Suspended graphene film and preparation method thereof
阅读说明：本技术 一种悬浮石墨烯薄膜及其制备方法 (Suspended graphene film and preparation method thereof ) 是由 李赫然 李青 宋亚滨 于卫昆 孙立红 于 2020-06-24 设计创作，主要内容包括：本发明提供一种悬浮石墨烯薄膜,所述薄膜包括依次层叠放置的底膜、石墨烯层和覆膜,所述底膜包括第一基材层和第一支撑层,所述覆膜包括第二基材层和第二支撑层,所述第一支撑层和所述第二支撑层均位于靠近所述石墨烯层的一面。本发明还提供一种悬浮石墨烯薄膜的制备方法。本发明采用层层组装的技术制备悬浮石墨烯薄膜,采用逐层制备的方法,将球状、线状支撑材料装备到基材上,将石墨烯夹在支撑物之间,形成支撑物-石墨烯-支撑物的三明治结构,其内部结构中石墨烯片有部分即形成悬浮状态。这种结构的悬浮石墨烯薄膜提高了石墨烯薄膜的整体性能,热传导率和电导率相比无悬浮点的石墨烯薄膜有将近40％的提高。(The invention provides a suspended graphene film which comprises a base film, a graphene layer and a laminating film, wherein the base film, the graphene layer and the laminating film are sequentially stacked, the base film comprises a first base material layer and a first supporting layer, the laminating film comprises a second base material layer and a second supporting layer, and the first supporting layer and the second supporting layer are both positioned on one surface close to the graphene layer. The invention also provides a preparation method of the suspended graphene film. The invention adopts the layer-by-layer assembly technology to prepare the suspended graphene film, adopts the layer-by-layer preparation method to equip spherical and linear supporting materials on a base material, and clamps the graphene between supports to form a sandwich structure of the supports, namely the graphene-supports, wherein the graphene sheets in the internal structure are partially in a suspended state. The suspended graphene film with the structure improves the overall performance of the graphene film, and compared with the graphene film without suspended points, the thermal conductivity and the electric conductivity of the suspended graphene film are improved by nearly 40%.)
1. The utility model provides a suspension graphite alkene film, its characterized in that, the film is including the basement membrane, graphite alkene layer and the tectorial membrane of stacking gradually placing, the basement membrane includes first substrate layer and first supporting layer, the tectorial membrane includes second substrate layer and second supporting layer, first supporting layer with the second supporting layer all is located and is close to the one side of graphite alkene layer.
2. The graphene-suspended thin film according to claim 1, wherein the graphene-suspended thin film has a thickness of 1.5 to 4.5 μm.
3. The suspended graphene film of claim 1, wherein the graphene layer thickness is 0.5-1.5 μm.
4. The suspended graphene film according to claim 1, wherein the thickness of the base film is 0.5-1.5 μm.
5. The graphene-suspended thin film according to claim 1, wherein the coating film has a thickness of 0.5 to 1.5 μm.
6. The suspended graphene film according to any one of claims 1 to 5, wherein the material shapes of the first support layer and the second support layer are selected from at least one of the following: granular particles, tubular particles, and linear particles.
7. The graphene-suspended membrane according to claim 6, wherein the particle size of the particulate particles is 0.05-1.45 μm.
8. The graphene suspension film according to claim 6, wherein the tubular particles and the linear particles have a linear diameter of 10-50nm and a linear length of 10-20 μm.
9. The suspended graphene film of any one of claims 1 to 5, wherein at least one of the first substrate layer and the second substrate layer comprises an adhesion layer on a face adjacent to the graphene layer.
10. The suspended graphene film of claim 9, wherein the adhesion layer is comprised of a thermoplastic polymer.
Technical Field
The invention relates to the technical field of material preparation, in particular to a suspended graphene film and a preparation method thereof.
Background
The graphene has excellent performance, so that the graphene is expected to become a subversive material in the fields of future semiconductors and micro-electro-mechanical systems. The application of graphene in various related fields is continuously paid attention and researched, the research on the intrinsic characteristics of graphene becomes the key of high-efficiency application of graphene, but the strong carrier scattering of graphene limits the electron mean free path to be small by 1 μm, and the graphene is a main obstacle of research. In the study of the heat transfer performance of graphene, it is generally considered that heat loss between graphene and layers at both ends of the channel can be ignored. Thus, the non-suspended is as thermally conductive as the suspended graphene. However, research shows that the thermal conductivity of non-suspended graphene is lower than that of suspended graphene due to phonon leakage between the graphene and the substrate interface, and research results show that the thermal conductivity of suspended graphene is 1 time higher than that of common non-graphene.
