阅读说明：本技术 一种直立型石墨烯-高分子聚合物复合材料及其制备方法 (Vertical graphene-high molecular polymer composite material and preparation method thereof ) 是由 郑伟 赵鑫 于 2019-05-24 设计创作，主要内容包括：本发明属于石墨烯复合材料技术领域,尤其涉及一种直立石墨烯-高分子聚合物复合材料,包括衬底、直立型石墨烯和高分子聚合物,所述直立型石墨烯生长于衬底表面,所述高分子聚合物固化成膜并均匀负载于直立型石墨烯表面和边缘。相对于现有技术,本发明提供的直立型石墨烯-高分子聚合物复合材料,在脱离衬底的同时,保持直立型石墨烯的独特形貌和超大表面积,并利用其底部的平面石墨烯层。同时,高分子聚合物可对直立型石墨烯和表面负载的活性物质进行保护固化,增加材料使用寿命,此外,通过调节高分子聚合物薄膜的孔道结构,促进直立型石墨烯与外界的物质交换,提高反应效率。本发明还公开了一种直立石墨烯-高分子聚合物复合材料的制备方法。(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.)

1. 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.

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 of claim 1, wherein the graphene is prepared by a plasma assisted chemical vapor deposition method under low pressure, and the structure of the graphene-high molecular polymer composite material comprises two parts, namely a planar graphene layer close to a substrate and a vertical graphene layer embedded in a high molecular polymer.

4. the vertical graphene ~ high molecular polymer composite material according to claim 1, wherein the thickness of the planar graphene layer is 2nm ~ 30nm, the height of the vertical graphene layer is 10nm ~ 20 μm, and the specific surface area is 1000 ~ 2600m²and/g, other morphological characteristics such as density and bending can be modulated.

5. the vertical 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 vertical graphene is controlled to be 0 ~ 100%, the thickness is controlled to be 0.1 ~ 500 μm, the porosity is controlled to be more than 0 ~ 90%, and the typical porosity is 10nm ~ 10 μm.

6. 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.

7. the method for preparing a vertical graphene-high molecular polymer composite material according to any one of claims 1 to 6, 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.

8. the method according Pa ~ claim 7, 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 5Pa ~ 30 Pa.

9. The method according to claim 7, 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.

10. 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 direct current high voltage plasma, and the power density provided by the plasma equipment is 1-50 watts per square centimeter.

11. the method of claim 7, wherein the reaction temperature of the plasma chemical vapor deposition reaction is 400 ℃ ~ 1500 ℃, preferably 690 ℃ ~ 950 ℃.

12. the method according to claim 7, wherein the etching reaction time is 1 ~ 30min, and the plasma chemical vapor deposition reaction time is 3 ~ 200 min.

13. The method according to claim 7, 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.

14. the method according to claim 7, 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.

15. the preparation method according to claim 7, 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.

16. The preparation method according to claim 7, 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.

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 2nm ~ 30nm, the height of the upright graphene layer is 10nm ~ 20 mu m, and the specific surface area is 1000 ~ 2600m²and/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 10nm ~ 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 ~ 30min, 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.