CN110564087B - Vertical graphene-high molecular polymer composite material and preparation method thereof - Google Patents

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

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CN110564087B
CN110564087B CN201910439964.9A CN201910439964A CN110564087B CN 110564087 B CN110564087 B CN 110564087B CN 201910439964 A CN201910439964 A CN 201910439964A CN 110564087 B CN110564087 B CN 110564087B
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molecular polymer
graphene
vertical graphene
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CN110564087A (en
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郑伟
赵鑫
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Shenzhen Yixin Technology R & D Co ltd
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Abstract

The invention belongs to the technical field of graphene composite materials, and particularly relates to a vertical graphene-high molecular polymer composite material which comprises a substrate, vertical graphene and a high molecular polymer, wherein the vertical graphene grows on the surface of the substrate, and the high molecular polymer is solidified into a film and is uniformly loaded on the surface and the edge of the vertical graphene. Compared with the prior art, the vertical graphene-high molecular polymer composite material provided by the invention keeps the unique appearance and the ultra-large surface area of the vertical graphene while being separated from the substrate, and utilizes the planar graphene layer at the bottom of the vertical graphene. Meanwhile, the high molecular polymer can protect and solidify the vertical graphene and active substances loaded on the surface, so that the service life of the material is prolonged, and in addition, the pore structure of the high molecular polymer film is adjusted, so that the vertical graphene is promoted to exchange with external substances, and the reaction efficiency is improved. The invention also discloses a preparation method of the 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
Since the upright graphene is successfully prepared in 2003, the star material is easy to industrially produce and has excellent performance due to the special structure. The material which directly grows on the surface of the substrate without adhesive has huge specific surface area and micro mechanical strength. Researches show that the vertical graphene has wide application prospects, such as application in the fields of catalyst loading, biosensors, energy storage, electrochemical electrodes, flexible electrodes, transparent electrodes, heating, heat conduction and the like.
However, as a nano material, the vertical graphene is macroscopically fragile, is afraid of scraping and wiping, is not resistant to direct contact of foreign matters, and even strong airflow, water flow and the like can destroy the vertical morphology and microstructure of the vertical graphene, and the large surface area is also easy to be contaminated by various pollutants such as dust and the like, so that the active substance loses effectiveness. In addition, as the nano-material vertical graphene grows on the surface of a high-temperature-resistant substrate in situ, the substrate materials are often thick, heavy and firm, and if the unique structure of the vertical graphene is required to be maintained, the structure of the vertical graphene is damaged by means of the substrate, powder scraping and stripping and the like. The application of the vertical graphene is greatly limited by the substrate, and the application potential of the vertical graphene is limited in many aspects. Therefore, the surface of the vertical graphene is protected, the vertical graphene sheet layer is prevented from being directly contacted with foreign matters, the contact chance with external pollutants is reduced, the storage rate of active ingredients is improved, the application scene of the vertical graphene is remarkably expanded, and the service life is prolonged, so that the hard requirement of application and development of the vertical graphene is met. In addition, the application field of the vertical graphene nano structure can be greatly expanded if the vertical graphene nano structure exists apart from the substrate which grows in situ.
The production process of graphene can be divided into three major categories, namely a graphite swelling method, an oxidation-reduction method and a chemical vapor deposition in-situ growth method. The chemical vapor deposition in-situ growth method is characterized in that a carbon source gas is cracked, carbon elements are deposited into graphene, few layers or single-layer graphene can be grown through the pilot production process, no pollution is caused, and impurities are almost zero. The vertical graphene grown by the plasma enhanced chemical vapor deposition method vertically grows on the surface of the substrate, has a large surface area and a special spatial appearance, and simultaneously keeps a planar graphene layer.
High molecular weight polymers fall into many classes, and the general characteristics include: the graphene can be prepared into micron or submicron films, has certain strength and elasticity, small density, acid and alkali resistance, softness and good light transmittance, and can well protect the vertical graphene. Meanwhile, the high molecular polymer film can solidify active substances such as enzyme, catalyst and the like, so that the active substances cannot be easily peeled off and fall off. In the application of the vertical graphene, besides a better protective layer and the solidification of active substances, the protective layer is required to have a certain pore structure, so that the material exchange between the vertical graphene and the outside is facilitated, for example, the application in the fields of sensing and energy storage is realized. The pore structure of different high molecular polymer films is controllable within a certain range according to different preparation conditions. If the vertical graphene sheet layer is embedded into the high polymer film to prepare the composite material with the functions of protecting, supporting, solidifying active substances and conveying pore channels, multiple purposes can be achieved.
