WO2020238260A1

WO2020238260A1 - Vertical graphene-high molecular polymer composite material and preparation method therefor

Info

Publication number: WO2020238260A1
Application number: PCT/CN2020/072297
Authority: WO
Inventors: 郑伟; 赵鑫
Original assignee: 深圳市溢鑫科技研发有限公司
Priority date: 2019-05-24
Filing date: 2020-01-15
Publication date: 2020-12-03
Also published as: CN110564087B; CN110564087A

Abstract

The present invention relates to the technical field of graphene composite materials, and in particular, to a vertical graphene-high molecular polymer composite material, comprising a substrate, vertical graphene, and a high molecular polymer. The vertical graphene grows on the surface of the substrate. The high molecular polymer is cured into a film and uniformly loaded on the surface and edge of the vertical graphene. Compared with the prior art, according to the vertical graphene-high molecular polymer composite material provided by the present invention, the unique morphology and super large surface area of the vertical graphene are maintained while the vertical graphene is separated from the substrate, and the flat graphene layer at the bottom is used. Moreover, the high molecular polymer can protect and cure the vertical graphene and the active substance loaded on the surface to increase the service life of the material. In addition, by adjusting the pore structure of a high molecular polymer thin film, substance exchange between the vertical graphene and the outside world is facilitated, and reaction efficiency is improved. Also disclosed is a preparation method for a vertical graphene-high molecular polymer composite material.

Description

Vertical graphene-high molecular polymer composite material and preparation method thereof

Technical field

The invention belongs to the technical field of graphene composite materials, and particularly relates to a vertical graphene-high molecular polymer composite material and a preparation method thereof.

Background technique

Since the vertical graphene was successfully prepared in 2003, this star material has attracted people's attention because of its special structure, ease of industrial production and excellent performance. This material that directly grows on the surface of the substrate without a binder has a huge specific surface area and micro-mechanical strength. Studies have shown that vertical graphene has broad application prospects, such as catalyst loading, biosensors, energy storage, electrochemical electrodes, flexible electrodes, transparent electrodes, heating, heat conduction and other fields.

However, as a kind of nano material, the vertical graphene is macroscopically fragile, afraid of scratching, scratching, and not resistant to direct contact with foreign objects. Even strong air currents, water currents, etc. may destroy its vertical morphology and microstructure. Large surface area is also easy Contamination of various pollutants such as fine dust makes the active material useless. In addition, as a nanomaterial, upright graphene is grown in situ on the surface of a high-temperature resistant substrate. These substrate materials are often thick and strong. If you want to maintain the unique structure of upright graphene, you must rely on the substrate. Destroy its structure. Relying on the substrate greatly limits the application of vertical graphene and limits its application potential in many aspects. Therefore, the surface of the upright graphene is protected to avoid direct contact between the upright graphene sheet and foreign matter, reduces the chance of contact with external contaminants, and improves the preservation rate of active ingredients, thereby significantly expanding the application scenarios of upright graphene, and Increasing life span has become a rigid requirement for the development of vertical graphene applications. In addition, if the vertical graphene nanostructure can exist without the substrate grown in situ, it can greatly expand its application field.

The production process of graphene can be divided into three categories: graphite expansion method, redox method and chemical vapor deposition in-situ growth method. Among them, the chemical vapor deposition in-situ growth method is to crack the carbon source gas and deposit the carbon element into graphene. The trial production process of this method can grow a few or single layers of graphene without pollution and almost zero impurities. The vertical graphene grown by plasma-enhanced chemical vapor deposition is grown upright on the surface of the substrate. It has a large surface area and a special spatial morphology, while maintaining a flat graphene layer. From the future development of graphene applications In terms of trends, with the improvement and optimization of the process, this vertical graphene is the first choice for industries such as sensors, catalysis, and energy storage.

There are many types of macromolecule polymers. The general characteristics include: they can be made into micron or sub-micron films, with certain strength and elasticity, low density, acid and alkali resistance, softness, and good light transmittance. They can perform well on upright graphene. protection of. At the same time, the high-molecular polymer film can solidify active materials such as enzymes and catalysts, so that they will not easily peel off. In the application of vertical graphene, in addition to a good protective layer and curing of active materials, the protective layer also needs to have a certain pore structure, which facilitates the exchange of materials between the vertical graphene and the outside, such as in transmission Applications in the field of sensing and energy storage. The pore structure of different high molecular polymer films can be controlled within a certain range according to different production conditions. If the upright graphene sheets are embedded in a polymer film to prepare a composite material that has both protective support and curing active materials, as well as a channel transport function, it will do more than one.

