WO2020238260A1 - Matériau composite de graphène vertical-polymère à haut poids moléculaire et procédé de préparation s'y rapportant - Google Patents

Matériau composite de graphène vertical-polymère à haut poids moléculaire et procédé de préparation s'y rapportant Download PDF

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WO2020238260A1
WO2020238260A1 PCT/CN2020/072297 CN2020072297W WO2020238260A1 WO 2020238260 A1 WO2020238260 A1 WO 2020238260A1 CN 2020072297 W CN2020072297 W CN 2020072297W WO 2020238260 A1 WO2020238260 A1 WO 2020238260A1
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molecular polymer
high molecular
graphene
vertical graphene
composite material
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郑伟
赵鑫
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深圳市溢鑫科技研发有限公司
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • macromolecule polymers 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the thickness of the planar graphene layer is 2nm-30nm
  • the height of the vertical graphene layer is 10nm-20 ⁇ m
  • the specific surface area is between 1000 ⁇ 2600m 2 /g, other morphological features such as density and curvature can be adjusted.
  • 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 ⁇ 500 ⁇ m, the porosity can be controlled above 0-90%, and the typical hole line size is 10nm ⁇ 10 ⁇ m.
  • 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:
  • 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;
  • 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
  • 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 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 protective gas is at least one of nitrogen and argon
  • the carbon source is methane, ethane, ethylene, propylene, acetylene, methanol, ethanol, acetone, benzene, toluene, At least one of xylene and benzoic acid
  • the buffer gas is at least one of hydrogen and argon.
  • 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 .
  • the reaction temperature of the plasma chemical vapor deposition reaction is 400°C to 1500°C, preferably 690°C to 950°C.
  • the etching reaction time is 1 to 30 minutes, and the plasma chemical vapor deposition reaction time is 3 to 200 minutes.
  • 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, P
  • It is prepared by high-molecular polymer with additives of different components and proportions, and solvents after heating and melting, mixing and stirring.
  • 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.
  • 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.
  • 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.
  • the present invention has at least the following beneficial effects:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • active substances loaded on the surface of the vertical graphene such as platinum nanoparticles and catalytic enzymes
  • 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.
  • Example 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.
  • 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:
  • 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;
  • 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.
  • the fourth step is to prepare a 15wt% Nafion formaldehyde solution
  • the spin coater spins for 15 seconds at a speed of 500 RPM;
  • 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 ⁇ m
  • the average thickness of the planar graphene layer is 2 nm
  • 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.
  • 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.
  • 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 1 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:
  • 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;
  • 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.
  • 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;
  • 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;
  • 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 5 ⁇ m.
  • 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 4 ⁇ m.
  • 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 1 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:
  • 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;
  • 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 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.
  • 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;
  • 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.
  • the sixth step is to prepare a 15wt% Nafion formaldehyde solution
  • 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 1 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:
  • 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;
  • 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;
  • 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;
  • 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 ⁇ m, 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%.
  • 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 1 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:
  • 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;
  • 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.
  • the temperature of the equipment is reduced to room temperature, and vertical graphite is grown. Olefin polished silicon wafers;
  • 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°C 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;
  • 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.
  • 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 1 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:
  • 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 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 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.
  • the fourth step is to prepare a PEDOT/PSS aqueous solution, the formula is 10mM PEDOT and 2wt% PSS;
  • 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 ;
  • 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 ⁇ m, 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 1 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:
  • 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 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 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.
  • 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 20 ⁇ L/min. 10min;
  • 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 ⁇ m. 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 1 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:
  • 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;
  • 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, 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;
  • 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;
  • 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 ⁇ m and strong hardness.

Abstract

La présente invention concerne le domaine technique des matériaux composites de graphène, et en particulier, un matériau composite de graphène vertical-polymère à haut poids moléculaire, comprenant un substrat, du graphène vertical et un polymère à haut poids moléculaire. Le graphène vertical croît sur la surface du substrat. Le polymère à haut poids moléculaire est durci en un film et chargé uniformément sur la surface et le bord du graphène vertical. Par comparaison avec l'état de la technique, selon le matériau composite de graphène vertical-polymère à haut poids moléculaire fourni par la présente invention, la morphologie unique et la super-grande surface du graphène vertical sont maintenues tandis que le graphène vertical est séparé du substrat, et la couche de graphène plate au niveau du fond est utilisée. De plus, le polymère à haut poids moléculaire peut protéger et durcir le graphène vertical et la substance active chargée sur la surface afin d'augmenter la durée de vie du matériau. De plus, en ajustant la structure des pores d'un film mince de polymère à haut poids moléculaire, un échange de substance entre le graphène vertical et le monde extérieur est facilité, et l'efficacité de réaction est améliorée. L'invention concerne également un procédé de préparation d'un matériau composite de graphène vertical-polymère à haut poids moléculaire.
PCT/CN2020/072297 2019-05-24 2020-01-15 Matériau composite de graphène vertical-polymère à haut poids moléculaire et procédé de préparation s'y rapportant WO2020238260A1 (fr)

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CN112218496B (zh) * 2020-10-10 2021-08-17 江南大学 一种热整流器件及在调控石墨烯热整流效应中的应用
CN112520729B (zh) * 2020-12-04 2022-08-26 杭州高烯科技有限公司 一种石墨烯基太赫兹分子检测器件及其制备方法
CN113410335B (zh) * 2021-06-17 2022-10-21 河北大学 一种空穴传输层的制备方法及晶硅太阳电池
CN113921826B (zh) * 2021-10-09 2023-08-04 深圳石墨烯创新中心有限公司 一种直立石墨烯/纳米银复合材料及其制备方法和应用
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