In view of the above, the present invention aims to provide a vertical graphene/high molecular polymer and a preparation method thereof, which can maintain the unique morphology and the ultra-large surface area of the vertical graphene while the vertical graphene is separated from the growth substrate thereof, and effectively utilize and expose the planar graphene on the bottom layer of the vertical graphene during in-situ growth. Meanwhile, the fragile structure of the vertical graphene is better protected by the high molecular polymer film, the active substances loaded on the surface of the vertical graphene can be protected and cured, the vertical graphene is prevented from falling off, and the service life is prolonged. Furthermore, the pore structure of the high molecular polymer film is adjusted and controlled, so that the material exchange between the vertical graphene and the outside is facilitated, and the reaction efficiency of the vertical graphene is improved.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the upright graphene-high molecular polymer composite material is provided, the unique appearance and the ultra-large surface area of the upright graphene can be kept while the composite material is separated from the growth substrate of the upright graphene, and the planar graphene layer at the bottom of the upright graphene is effectively utilized and exposed. Meanwhile, the fragile structure of the vertical graphene is better protected by the high-molecular polymer film, the active substances loaded on the surface of the vertical graphene can be protected and solidified, the vertical graphene is prevented from falling off, the service life is prolonged, and further, the material exchange between the vertical graphene and the outside is facilitated by adjusting and controlling the pore structure of the high-molecular polymer film, so that the reaction efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the vertical graphene-high molecular polymer composite material comprises a substrate, vertical graphene and a high molecular polymer, wherein the vertical graphene grows on the surface of the substrate, and the high molecular polymer is solidified into a film and is uniformly loaded on the surface and the edge of the vertical graphene.
As an improvement of the vertical graphene-high molecular polymer composite material, the substrate is a smooth hard material and is at least one of high-conductivity carbon paper, polished silicon wafers, polished quartz plates, magnesium oxide, silicon dioxide, aluminum oxide and aluminum nitride, so that the vertical graphene-high molecular polymer composite material can be conveniently peeled from the substrate.
As an improvement of the vertical graphene-high molecular polymer composite material, the vertical graphene is prepared by a plasma assisted chemical vapor deposition method under low pressure, and the structure of the vertical graphene comprises a planar graphene layer close to a substrate and a vertical graphene layer embedded in a high molecular polymer.
As an improvement of the upright graphene-high molecular polymer composite material, the thickness of the planar graphene layer is 2 nm-30 nm, the height of the upright graphene layer is 10 nm-20 mu m, and the specific surface area is 1000-2600 m2And/g, other morphological characteristics such as density and bending can be modulated.
As an improvement of the vertical graphene-high molecular polymer composite material, the coverage rate of a film of the high molecular polymer on the surface and the edge of the vertical graphene can be controlled to be 0-100%, the thickness can be controlled to be 0.1-500 mu m, the hole rate can be controlled to be more than 0-90%, and the typical hole linearity is 10 nm-10 mu m.
As an improvement of the vertical graphene-high molecular polymer composite material, the high molecular polymer is at least one of PVDF, PS, PE, PDMS, PMMA, Nafion, PEO, PP, PVC, PVB, PES, PA, PI, PO, 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 comprises the following steps:
firstly, putting a substrate into a vacuum chamber of a plasma chemical vapor deposition device, introducing reducing gas, maintaining a low-pressure state in the device through flow regulation, and carrying out plasma etching on the substrate;
secondly, introducing protective gas after the etching reaction is finished, introducing a carbon source and buffer gas after the temperature is raised, and maintaining the low-pressure state in the device through flow regulation;
thirdly, carrying out plasma chemical vapor deposition reaction on the etched substrate, and after the reaction is finished, cooling the equipment to room temperature, so that the vertical graphene can grow on the surface of the substrate;
fourthly, preparing a high molecular polymer solution;
fifthly, coating the high molecular polymer solution on the surface and the edge of the vertical graphene;
and sixthly, curing and film-forming the high molecular polymer coated on the surface and the edge of the vertical graphene to obtain the vertical graphene-high molecular polymer composite material.
As an improvement of the method, the reducing gas is at least one of hydrogen and argon, and the vacuum degree is stabilized at 5-30 Pa in the low-pressure state.