In view of this, the present invention aims to provide a vertical graphene/high molecular polymer and a preparation method thereof, which allows the vertical graphene to be separated from its growth substrate while maintaining its unique morphology and super large surface area, and effectively utilizes The planar graphene of the vertical graphene bottom layer is grown in situ and exposed. At the same time, the use of high-molecular polymer films better protects the fragile structure of the vertical graphene, and protects and cures the active substances loaded on the surface of the vertical graphene, prevents it from falling off, and increases the service life. Further, by adjusting and controlling the pore structure of the high molecular polymer film, it is beneficial to exchange materials between the vertical graphene and the outside, and the reaction efficiency of the vertical graphene is improved.

Summary of the invention

One of the objectives of the present invention is to provide an upright graphene-high molecular polymer composite material in view of the shortcomings of the prior art, which can maintain the unique morphology and oversize of upright graphene while being separated from its growth substrate. The surface area is effectively used and exposed on the flat graphene layer at the bottom of the vertical graphene. At the same time, the use of high-molecular polymer films better protects the fragile structure of the vertical graphene, and protects and cures the active substances loaded on the surface of the vertical graphene, prevents it from falling off, and increases the service life. Further, by adjusting and controlling the pore structure of the high molecular polymer film, it is beneficial to exchange materials between the vertical graphene and the outside and improve the reaction efficiency.

In order to achieve the above objective, the present invention adopts the following technical solutions:

An upright graphene-high molecular polymer composite material includes a substrate, an upright graphene, and a high molecular polymer. The vertical graphene is grown on the surface of the substrate, and the high molecular polymer is cured into a film. Load evenly on the surface and edge of the vertical graphene.

As an improvement of the vertical graphene-high molecular polymer composite material of the present invention, the substrate is a smooth and hard material, such as high-conductivity carbon paper, polished silicon wafer, polished quartz wafer, magnesium oxide, silicon dioxide, At least one of aluminum oxide and aluminum nitride facilitates the peeling of the vertical graphene-high molecular polymer composite material from the substrate.

As an improvement of the vertical graphene-polymer composite material of the present invention, the vertical graphene is prepared by a plasma-assisted chemical vapor deposition method under low pressure, and its structure includes a planar graphene layer close to the substrate And two parts of the vertical graphene layer embedded with polymer.

As an improvement of the vertical graphene-high molecular polymer composite material of the present invention, the thickness of the planar graphene layer is 2nm-30nm, the height of the vertical graphene layer is 10nm-20μm, and the specific surface area is between 1000 ~2600m ² /g, other morphological features such as density and curvature can be adjusted.

As an improvement of the vertical graphene-high molecular polymer composite material of the present invention, the coverage of the high molecular polymer film on the surface and edge of the vertical graphene can be controlled at 0-100%, and the thickness can be controlled at 0.1 ~500μm, the porosity can be controlled above 0-90%, and the typical hole line size is 10nm～10μm.

As an improvement of the vertical graphene-high molecular polymer composite material of the present invention, the high molecular polymer is PVDF, PS, PE, PDMS, PMMA, Nafion, PEO, PP, PVC, PVB, PES, PA, At least one of PI, P0, PC, PU, PTFE, PAN, PANI, PEDOT, PT, Polyfluorene, PVDC, PET, PPS, ABS, and epoxy resin.

Another object of the present invention is to provide a method for preparing a vertical graphene-high molecular polymer composite material, which at least includes the following steps:

In the first step, the substrate is placed in the vacuum chamber of the plasma chemical vapor deposition device, and reducing gas is introduced, and the low pressure state in the device is maintained through flow adjustment, and the substrate is plasma-etched;

In the second step, the protective gas is introduced after the etching reaction is completed, the carbon source and buffer gas are introduced after the temperature is raised, and the low pressure state in the device is maintained through flow adjustment;

The third step is to perform a plasma chemical vapor deposition reaction on the etched substrate. After the reaction is completed, when the temperature of the equipment drops to room temperature, vertical graphene can be grown on the surface of the substrate;

The fourth step is to prepare a high molecular polymer solution;

The fifth step is to coat the high molecular polymer solution on the surface and edges of the vertical graphene;

In the sixth step, the high-molecular polymer coated on the surface and edge of the vertical graphene is cured to form a film, and the vertical graphene-high-molecular polymer composite material can be obtained.