In the prior art, a conductive material skeleton with a reticular and parallel three-dimensional structure is also built, but the conductive material skeleton is manufactured into sol after being built successfully in a solution and then is coated on a base material, the sol is dried and forms a film without a solvent, the microstructure in the conductive material skeleton is difficult to form an ideal three-dimensional structure, even if a three-dimensional hollow structure is formed, the conductive material skeleton is fixed and filled in the whole film structure by substances such as a binder and the like, the suspension degree cannot be reached, and the performance of the graphene material is limited to the utmost extent.
The preparation of suspended graphene generally adopts a direct growth and transfer method: the direct growth method can avoid introducing impurities and reduce the possibility of damaging the graphene, but the controllability of the method needs to be further researched; the transfer method has the disadvantages of complicated operation flow and high pollution of substrate treatment.
Disclosure of Invention
Based on the defects of the prior art for preparing the suspended graphene, the invention provides a suspended graphene film and a preparation method thereof. The invention adopts the following technical scheme:
1. the utility model provides a suspension graphite alkene film, its characterized in that, the film is including the basement membrane, graphite alkene layer and the tectorial membrane of stacking gradually placing, the basement membrane includes first substrate layer and first supporting layer, the tectorial membrane includes second substrate layer and second supporting layer, first supporting layer with the second supporting layer all is located and is close to the one side of graphite alkene layer.
2. The graphene suspension thin film according to item 1, wherein the graphene suspension thin film has a thickness of 1.5 to 4.5 μm.
3. The suspended graphene film according to item 1, wherein the graphene layer thickness is 0.5 to 1.5 μm.
4. The suspended graphene film according to item 1, wherein the thickness of the base film is 0.5 to 1.5 μm.
5. The suspended graphene thin film according to item 1, wherein the thickness of the coating film is 0.5 to 1.5 μm.
6. The graphene suspension film according to any one of claims 1 to 5, wherein the material shapes of the first support layer and the second support layer are selected from at least one of the following: granular particles, tubular particles, and linear particles.
7. The graphene suspension thin film according to item 6, wherein the particle size of the particulate particles is 0.05 to 1.45 μm.
8. The suspended graphene film according to item 6, wherein the tubular particles and the linear particles have a linear diameter of 10 to 50nm and a linear length of 10 to 20 μm.
9. The suspended graphene film according to any one of claims 1 to 5, wherein at least one of the first substrate layer and the second substrate layer includes an adhesive layer on a face close to the graphene layer.
10. The suspended graphene film of item 9, wherein the adhesion layer is comprised of a thermoplastic polymer.
11. The suspended graphene film according to
12. The graphene suspension film according to any one of claims 1 to 5, wherein the materials of the first support layer and the second support layer are each selected from at least one of the following: carbon black, silicon dioxide, polystyrene, polymethyl methacrylate, carbon nano tubes, silver nano wires, SiO2 nano wires and TiO2 nano wires.
13. The suspended graphene thin film according to claim 12, wherein the carbon black, the silica, the polystyrene and the polymethyl methacrylate are in a granular shape, the particle size is 0.05-2 μm, the carbon nanotube, the silver nanowire, the SiO2 nanowire and the TiO2 nanowire are in a linear shape, the linear diameter size is 10-50nm, and the linear length is 10-20 μm.
14. The suspended graphene film according to any one of claims 1 to 5, wherein the material of each of the first substrate layer and the second substrate layer is at least one selected from the group consisting of: polycarbonate, polyvinyl chloride, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride. 15. A preparation method of a suspended graphene film is characterized by comprising the following steps:
preparing a graphene aqueous solution;
preparing an aqueous solution of a support material;
coating the supporting material aqueous solution on a base material, and drying to respectively prepare a base film and a covering film;
and coating the graphene aqueous solution on the bottom film, drying, and then covering the coated film on the surface coated with the graphene aqueous solution.