As an improvement of the method, the protective gas is at least one of nitrogen and argon, the carbon source is at least one of methane, ethane, ethylene, propylene, acetylene, methanol, ethanol, acetone, benzene, toluene, xylene and benzoic acid, and the buffer gas is at least one of hydrogen and argon.
As an improvement of the method, the ion source of the plasma is at least one of radio frequency plasma, microwave plasma or direct current 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, the reaction temperature of the plasma chemical vapor deposition reaction is 400-1500 ℃, and preferably 690-950 ℃.
As an improvement of the method, the etching reaction time is 1-30 min, and the plasma chemical vapor deposition reaction time is 3-200 min.
As an improvement of the method of the present invention, 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, and a solution with a lead agent, wherein the high molecular polymer is at least one of PVDF, Nafion, PE, PP, PVC, PS, PC, PET, PI, PVDC, PAN, PU, PEO, PO, PVB, and PES, or the high molecular polymer is melted into a liquid state at a higher temperature, the high molecular polymer is at least one of PE, PP, ABS, PET, PES, and PPS, or the high molecular polymer particles are dispersed and suspended in a medium liquid, the high molecular polymer is at least one of PP, PS, PTFE, and PEDOT, or the high molecular polymer is at least one of PA, PMMA, PANI, PDMS, PT, Polyfluorene, and an epoxy resin to form a generation stock solution of a target high molecular polymer through a mixing reaction of different chemical raw materials.
Is prepared by mixing high molecular polymer, additives and solvents with different components and proportions through heating, melting, mixing and stirring.
As an improvement of the method of the invention, the method for coating the high molecular polymer solution is spin coating, drop plating, knife edge rolling, electrochemical plating, spraying, electro-spinning, screen printing or printing.
As an improvement of the method, the method for curing the high molecular polymer into the film comprises at least one of natural placement at normal temperature, high-temperature placement, drying placement, vacuum placement, water washing, ultraviolet curing and additive curing, and the curing time is 0.1-10 hours.
As a further improvement of the method, the vertical graphene-high molecular polymer composite material can load active substances on the surface of the vertical graphene or strip the vertical graphene-high molecular polymer composite material from a growth substrate according to application requirements.
Compared with the prior art, the invention has at least the following beneficial effects:
1. aiming at different high polymer materials, the existing mature coating method in the industry and scientific research is used, new process, flow and method do not need to be developed, the preparation process is simple, the operation is convenient, the energy is saved, the environment is protected, and the method is suitable for large-scale production.
2. According to the invention, the vertical graphene is embedded into the high-molecular polymer, so that the vertical graphene which is a nano material with fragile macroscopic dimensions is effectively protected, the damage caused by scraping, rubbing, touching and touching can be effectively avoided, the transportation, packaging and cutting of the vertical graphene are increased, the operability of a device is further improved, and the service life of the vertical graphene is prolonged.
3. According to the invention, the vertical graphene is embedded into the high-molecular polymer, so that the nano material with fragile macroscopic dimension can be separated from the growth substrate and independently exists, the unique appearance and the super-large surface area of the nano material are preserved, and the application scene is wider.
4. According to the invention, the vertical graphene can be peeled off from the substrate, so that the planar graphene layer positioned at the bottom layer of the vertical graphene is exposed outside, the planar graphene layer is utilized, and the application field of the vertical graphene is further expanded.
5. According to the invention, the unique structure and the large surface area of the vertical graphene are protected by preserving the special pore channel structure of the high molecular polymer, and the vertical graphene can be ensured to exchange substances with the outside, and different high molecular polymers have different pore channel structures according to different film forming processes, so that the method is suitable for different application occasions.
6. The high molecular polymer can also solidify active substances loaded on the surface of the vertical graphene, such as the platinum nanoparticles and the catalytic enzyme, so that the active substances are prevented from falling off, the activity loss of the active substances is effectively prevented, and the reduction of the efficiency of the active substances due to agglomeration in use is avoided, thereby prolonging the service life.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the graphene of the present invention.
Fig. 2 is a SEM top view of the upright graphene-Nafion composite obtained in example 1 of the present invention.
Fig. 3 is a SEM image of a bottom planar graphene layer after the upright graphene-PVDF composite obtained in example 2 of the invention is detached from the growth substrate.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A vertical graphene-Nafion composite material comprises a high-conductivity carbon paper substrate, vertical graphene and a high-molecular polymer Nafion. The vertical graphene grows on the surface of the high-conductivity carbon paper substrate, and the high-molecular polymer Nafion is uniformly loaded on the surface and the edge of the vertical graphene.