As an improvement of the method of the present invention, the reducing gas is at least one of hydrogen and argon, and the low pressure state is that the vacuum degree is stable at 5Pa-30Pa.

As an improvement of the method of the present invention, the protective gas is at least one of nitrogen and argon, and the carbon source is methane, ethane, ethylene, propylene, acetylene, methanol, ethanol, acetone, benzene, toluene, At least one of xylene and benzoic acid, and the buffer gas is at least one of hydrogen and argon.

As an improvement of the method of the present invention, the ion source of the plasma is at least one of radio frequency plasma, microwave plasma or DC high voltage plasma, and the power density provided by the plasma equipment is 1-50 watts per square centimeter .

As an improvement of the method of the present invention, the reaction temperature of the plasma chemical vapor deposition reaction is 400°C to 1500°C, preferably 690°C to 950°C.

As an improvement of the method of the present invention, the etching reaction time is 1 to 30 minutes, and the plasma chemical vapor deposition reaction time is 3 to 200 minutes.

As an improvement of the method of the present invention, the preparation method of the high-molecular polymer solution includes dissolving the high-molecular polymer in an organic solution, an aqueous solution, a mixed solution, a solution with a lead agent, and the high-molecular polymer is PVDF, Nafion, PE At least one of, PP, PVC, PS, PC, PET, PI, PVDC, PAN, PU, PEO, PO, PVB, PES, or high molecular polymer melted into liquid at higher temperature, high molecular polymerization The substance is at least one of PE, PP, ABS, PET, PES, PPS, or high molecular polymer particles are dispersed and suspended in a medium liquid, and the high molecular polymer is at least one of PP, PS, PTFE, and PEDOT, or By mixing and reacting different chemical raw materials, it becomes the original solution of the target high molecular polymer. The high molecular polymer is at least one of PA, PMMA, PANI, PDMS, PT, Polyfluorene, and epoxy resin.

It is prepared by high-molecular polymer with additives of different components and proportions, and solvents after heating and melting, mixing and stirring.

As an improvement of the method of the present invention, the method for coating the high molecular polymer solution is spin coating, drop plating, knife edge calendering, roll pressing, electrochemical plating, spraying, electrospraying, and electroplating. Spinning, screen printing or printing.

As an improvement of the method of the present invention, the method of curing the polymer polymer to form a film is at least one of natural storage at room temperature, high temperature storage, dry storage, vacuum storage, water washing, ultraviolet curing, and additive curing, and the curing time is 0.1～10h.

As a further improvement of the method of the present invention, the vertical graphene-polymer composite material can be loaded with active substances on the surface of the vertical graphene according to application requirements, or the vertical graphene-polymer composite material can be combined with The growth substrate is peeled off.

Compared with the prior art, the present invention has at least the following beneficial effects:

1. For different polymer materials, the existing mature coating methods in industry and scientific research are used, without the need to develop new processes, processes, and methods. The preparation process is simple, easy to operate, energy-saving and environmentally friendly, and suitable for large-scale production.

2. The present invention embeds the vertical graphene into the high molecular polymer, which effectively protects the vertical graphene, which is a fragile macro-dimensional nanomaterial, can effectively avoid damage caused by scratching, rubbing, touching, and touching, and increases The vertical graphene is transported, packaged, and cut, and further becomes the operability of the device, while also increasing the service life of the vertical graphene.

3. The present invention embeds the vertical graphene into the high molecular polymer, which can make this macro-dimensional fragile nano material separate from its growth substrate and exist independently, and preserves its unique morphology and super large surface area, and has a broader Application scenarios.

4. The present invention can peel the vertical graphene from the substrate, thereby exposing the plane graphene layer at the bottom of the vertical graphene, so that the plane graphene layer can be used, and the application field of the vertical graphene is further expanded.

5. The present invention protects the unique structure and huge surface area of the vertical graphene by preserving the unique pore structure of the high molecular polymer, while ensuring that the vertical graphene can exchange materials with the outside world. Different high molecular polymers depend on the film forming process. There are different tunnel structures for different applications.