16. The production method according to item 15, characterized in that the method further comprises a substrate pretreatment step before the aqueous support material solution is applied to a substrate, the substrate pretreatment comprising:
firstly coating a thermoplastic polymer film on one side of a substrate to be coated with the supporting material aqueous solution, wherein the thickness of the thermoplastic polymer film is less than 1 mu m;
and heating to soften and melt the polymer film.
17. The method according to item 15, further comprising rolling the suspended graphene thin film after coating the coating film.
18. The preparation method according to any one of claims 15 to 17, wherein the graphene suspension is water, the number of graphene layers is 1 to 3, the sheet diameter is 5 to 10 μm, and the mass percentage of the graphene suspension in the suspension is 3 w%.
19. The production method according to any one of claims 15 to 17, wherein the support material in the aqueous support material solution is contained in an amount of 3 to 8 w% by mass.
20. The production method according to any one of claims 15 to 17, wherein the support material is selected from at least one of: carbon black, silicon dioxide, polystyrene, polymethyl methacrylate, carbon nano tubes, silver nano wires, SiO2 nano wires and TiO2 nano wires.
21. The production method according to
22. The production method according to any one of claims 15 to 17, characterized in that the substrate is selected from at least one of: polycarbonate, polyvinyl chloride, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride.
23. The production method according to item 16, characterized in that the thermoplastic polymer is selected from at least one of: ethylene-vinyl acetate copolymer, polyethylene, polyvinyl chloride, polyvinyl alcohol.
24. The preparation method according to any one of claims 15 to 17, wherein the graphene aqueous solution is coated on the base film and dried, and then the coated film is coated on the side coated with the graphene aqueous solution, and the process comprises:
coating the graphene aqueous solution on the bottom film, and heating and drying moisture in a stepped manner;
and covering the film, and rolling at high temperature to obtain the suspended graphene film.
25. The method of claim 24, wherein the step heating process comprises heating at 40-60 ℃ for 8-12min, heating at 70-90 ℃ for 8-12min, heating at 90-110 ℃ for 8-12min, and heating at 140-160 ℃ for 8-12 min.
26. The graphene thin film produced by the production method according to any one of claims 15 to 25.
The invention adopts the layer-by-layer assembly technology to prepare the suspended graphene film, adopts the layer-by-layer preparation method to equip spherical and linear supporting materials on a base material, and clamps the graphene between supports to form a sandwich structure of the supports, namely the graphene-supports, wherein the graphene sheets in the internal structure are partially in a suspended state. The suspended graphene film with the structure improves the overall performance of the graphene film, and compared with the graphene film without suspended points, the thermal conductivity and the electric conductivity of the suspended graphene film are improved by nearly 40%.
Drawings
Fig. 1 is a structural diagram of a suspended graphene thin film according to the present invention.
Description of reference numerals:
11-a first substrate layer, 12-a support layer, 10-a base membrane, 20-a graphene layer, 11-a substrate layer, 12-a support layer and 30-a laminating film.
Detailed description of the invention
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not intended to be limiting.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in experimental or practical applications, the materials and methods are described below. In case of conflict, the present specification, including definitions, will control, and the materials, methods, and examples are illustrative only and not intended to be limiting. The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The invention provides a suspended graphene film, which has a structure shown in fig. 1 and comprises a
In a preferred embodiment, the suspended graphene thin film has a thickness of 1.5 to 4.5 μm, and may be, for example, 1.5 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.9 μm, 3.0 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.6 μm, 4.0 μm, 4.5 μm.
In a preferred embodiment, the
In a preferred embodiment, the thickness of the
In a preferred embodiment, the material shapes of the first support layer 12 and the
In a preferred embodiment, the materials of the first support layer 12 and the
Further, the carbon black, silica, polystyrene and polymethyl methacrylate are in the form of particles having a particle diameter of 0.05 to 2 μm, and may be, for example, 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm or 2 μm. The carbon nano tube, the silver nano wire and the SiO2Nanowire, TiO2The nanowires are linear, with a wire diameter size of 10-50nm, e.g., 10nm, 20nm, 30nm, 40nm, 50nm, and a wire length of 10-20 μm, e.g., 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm.