The vertical graphene comprises two parts, namely a planar graphene layer close to a substrate and a vertical graphene layer embedded in a high molecular polymer.
A preparation method of a vertical graphene-Nafion composite material at least comprises the following steps:
step one, putting the high-conductivity carbon paper into a vacuum chamber of a plasma chemical vapor deposition device, and 1: 1, introducing reducing gases of hydrogen and argon, maintaining a low-pressure state in a device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the high-conductivity carbon paper, wherein the reaction time is 10min, and the power density of plasma equipment is 10 watts per square centimeter;
and step two, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the highly conductive carbon paper, wherein the reaction time is 15min, the power density provided by plasma equipment is 10 watts per square centimeter, and after the reaction is finished, the temperature of the equipment is reduced to room temperature, so that the highly conductive carbon paper on which the upright graphene grows is obtained;
fourthly, preparing 15wt% Nafion formaldehyde solution;
fifthly, uniformly dripping 15wt% of Nafion formaldehyde solution in the center of the high-conductivity carbon paper on which the vertical graphene grows, and spin-coating for 15 seconds by a spin-coating machine at the rotating speed of 500 RPM;
and sixthly, standing the high-conductivity carbon paper in the air at room temperature for 5 hours to enable the Nafion to be solidified into a film, and thus obtaining the vertical graphene-Nafion composite material.
FIG. 1 is an SEM image of a vertical graphene prepared by the method, wherein the average thickness of the vertical graphene layer is 2 μm, the average thickness of the planar graphene layer is 2nm, and the prepared vertical graphene is flatThe average specific surface area is 1300m2(ii) in terms of/g. Fig. 2 is a SEM top view of the vertical graphene-Nafion composite material prepared in this embodiment, in which a high molecular polymer Nafion covers and protects a vertical graphene structure, and can embody a certain vertical graphene structural profile. The thickness of the Nafion film in this example 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 lightly touched, cut and operated by hands without damaging the vertical graphene structure. The vertical graphene-Nafion composite material in the embodiment is used as an electrochemical electrode, the sensitivity reaches 80% of that of an unloaded Nafion and exposed vertical graphene electrode in various electrochemical experiments, and the Nafion film is proved to have excellent ion transmittance and be capable of perfectly protecting the structure of the vertical graphene. Meanwhile, due to the protection of Nafion, the service life of the electrode reaches more than 500h, and the stability is greatly improved. Has revolutionary application prospect in a new generation of biochemical sensors for hydrogen peroxide metabolism.
Example 2
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
the first step, putting the polished silicon wafer into a vacuum chamber of a plasma chemical vapor deposition device, 1: 1, introducing reducing gases of hydrogen and argon, maintaining the low-pressure state in the device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on a substrate for 10min, wherein the power density of plasma equipment is 10 watts per square centimeter;
and step two, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the polished silicon wafer for 15min, wherein the power density provided by plasma equipment is 10 watts per square centimeter, and obtaining the polished silicon wafer on which the upright graphene grows after the reaction is finished and the temperature of the equipment is reduced to room temperature;
fourthly, preparing a high molecular polymer PVDF/PEO solution, mixing 8% PVDF and 2% PEO powder by weight ratio with 90% NMP solution, uniformly stirring, standing in an oven at 80 ℃ for 2 hours to obtain a transparent solution, adding 1/20 volumes of glycerol, and uniformly stirring;
fifthly, uniformly pouring the PVDF/PEO solution onto a polished silicon wafer on which the vertical graphene grows, and spin-coating for 30s by a spin coater at the rotating speed of 1000 RPM;
sixthly, placing the polished silicon wafer in an oven at 100 ℃ for 2h to solidify PVDF/PEO into a film;
and seventhly, peeling the vertical graphene-PVDF/PEO composite material from the polished silicon wafer integrally, and then placing the polished silicon wafer in purified water for standing for 2 hours to obtain the vertical graphene-PVDF/PEO composite material with the pore channel structure.
Fig. 3 is a SEM image of the bottom planar graphene layer after the upright graphene-PVDF/PEO composite prepared in this example is detached from the polished silicon wafer. The thickness of the PVDF/PEO film is about 5 mu m, the upright type graphene is uniformly embedded in the PVDF/PEO film, the planar graphene layer at the bottom of the upright type graphene is smooth and flat and is completely exposed outside, the hole rate of the PVDF/PEO layer is 60%, and the average hole diameter is 4 mu m. The ionic conductivity of the vertical graphene-PVDF/PEO composite material prepared by the embodiment in 1M LiClO4/PC reaches 1.2mS/cm2. By combining the extremely large surface area of the vertical graphene, the vertical graphene-PVDF/PEO composite material prepared by the embodiment can be used for energy storage devices such as a new-generation graphene supercapacitor.