6. The high-molecular polymer of the present invention can also solidify the active substances loaded on the surface of the vertical graphene, such as platinum nanoparticles and catalytic enzymes, to prevent them from falling off, effectively prevent the active substances from losing their activity, and at the same time avoid the active substances in use Due to agglomeration, the efficiency is reduced, thereby increasing the life span.

Description of the drawings

Figure 1 is a scanning electron microscope (SEM) image of the upright graphene of the present invention.

Fig. 2 is an SEM top view of the vertical graphene-Nafion composite material obtained in Example 1 of the present invention.

3 is an SEM image of the bottom plane graphene layer of the vertical graphene-PVDF composite material obtained in Example 2 of the present invention after being separated from the growth substrate.

Detailed ways

The present invention and its beneficial effects will be described in detail below in conjunction with specific embodiments, but the embodiments of the present invention are not limited thereto.

Example 1

An upright graphene-Nafion composite material includes a high-conductivity carbon paper substrate, upright graphene and high molecular polymer Nafion. Upright graphene is grown on the surface of a high-conductivity carbon paper substrate, and the polymer Nafion is uniformly supported on the surface and edges of the upright graphene.

Vertical graphene includes two parts: a planar graphene layer close to the substrate and a vertical graphene layer embedded with a polymer.

A method for preparing an upright graphene-Nafion composite material includes at least the following steps:

In the first step, the highly conductive carbon paper is put into the vacuum chamber of the plasma chemical vapor deposition device, and the reducing gas hydrogen and argon are introduced 1:1, and the low pressure state in the device is maintained through flow adjustment, so that the vacuum degree is stable. 15Pa, plasma etching reaction on high-conductivity carbon paper, the reaction time is 10min, the power density of the plasma equipment is 10 watts per square centimeter;

In the second step, after the etching reaction is completed, argon gas is introduced, and the temperature is heated to 700°C at a heating rate of 20°C/min. After the temperature is raised, hydrogen and methane are introduced 1:1, and the low pressure in the device is maintained through flow adjustment and the vacuum The degree is 15Pa;

The third step is to perform plasma chemical vapor deposition reaction on the high-conductivity carbon paper. The reaction time is 15 minutes, and the power density provided by the plasma equipment is 10 watts per square centimeter. After the reaction is completed, the temperature of the equipment is reduced to room temperature, and the vertical growth is obtained. Graphene highly conductive carbon paper;

The fourth step is to prepare a 15wt% Nafion formaldehyde solution;

In the fifth step, evenly drop 15wt% Nafion's formaldehyde solution on the center of the high-conductivity carbon paper on which the vertical graphene is grown. The spin coater spins for 15 seconds at a speed of 500 RPM;

In the sixth step, the high-conductivity carbon paper is allowed to stand for 5 hours in the air at room temperature to solidify Nafion into a film to obtain a vertical graphene-Nafion composite material.

Figure 1 is an SEM image of the vertical graphene prepared by the present invention. The average thickness of the vertical graphene layer is 2 μm, the average thickness of the planar graphene layer is 2 nm, and the average specific surface area of the prepared vertical graphene is 1300 m ² /g. 2 is a top view of the vertical graphene-Nafion composite material prepared in this embodiment by SEM. The high molecular polymer Nafion covers and protects the vertical graphene structure and can reflect a certain vertical graphene structure profile. The thickness of the Nafion film in this embodiment is about 300 nm. The high-molecular polymer Nafion is used as a protective layer, so that the vertical graphene-Nafion composite material can be touched, cut, and manipulated without damaging the vertical graphene structure. The vertical graphene-Nafion composite material in this example was used as an electrochemical electrode. In various electrochemical experiments, the sensitivity reached 80% of that of unsupported Nafion and bare vertical graphene electrodes, which proved that Nafion film has excellent properties. Ion permeability, and can perfectly protect the structure of upright graphene. At the same time, due to the protection of Nafion, the service life of the electrode reaches more than 500h, and the stability is greatly increased. It has revolutionary application prospects in the new generation of biochemical sensors for hydrogen peroxide metabolism.

