the embodiment of the present invention, and fig. 3 is a scanning electron microscope image of the surface of the graphene-metal foil composite structure prepared by the preparation method according to the embodiment of the present invention, it can be seen that graphene layers are uniformly deposited on the surfaces of the metal wires and the metal foils, and the coverage rate of the graphene layers reaches 98%. Fig. 4 is a graph of the thickness of graphene in the graphene metal foil composite structure prepared by the preparation method provided by the embodiment of the invention, and it can be seen that the thickness of the graphene layer prepared by the preparation method of the invention is uniform and is greater than 1 nm.

The invention also provides a device for preparing the graphene-metal composite structure. Fig. 5 is a schematic structural diagram of an apparatus for preparing a graphene metal composite structure according to an embodiment of the present invention. Referring to fig. 5, the apparatus includes a carbon source mixing container 50 and a reaction chamber 60.

The carbon source mixing vessel 50 is configured to mix at least one of a solid organic carbon source, a liquid organic carbon source, and a gaseous organic carbon source to form a carbon source mixture, and is configured to heat the carbon source mixture to crack the carbon source mixture into gaseous reactive carbon-containing radicals.

The reaction cavity 60 is communicated with the carbon source mixing container 50 and is used for receiving the gaseous active carbon-containing groups, a metal substrate can be placed in the reaction cavity, and the gaseous active carbon-containing groups are deposited on the metal substrate at a growth temperature and a growth pressure to form a graphene layer so as to form a graphene metal composite structure.

Further, in the present embodiment, the carbon source mixing container 50 further comprises a solid-liquid mixing device 51, a gaseous organic carbon source supply device 52, and a multi-phase carbon source mixing tank 53.

The solid-liquid mixing device 51 is used for mixing the solid organic carbon source and the liquid organic carbon source to form a solid-liquid mixture. Specifically, a solid organic carbon source is placed in the solid-liquid mixing device 51, and a liquid organic carbon source is added to the solid-liquid mixing device 51 to form a solid-liquid mixture.

The gaseous organic carbon source supply device 52 is used for supplying a gaseous organic carbon source.

One end of the multi-phase carbon source mixing tank 53 is communicated with the solid-liquid mixing device 51 and the gaseous organic carbon source supply device 52, and is used for receiving the solid-liquid mixture and the gaseous organic carbon source to form a carbon source mixture. Further, the solid-liquid mixing device 51 is connected with one end of the multiphase carbon source mixing tank 53 through a peristaltic pump 54, and the peristaltic pump 54 pumps the solid-liquid mixture in the solid-liquid mixing device 51 into the multiphase carbon source mixing tank 53.

The other end of the multiphase carbon source mixing tank 53 is communicated with the reaction chamber 60 and is used for providing gaseous active carbon-containing radicals into the reaction chamber 60.

The multiphase carbon source mixing tank 53 can also be heated to crack the carbon source mixture into gaseous activated carbon-containing radicals.

Further, in the present embodiment, the multi-phase carbon source mixing tank 53 includes a heating chamber 531 and a lysis chamber 532 disposed in the heating chamber 531. The heating cavity 531 is used for heating the pyrolysis cavity 532, so that the temperature in the pyrolysis cavity 532 reaches the pyrolysis temperature of the carbon source. Wherein, one end of the cracking cavity 532 is communicated with the solid-liquid mixing device 51 and the gaseous organic carbon source supply device 52, that is, the solid-liquid mixture and the gaseous organic carbon source enter the cracking cavity 532 through one end of the cracking cavity 532, so as to form a carbon source mixture.

The inner wall of the cracking cavity 532 is in a spiral configuration, a carbon source mixture flows to the other end of the cracking cavity 532 along a spiral configuration route, and under the action of high temperature, the front end of the carbon source mixture is pyrolyzed into gaseous active carbon-containing radicals.

The other end of the cracking cavity 532 is communicated with the reaction cavity 60, and gaseous active carbon-containing radicals generated by pyrolysis at the front end of the carbon source mixture are introduced into the reaction cavity 60 to participate in deposition reaction.

The device can realize high-temperature pyrolysis of a carbon source mixture before the carbon source mixture enters the reaction cavity to form the gaseous active carbon-containing group, and the gaseous active carbon-containing group is deposited on the surface of the metal substrate to form the graphene metal composite structure. According to the preparation method of the graphene metal composite structure, the carbon source is subjected to pyrolysis at first, so that the carbon source is not required to be catalyzed by a metal substrate, and the optional range of the metal substrate material is expanded.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.