Example 3
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
step one, putting the high-conductivity carbon paper into a vacuum chamber of a plasma chemical vapor deposition device, and 1: 1, introducing reducing gases of hydrogen and argon, maintaining a low-pressure state in a device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the high-conductivity carbon paper, wherein the reaction time is 10min, and the power density of plasma equipment is 10 watts per square centimeter;
and step two, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the highly conductive carbon paper, wherein the reaction time is 15min, the power density provided by plasma equipment is 10 watts per square centimeter, and after the reaction is finished, the temperature of the equipment is reduced to room temperature, so that the highly conductive carbon paper on which the upright graphene grows is obtained;
fourthly, selecting a platinum target material, placing the obtained material in a physical vapor deposition device, and vacuumizing to 2x10-3pa, filling argon to stabilize the air pressure at 5pa, and starting magnetron sputtering, wherein the power is 0.7W/cm2, and the time is 10 s;
fifthly, after the magnetron sputtering is finished, filling argon to 1x105pa, raising the temperature to 300 ℃, keeping the temperature for 30min, and carrying out annealing treatment, wherein after the annealing reaction is finished, the temperature of the equipment is reduced to room temperature, namely platinum nanoparticles are loaded on the surface of the vertical graphene;
sixthly, preparing 15wt% Nafion formaldehyde solution;
seventhly, uniformly dripping 15wt% of Nafion formaldehyde solution in the center of the high-conductivity carbon paper on which the vertical graphene grows, and spin-coating for 15 seconds by a spin coater at the rotating speed of 500 RPM;
and step eight, standing the high-conductivity carbon paper in the air at room temperature for 5 hours to enable Nafion to be solidified into a film, and obtaining the vertical graphene-Nafion composite material.
The average specific surface area of the graphene prepared by the embodiment is about 1300m2/g, the particle size of the supported platinum nanoparticles is less than 2nm, and the supporting amount is 1mg/cm2The loading capacity is reduced by 3 orders of magnitude compared with the similar products, and the use amount of noble metal is greatly reduced.
Example 4
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
the first step, putting the polished silicon wafer into a vacuum chamber of a plasma chemical vapor deposition device, 1: 1 introducing reducing gases of hydrogen and argon, maintaining the low-pressure state in the device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the polished silicon wafer for 10min, wherein the power density of plasma equipment is 10 watts per square centimeter;
secondly, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, introducing methane after heating, maintaining the low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the polished silicon wafer, wherein the reaction time is 15min, the power density provided by plasma equipment is 10 watts per square centimeter, and after the reaction is finished, the temperature of the equipment is reduced to room temperature to obtain the polished silicon wafer on which the upright graphene grows;
fourthly, preparing a high molecular polymer PDMS solution, wherein the mass ratio of the PDMS main agent to the hardening agent is 10: 1, mixing and stirring uniformly;
fifthly, uniformly pouring the PDMS solution on a polished silicon wafer on which the vertical graphene grows, and spin-coating for 30s by a spin coater at the rotating speed of 500 RPM;
sixthly, placing the polished silicon wafer in an oven at 60 ℃ for 2h to cure PDMS into a film;
and seventhly, peeling the whole vertical graphene-PDMS composite material off the polished silicon wafer to obtain the vertical graphene-PDMS composite material.
The thickness of the PDMS film prepared in the embodiment is 10 mu m, and the upright graphene is uniformly embedded in the PDMS. The initial material resistance was 90 ohms/square, the resistance after 20% stretch was about 800 ohms/square, and the conductivity remained after 100% stretch. When the stretching amplitude is 10 percent and the stretching is repeated for 1000 times, the resistance of the material only rises by 30 percent. The bending, curling and folding of the diameter larger than two millimeters do not affect the conductivity of the upright graphene-PDMS composite material of the embodiment. The vertical graphene-PDMS composite material prepared by the embodiment can be used as a flexible and stretchable electrode material and can be applied to new generation wearable electronics.