Example 2

The difference from Example 1 is the method for preparing the vertical graphene/high molecular polymer composite material, which at least includes the following steps:

In the first step, the polished silicon wafer is placed in the vacuum chamber of the plasma chemical vapor deposition device, and the reducing gas hydrogen and argon are introduced 1:1, and the low pressure state in the device is maintained through flow adjustment to stabilize the vacuum at 15Pa , Plasma etching reaction is performed on the substrate, the reaction time is 10 minutes, and the power density of the plasma equipment is 10 watts per square centimeter;

In the second step, after the etching reaction is completed, argon is introduced, and the temperature is heated to 700°C at a heating rate of 20°C/min. After the temperature is raised, hydrogen and methane are introduced 1:1, and the low pressure in the device is maintained through flow adjustment and the vacuum is maintained. The degree is 15Pa;

The third step is to perform plasma chemical vapor deposition reaction on the polished silicon wafer. The reaction time is 15 minutes. The power density provided by the plasma equipment is 10 watts per square centimeter. After the reaction is completed, the temperature of the equipment is reduced to room temperature, and vertical graphite is grown. Olefin polished silicon wafers;

The fourth step is to prepare a high-molecular polymer PVDF/PEO solution, mix 8% PVDF and 2% PEO powder with 90% NMP solution in a weight ratio, stir evenly, and let stand in an oven at 80°C for 2 hours to become a transparent solution. Add 1/20 volume of glycerin and mix well;

In the fifth step, pour the PVDF/PEO solution evenly on the polished silicon wafer on which the vertical graphene has been grown, and spin the coating machine for 30 seconds at 1000 RPM;

In the sixth step, place the polished silicon wafer in an oven at 100°C for 2 hours to solidify the PVDF/PEO into a film;

In the seventh step, the upright graphene-PVDF/PEO composite material was peeled off and polished the silicon wafer as a whole, and then placed in pure water to stand for 2 hours to obtain an upright graphene-PVDF/PEO composite material with a pore structure.

Fig. 3 is an SEM image of the bottom plane graphene layer of the vertical graphene-PVDF/PEO composite material prepared in this embodiment after being separated from the polished silicon wafer. The thickness of the PVDF/PEO film is about 5μm. The vertical graphene is evenly embedded in the PVDF/PEO film. The bottom plane graphene layer of the vertical graphene is smooth and flat, completely exposed. The hole rate of the PVDF/PEO layer is 60%, and the average hole is The diameter is 4μm. The ionic conductivity of the vertical graphene-PVDF/PEO composite prepared in this embodiment reached 1.2 mS/cm ² in 1M LiClO4/PC. Combined with the extremely large surface area of the vertical graphene, the vertical graphene-PVDF/PEO composite prepared in this embodiment can be used in a new generation of graphene supercapacitors and other energy storage devices.

Example 3

The fourth step is to select platinum target material and place the obtained material in a physical meteorological deposition device, evacuate to 2x10-3pa, fill in argon gas to stabilize the pressure at 5pa, and start magnetron sputtering, where the power is 0.7W/cm2, The time is 10s;

In the fifth step, after the magnetron sputtering is finished, argon gas is injected to 1x105pa, and the temperature is increased to 300°C and kept for 30 minutes for annealing treatment. After the annealing reaction, the temperature of the equipment is reduced to room temperature, that is, platinum is loaded on the surface of the vertical graphene. Nanoparticle

The sixth step is to prepare a 15wt% Nafion formaldehyde solution;

In the seventh step, drop 15wt% Nafion's formaldehyde solution evenly on the center of the high-conductivity carbon paper on which the vertical graphene has been grown, and spin the coating machine at 500 RPM for 15 seconds;

In the eighth step, the high-conductivity carbon paper is allowed to stand for 5 hours in the air at room temperature to cure Nafion into a film to obtain a vertical graphene-Nafion composite material.

Graphite upright type prepared in the present embodiment the alkenyl average specific surface area of about 1300m2 / g, platinum supported gold particle size is less than 2nm, loading of 1mg / cm ^2, similar products loading ratio reduced by 3 orders of magnitude, greatly reduced The amount of precious metals used.