Example 5
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
the first step, putting the polished silicon wafer into a vacuum chamber of a plasma chemical vapor deposition device, 1: 1 introducing reducing gases of hydrogen and argon, maintaining the low-pressure state in the device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the polished silicon wafer for 10min, wherein the power density of plasma equipment is 10 watts per square centimeter;
and secondly, introducing argon after the etching reaction is finished, heating to 700 ℃ at a heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the polished silicon wafer for 15min, wherein the power density provided by plasma equipment is 10 watts per square centimeter, and obtaining the polished silicon wafer on which the upright graphene grows after the reaction is finished and the temperature of the equipment is reduced to room temperature;
fourthly, preparing two solutions which are respectively: 0.45 mL of phytic acid, 0.40 mL of aniline, 2mL of a distilled water mixed solution, and 0.24g of ammonium persulfate dissolved in 0.85mL of an aqueous solution. Placing in two containers respectively, and cooling to 4 deg.C in refrigerator;
fifthly, mixing the two solutions quickly, pouring the mixed solution on the surface of a polished silicon wafer with the vertical graphene growing thereon uniformly, and performing edge extension coating by using the distance between the edge of a scraper and the surface of the polished silicon wafer of 1 mm;
and sixthly, naturally standing the polished silicon wafer at normal temperature for 1h to solidify the PANI hydrogel into a film, thus obtaining the vertical graphene-PANI hydrogel composite material.
According to the upright graphene-PANI hydrogel composite material prepared by the embodiment, the upright graphene is coated and protected by the jelly-like PANI hydrogel, and the PANI hydrogel has strong adsorption performance due to the excellent pore channel structure, so that the composite material can further adsorb enzyme, catalyst and solution to be detected, and is widely applied to the field of biochemical detection.
Example 6
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
step one, putting conductive graphite paper into a vacuum chamber of a plasma chemical vapor deposition device, and 1: 1, introducing reducing gases of hydrogen and argon, maintaining the low-pressure state in the device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the conductive graphite paper, wherein the reaction time is 10min, and the power density of plasma equipment is 10 watts per square centimeter;
and step two, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the conductive graphite paper, wherein the reaction time is 15min, the power density provided by plasma equipment is 10 watts per square centimeter, and after the reaction is finished, the temperature of the equipment is reduced to room temperature to obtain the conductive graphite paper on which the upright graphene grows;
fourthly, preparing a PEDOT/PSS aqueous solution with a formula of 10mM PEDOT and 2wt% PSS;
fifthly, placing the conductive graphite paper with the upright graphene in a PEDOT/PSS aqueous solution at a rate of 5mA/mm2Current density plating for 400 s;
and sixthly, standing the conductive graphite carbon paper for 5 hours at normal temperature to solidify PEDOT into a film, thus obtaining the vertical graphene-PEDOT composite material.
The thickness of the PEDOT thin film prepared in this example is 1 μm, and the PEDOT thin film is uniformly attached to the surface of the upright graphene. The thickness of the coating can be accurately controlled through electroplating, and the PEDOT film obtained through electroplating has strong adhesive force.
Example 7
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
step one, putting conductive graphite paper into a vacuum chamber of a plasma chemical vapor deposition device, and 1: 1, introducing reducing gases of hydrogen and argon, maintaining the low-pressure state in the device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the conductive graphite paper, wherein the reaction time is 10min, and the power density of plasma equipment is 10 watts per square centimeter;
and step two, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the conductive graphite paper, wherein the reaction time is 15min, the power density provided by plasma equipment is 10 watts per square centimeter, and after the reaction is finished, the temperature of the equipment is reduced to room temperature to obtain the conductive graphite paper on which the vertical graphene grows;
and fourthly, mixing the PTFE concentrated dispersion liquid with a PVA aqueous solution, and controlling the mass ratio of PTFE to PVA to be 7: 3, stirring uniformly;
fifthly, using an electrospinning spray head with the inner diameter of 0.6mm, wherein the distance between the spray head and the conductive graphite paper on which the vertical graphene grows is about 10cm, applying 10kV voltage to the spray head and the conductive graphite paper, and carrying out electrospinning for 10min at the flow velocity of the electrospinning spray head of 20 mu L/min;
and sixthly, sintering the electro-spun conductive graphite carbon paper in a muffle furnace at 300 ℃ for 5min, removing PVA (polyvinyl alcohol) components, and solidifying PTFE (polytetrafluoroethylene) into a film to obtain the vertical graphene-PTFE composite material.