Example 4

In the first step, the polished silicon wafer is placed in the vacuum chamber of the plasma chemical vapor deposition device, and the reducing gas hydrogen and argon are introduced 1:1, and the low pressure state in the device is maintained through flow adjustment to stabilize the vacuum at 15Pa , Plasma etching reaction on the polished silicon wafer, the reaction time is 10 minutes, and the power density of the plasma equipment is 10 watts per square centimeter;

In the second step, after the etching reaction is completed, argon gas is introduced, and the temperature is heated to 700°C at a heating rate of 20°C/min. After the temperature is raised, methane is introduced, and the low pressure in the device is maintained through flow adjustment, and the vacuum degree is 15Pa;

The third step is to perform plasma chemical vapor deposition reaction on the polished silicon wafer. The reaction time is 15 minutes. The power density provided by the plasma equipment is 10 watts per square centimeter. After the reaction, the temperature of the equipment is reduced to room temperature, and vertical graphene is grown. Polished silicon wafers;

The fourth step is to prepare a high molecular polymer PDMS solution. The PDMS main agent and the hardening agent are mixed at a mass ratio of 10:1, and the mixture is stirred evenly;

In the fifth step, pour the PDMS solution evenly on the polished silicon wafer on which the upright graphene has been grown, and spin the spin coater for 30 seconds at 500 RPM;

In the sixth step, place the polished silicon wafer in an oven at 60°C for 2 hours to cure the PDMS into a film;

In the seventh step, the upright graphene-PDMS composite material is completely peeled off and polished from the silicon wafer to obtain the upright graphene-PDMS composite material.

The thickness of the PDMS film prepared in this embodiment is 10 μm, and the vertical graphene is evenly embedded in the PDMS. The initial material resistance is 90 ohms/square, and the resistance is about 800 ohms/square after being stretched by 20%, and it is still conductive when stretched by 100%. When the stretching width is 10%, and the stretching is repeated 1000 times, the material resistance only increases by 30%. Bending, curling, and folding with a diameter greater than two millimeters do not affect the conductivity of the vertical graphene-PDMS composite material of this embodiment. The vertical graphene-PDMS composite material prepared in this embodiment is used as a flexible and stretchable electrode material and can be applied to a new generation of wearable electronics.

Example 5

In the fourth step, two solutions are prepared: 0.45mL phytic acid, 0.40mL aniline, 2mL distilled water mixed solution, and 0.24g ammonium persulfate dissolved in 0.85mL aqueous solution. Put them in two containers and cool them to 4℃ in the refrigerator;

The fifth step is to quickly mix the above two solutions, and evenly pour them on the surface of the polished silicon wafer on which the vertical graphene has grown, and use the blade edge of the squeegee at a distance of 1 mm from the surface of the polished silicon wafer to apply knife edge rolling;

In the sixth step, the polished silicon wafer is allowed to stand at room temperature for 1 hour to solidify the PANi hydrogel to form a film, thereby obtaining a vertical graphene-PANi hydrogel composite material.

In the vertical graphene-PANi hydrogel composite material prepared in this embodiment, the vertical graphene is coated and protected by a jelly-like PANi hydrogel, and the PANi hydrogel has strong adsorption performance due to its excellent pore structure. It can further adsorb enzymes and catalysts and the solution to be tested, and has a wide range of applications in the field of biochemical testing.

Example 6

In the first step, the conductive graphite paper is placed in the vacuum chamber of the plasma chemical vapor deposition device, and the reducing gases hydrogen and argon are introduced 1:1, and the low pressure state in the device is maintained through flow adjustment to stabilize the vacuum at 15Pa , Plasma etching reaction on conductive graphite paper, the reaction time is 10 minutes, and the power density of the plasma equipment is 10 watts per square centimeter;

The third step is to perform plasma chemical vapor deposition reaction on the conductive graphite paper. The reaction time is 15 minutes. The power density provided by the plasma equipment is 10 watts per square centimeter. After the reaction, the temperature of the equipment is reduced to room temperature, and vertical graphite is grown. Conductive graphite paper;

The fourth step is to prepare a PEDOT/PSS aqueous solution, the formula is 10mM PEDOT and 2wt% PSS;

In the fifth step, the conductive graphite paper on which the vertical graphene has been grown is placed in the PEDOT/PSS aqueous solution and electroplated for 400s at a current density of 5mA/mm ² ;

In the sixth step, the conductive graphite carbon paper is allowed to stand at room temperature for 5 hours to solidify the PEDOT into a film to obtain a vertical graphene-PEDOT composite material.