The diameter of the PTFE fiber prepared in the embodiment is 500nm, the PTFE fiber is interwoven to form a film and uniformly covers the surface of the vertical graphene, and the average hole diameter is 5 μm. The PTFE fiber has excellent ion transmittance while protecting the vertical graphene. Meanwhile, the vertical graphene-PTFE composite material prepared by the embodiment has very strong hydrophobic and anti-fouling performances.
Example 8
Different from the embodiment 1, the method for preparing the vertical graphene/high molecular polymer composite material at least comprises the following steps:
the first step, putting the polished silicon wafer into a vacuum chamber of a plasma chemical vapor deposition device, 1: 1 introducing reducing gases of hydrogen and argon, maintaining the low-pressure state in the device through flow regulation to ensure that the vacuum degree is stabilized at 15Pa, and carrying out plasma etching reaction on the polished silicon wafer for 10min, wherein the power density of plasma equipment is 10 watts per square centimeter;
and step two, introducing argon after the etching reaction is finished, heating to 700 ℃ at the heating rate of 20 ℃/min, and heating to 1: 1, introducing hydrogen and methane, maintaining a low-pressure state in the device through flow regulation, and keeping the vacuum degree at 15 Pa;
thirdly, carrying out plasma chemical vapor deposition reaction on the polished silicon wafer for 15min, wherein the power density provided by plasma equipment is 10 watts per square centimeter, and obtaining the polished silicon wafer on which the upright graphene grows after the reaction is finished and the temperature of the equipment is reduced to room temperature;
fourthly, preparing a molten PMMA liquid, wherein the temperature of the liquid is 150 ℃;
fifthly, preheating the polished silicon wafer with the vertical graphene grown and a tray of a spin coater at 150 ℃, then rapidly installing the polished silicon wafer and the tray of the spin coater on the spin coater, uniformly pouring the molten PMMA solution on the surface of the polished silicon wafer, and spin-coating at the rotating speed of 100RPM for 20 s;
and sixthly, standing the polished silicon wafer for 1 hour at normal temperature to solidify PMMA into a film, thus obtaining the vertical graphene-PMMA composite material.
The thickness of the vertical graphene-PMMA composite material prepared by the embodiment is about 30 micrometers, and the vertical graphene-PMMA composite material has high hardness.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (14)

1. The vertical graphene-high molecular polymer composite material is characterized by comprising a substrate, vertical graphene and a high molecular polymer, wherein the vertical graphene grows on the surface of the substrate, and the high molecular polymer is solidified into a film and uniformly loaded on the surface and the edge of the vertical graphene;
the preparation method of the vertical graphene-high molecular polymer composite material at least comprises the following steps:
firstly, putting a substrate into a vacuum chamber of a plasma chemical vapor deposition device, introducing reducing gas, maintaining a low-pressure state in the device through flow regulation, and carrying out plasma etching on the substrate;
secondly, introducing protective gas after the etching reaction is finished, introducing a carbon source and buffer gas after the temperature is raised, and maintaining the low-pressure state in the device through flow regulation;
thirdly, carrying out plasma chemical vapor deposition reaction on the etched substrate, and after the reaction is finished, cooling the equipment to room temperature, so that the vertical graphene can grow on the surface of the substrate;
fourthly, preparing a high molecular polymer solution;
fifthly, coating the high molecular polymer solution on the surface and the edge of the vertical graphene;
sixthly, curing and film-forming the high molecular polymer coated on the surface and the edge of the vertical graphene to obtain a vertical graphene-high molecular polymer composite material;
wherein the vacuum degree in the low-pressure state is stabilized at 5Pa to 30Pa, and the power density provided by the plasma equipment is 1 watt to 50 watts per square centimeter;
the vertical graphene is prepared by a plasma assisted chemical vapor deposition method under low pressure, and structurally comprises a planar graphene layer close to a substrate and a vertical graphene layer embedded with a high polymer;
the thickness of the planar graphene layer is 2-30 nanometers, and the vertical grapheneThe height of the layer is 0.01 to 20 μm, and the specific surface area is 1000 to 2600m2The density and the bending degree of the product can be modulated.
2. The graphene-high molecular weight polymer composite material according to claim 1, wherein the substrate is a smooth and hard material, and is at least one of highly conductive carbon paper, polished silicon wafer, polished quartz plate, magnesium oxide, silicon dioxide, aluminum oxide, and aluminum nitride, for facilitating peeling of the graphene-high molecular weight polymer composite material from the substrate, and the substrate is also a high temperature resistant conductive material, and is at least one of conductive carbon paper, graphite paper, carbon cloth, metal foil, and metal mesh for facilitating a device conduction circuit.
3. The graphene-high molecular polymer composite material according to claim 1, wherein the coverage rate of the thin film of the high molecular polymer on the surface and the edge of the graphene is controlled to be 0-100%, the thickness is controlled to be 0.1-500 μm, the porosity is controlled to be 0-90%, and the porosity is 0.01-10 μm.
4. The graphene-polymer composite material according to claim 1, wherein the polymer is at least one of PVDF, PS, PE, PDMS, PMMA, Nafion, PEO, PP, PVC, PVB, PES, PA, PI, PO, PC, PU, PTFE, PAN, PANI, PEDOT, PT, Polyfluorene, PVDC, PET, PPS, ABS, and epoxy resin.
5. The method for preparing a vertical graphene-high molecular polymer composite material according to any one of claims 1 to 4, comprising at least the steps of:
firstly, putting a substrate into a vacuum chamber of a plasma chemical vapor deposition device, introducing reducing gas, maintaining a low-pressure state in the device through flow regulation, and carrying out plasma etching on the substrate;
secondly, introducing protective gas after the etching reaction is finished, introducing a carbon source and buffer gas after the temperature is raised, and maintaining the low-pressure state in the device through flow regulation;
thirdly, carrying out plasma chemical vapor deposition reaction on the etched substrate, and after the reaction is finished, cooling the equipment to room temperature, so that the vertical graphene can grow on the surface of the substrate;
fourthly, preparing a high molecular polymer solution;
fifthly, coating the high molecular polymer solution on the surface and the edge of the vertical graphene;
and sixthly, curing and film-forming the high molecular polymer coated on the surface and the edge of the vertical graphene to obtain the vertical graphene-high molecular polymer composite material.
6. The method according to claim 5, wherein the reducing gas is at least one of hydrogen and argon, and the low-pressure state is a state in which a degree of vacuum is stabilized at 5 to 30 Pa.
7. The method according to claim 5, wherein the protective gas is at least one of nitrogen and argon, the carbon source is at least one of methane, ethane, ethylene, propylene, acetylene, methanol, ethanol, acetone, benzene, toluene, xylene, and benzoic acid, and the buffer gas is at least one of hydrogen and argon.
8. The preparation method according to claim 5, wherein the ion source of the plasma is at least one of radio frequency plasma, microwave plasma or direct current high voltage plasma, and the power density provided by the plasma equipment is 1-50 watts per square centimeter.
9. The method according to claim 5, wherein the reaction temperature of the plasma chemical vapor deposition reaction is 690-950 ℃.
10. The method according to claim 5, wherein the etching reaction time is 1-30 min, and the plasma chemical vapor deposition reaction time is 3-200 min.
11. The method according to claim 5, wherein the method for preparing the solution of the high molecular polymer comprises dissolving the high molecular polymer in an organic solution, an aqueous solution, a mixed solution, or a solution containing a precursor, wherein the high molecular polymer is at least one of PVDF, Nafion, PE, PP, PVC, PS, PC, PET, PI, PVDC, PAN, PU, PEO, PO, PVB, and PES, or the high molecular polymer is melted into liquid at higher temperature, the high molecular polymer is at least one of PE, PP, ABS, PET, PES and PPS, or high molecular polymer particles are dispersed and suspended in the medium liquid, the high molecular polymer is at least one of PP, PS, PTFE and PEDOT, or mixing different chemical materials for reaction to obtain the target high molecular polymer solution, wherein the high molecular polymer is at least one of PA, PMMA, PANI, PDMS, PT, Polyfluorene and epoxy resin.
12. The method according to claim 5, wherein the solution of the high molecular weight polymer is applied by spin coating, drop plating, knife-edge rolling, electrochemical plating, spray coating, electro-spraying, electro-spinning, screen printing or printing.
13. The preparation method according to claim 5, wherein the high molecular polymer is cured to form a film by at least one of natural standing at normal temperature, standing at high temperature, drying and standing, standing in vacuum, washing with water, ultraviolet curing and additive curing, and the curing time is 0.1-10 h.
14. The preparation method according to claim 5, wherein the vertical graphene-high molecular polymer composite material can be used for loading an active substance on the surface of the vertical graphene or peeling the vertical graphene-high molecular polymer composite material from a growth substrate according to application requirements.
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