The thickness of the PEDOT film prepared in this embodiment is 1 μm, and is uniformly attached to the surface of the vertical graphene. The thickness of the plating layer can be precisely controlled by electroplating, and the PEDOT film obtained by electroplating has strong adhesion.

Example 7

The third step is to perform plasma chemical vapor deposition reaction on the conductive graphite paper. The reaction time is 15 minutes. The power density provided by the plasma equipment is 10 watts per square centimeter. After the reaction, the temperature of the equipment is reduced to room temperature, and vertical graphene is grown. Conductive graphite paper;

The fourth step is to mix the concentrated PTFE dispersion with the PVA aqueous solution, control the mass ratio of PTFE and PVA to 7:3, and stir evenly;

The fifth step is to use an electrospinning nozzle with an inner diameter of 0.6mm. The nozzle is about 10cm away from the conductive graphite paper on which vertical graphene is grown. Apply a voltage of 10kV between the nozzle and the conductive graphite paper. The electrospinning nozzle has a flow rate of 20μL/min. 10min;

In the sixth step, the electrospun conductive graphite carbon paper is sintered in a muffle furnace at 300°C for 5 minutes to remove the PVA component and solidify the PTFE into a film to obtain a vertical graphene-PTFE composite material.

The PTFE fiber prepared in this embodiment has a diameter of 500 nm, which is interwoven to form a film and uniformly covers the surface of the vertical graphene, with an average hole diameter of 5 μm. While PTFE fiber protects the vertical graphene, it has excellent ion permeability. At the same time, the vertical graphene-PTFE composite material prepared in this embodiment has very strong hydrophobic and antifouling properties.

Example 8

The third step is to perform plasma chemical vapor deposition reaction on the polished silicon wafer. The reaction time is 15 minutes, and the power density provided by the plasma equipment is 10 watts per square centimeter. After the reaction, the temperature of the equipment is reduced to room temperature, and vertical graphite is grown. Olefin polished silicon wafers;

The fourth step is to prepare a molten PMMA liquid with a liquid temperature of 150°C;

In the fifth step, preheat the polished silicon wafer and the spin coater tray on which the vertical graphene has grown, and then quickly install the polished silicon wafer and the spin coater tray on the spin coater, and put the molten PMMA solution Pour evenly on the surface of the polished silicon wafer, spin-coating at 100RPM for 20s;

In the sixth step, the polished silicon wafer is allowed to stand at room temperature for 1 hour to solidify the PMMA into a film to obtain a vertical graphene-PMMA composite material.

The vertical graphene-PMMA composite material prepared in this embodiment has a thickness of about 30 μm and strong hardness.

Based on the disclosure and teaching of the foregoing specification, those skilled in the art to which the present invention belongs can also make changes and modifications to the foregoing embodiments. Therefore, the present invention is not limited to the above-mentioned specific embodiments. Any obvious improvement, replacement or modification made by those skilled in the art on the basis of the present invention shall fall within the protection scope of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the present invention.

Claims

An upright graphene high-molecular polymer composite material, comprising a substrate, upright graphene, and a high-molecular polymer. The vertical graphene is grown on the surface of the substrate, and the high-molecular polymer is cured into a film and uniform Loaded on the surface and edge of upright graphene.
The vertical graphene-high molecular polymer composite material according to claim 1, wherein the substrate can be a smooth hard material, such as high-conductivity carbon paper, polished silicon wafer, polished quartz wafer, and magnesium oxide At least one of silicon dioxide, aluminum oxide, and aluminum nitride, which facilitates the peeling of the vertical graphene-polymer composite material from the substrate. The substrate can also be a high-temperature resistant conductive material, which is At least one of conductive carbon paper, graphite paper, carbon cloth, metal foil, and metal mesh is convenient to be used as a device to conduct a circuit.
The vertical graphene-high molecular polymer composite material according to claim 1, wherein the vertical graphene is prepared by plasma-assisted chemical vapor deposition at low pressure, and its structure includes The planar graphene layer and the vertical graphene layer embedded with high molecular polymer are two parts.
The vertical graphene-high molecular polymer composite material according to claim 1, wherein the thickness of the planar graphene layer is 2 nm to 30 nm, and the height of the vertical graphene layer is 10 nm to 20 μm. The surface area is between 1000-2600m 2 /g, and other morphological features such as density and curvature can be adjusted.
The vertical graphene-high molecular polymer composite material according to claim 1, wherein the coverage of the high molecular polymer film on the surface and edge of the vertical graphene can be controlled within 0-100%, and the thickness It can be controlled within 0.1～500μm, and the porosity can be controlled above 0-90%, and its typical pore linearity is 10nm～10μm.
The vertical graphene-high molecular polymer composite material of claim 1, wherein the high molecular polymer is PVDF, PS, PE, PDMS, PMMA, Nafion, PEO, PP, PVC, PVB, At least one of PES, PA, PI, PO, PC, PU, PTFE, PAN, PANI, PEDOT, PT, Polyfluorene, PVDC, PET, PPS, ABS, and epoxy resin.
The method for preparing an upright graphene-high molecular polymer composite material according to any one of claims 1 to 6, characterized in that it comprises at least the following steps:

In the first step, the substrate is placed in the vacuum chamber of the plasma chemical vapor deposition device, and reducing gas is introduced, and the low pressure state in the device is maintained through flow adjustment, and the substrate is plasma-etched;

In the second step, the protective gas is introduced after the etching reaction is completed, the carbon source and buffer gas are introduced after the temperature is raised, and the low pressure state in the device is maintained through flow adjustment;

The third step is to perform a plasma chemical vapor deposition reaction on the etched substrate. After the reaction is completed, when the temperature of the equipment drops to room temperature, vertical graphene can be grown on the surface of the substrate;

The fourth step is to prepare a high molecular polymer solution;

The fifth step is to coat the high molecular polymer solution on the surface and edge of the vertical graphene;

In the sixth step, the high-molecular polymer coated on the surface and edge of the vertical graphene is cured to form a film, and the vertical graphene-high-molecular polymer composite material can be obtained.
The preparation method according to claim 7, wherein the reducing gas is at least one of hydrogen and argon, and the low pressure state is that the vacuum degree is stable at 5Pa-30Pa.
The preparation method according to claim 7, wherein the protective gas is at least one of nitrogen and argon, and the carbon source is methane, ethane, ethylene, propylene, acetylene, methanol, ethanol, acetone , Benzene, toluene, at least one of xylene and benzoic acid, and the buffer gas is at least one of hydrogen and argon.
The preparation method according to claim 7, wherein the ion source of the plasma is at least one of radio frequency plasma, microwave plasma or DC high voltage plasma, and the power density provided by the plasma equipment is 1 to 1 50 watts per square centimeter.
The preparation method according to claim 7, wherein the reaction temperature of the plasma chemical vapor deposition reaction is 400°C to 1500°C, preferably 690°C to 950°C.
7. The preparation method according to claim 7, wherein the etching reaction time is 1-30 min, and the plasma chemical vapor deposition reaction time is 3-200 min.
The preparation method according to claim 7, wherein the preparation method of the high molecular polymer solution comprises dissolving the high molecular polymer in an organic solution, an aqueous solution, a mixed solution, a solution with a lead agent, and the high molecular polymer is At least one of PVDF, Nafion, PE, PP, PVC, PS, PC, PET, PI, PVDC, PAN, PU, PEO, PO, PVB, PES, or high-molecular polymer melted at a higher temperature Liquid, high molecular polymer is at least one of PE, PP, ABS, PET, PES, PPS, or high molecular polymer particles are dispersed and suspended in the medium liquid, high molecular polymer is PP, PS, PTFE, PEDOT At least one, or through mixing and reaction of different chemical raw materials, becomes the original solution of the target high molecular polymer, the high molecular polymer is at least one of PA, PMMA, PANI, PDMS, PT, Polyfluorene, and epoxy resin.
The preparation method according to claim 7, characterized in that the method of coating the high molecular polymer solution is spin coating, drop plating, knife edge calendering, roll pressing, electrochemical plating, spraying, Electrospray, electrospin, screen printing or printing.
The preparation method according to claim 7, wherein the method for curing the high molecular polymer to form a film is at least one of natural storage at room temperature, high temperature storage, dry storage, vacuum storage, water washing, ultraviolet curing, and additive curing. Kind, curing time is 0.1～10h.
The preparation method according to claim 7, wherein the vertical graphene-high molecular polymer composite material can be loaded with active material on the surface of the vertical graphene, or the vertical graphene-high The molecular polymer composite material is peeled from the growth substrate.