In a preferred embodiment, the first support layer 12 and the
In a preferred embodiment, the
The invention also provides a preparation method of the suspended graphene film, which comprises the following steps: preparing a graphene aqueous solution; preparing an aqueous solution of a support material; coating the supporting material aqueous solution on a base material, and drying to respectively prepare a base film and a covering film; and coating the graphene aqueous solution on the bottom film, and covering the coated film on the surface coated with the graphene to obtain the suspended graphene film.
Wherein, the supporting materials for preparing the basement membrane and the tectorial membrane can be the same or different, namely, one supporting material aqueous solution can be prepared, and two or more different supporting material aqueous solutions can also be prepared. The base materials for preparing the primary coating and the cover coating may be the same or different, and the same base material or different base materials may be selected. The thicknesses of the prepared basement membrane and the prepared tectorial membrane can be the same or different.
In a preferred embodiment, the support material is selected from the group consisting of carbon black, silica, polystyrene, polymethylmethacrylate, carbon nanotubes, silver nanowires, SiO2Nanowire, TiO2One or more than two nanowires.
Further, the carbon black, silica, polystyrene and polymethyl methacrylate are in the form of particles having a particle diameter of 0.05 to 2 μm, and may be, for example, 0.05 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm or 2 μm. The carbon nano tube, the silver nano wire and the SiO2Nanowire, TiO2The nanowires are linear, with a wire diameter size of 10-50nm, e.g., 10nm, 20nm, 30nm, 40nm, 50nm, and a wire length of 10-20 μm, e.g., 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm.
In a preferred embodiment, the support material is selected from the granular materials described above.
The graphene aqueous solution and the supporting material aqueous solution can be commercially obtained and can be prepared according to the needs.
In a preferred embodiment, the base material is selected from one or more of polycarbonate, polyvinyl chloride, polyethylene, polypropylene, polytetrafluoroethylene and polyvinylidene fluoride. The materials of the
In a preferred embodiment, the method further comprises a substrate pretreatment step prior to coating the aqueous support material solution onto a substrate, the substrate pretreatment comprising: firstly coating a thermoplastic polymer film on one side of a substrate to be coated with the supporting material aqueous solution, wherein the thickness of the thermoplastic polymer film is less than 1 mu m; and heating to soften and melt the polymer film. Preferably, the thermoplastic polymer is selected from one or more of ethylene-vinyl acetate copolymer, polyethylene, polyvinyl chloride and polyvinyl alcohol.
In a preferred embodiment, the graphene aqueous solution is water, the number of graphene layers is 1-3, the sheet diameter is 5-10 μm, and the mass percentage of the graphene aqueous solution in the suspension is 3 w%. The mass percentage of the supporting material in the supporting material aqueous solution is 3-8 w%.
In a preferred embodiment, the process of coating the aqueous graphene solution on the base film and covering the graphene-coated side with the covering film to obtain the suspended graphene film comprises: coating the graphene aqueous solution on the bottom film, and heating and drying moisture in a stepped manner; and covering the film, and rolling at high temperature to obtain the suspended graphene film. Preferably, the step heating process comprises heating at 40-60 deg.C for 8-12min, heating at 70-90 deg.C for 8-12min, heating at 90-110 deg.C for 8-12min, and heating at 140-160 deg.C for 8-12 min.
In a preferred embodiment, the temperature for applying the aqueous support material solution to the substrate and drying is 100-120 ℃. The drying temperature is determined according to the glass transition temperature of the thermoplastic polymer, and is higher than the glass transition temperature of the thermoplastic polymer.
The coating used in the above method may be any coating method in the art, including dipping, spraying, spin coating, screen printing, gravure printing, and the like.
Example 1
(1) Preparation of aqueous graphene solution
And (3) obtaining the graphene aqueous solution from the graphene oxide prepared by the Hunmers method by using a hydrazine hydrate reduction method.
In the prepared graphene aqueous solution, the mass percent of graphene is 3%, the number of layers of graphene is about 2, and the sheet diameter is about 5 m.
(2) Preparation of an aqueous support Material solution
Wherein the base film and the coating film are made of the same supporting material, and are prepared from a commercially available aqueous solution of silicon dioxide particle material (manufactured by Shanghai initiating laboratory reagent Co., Ltd., model number: 140210-10. preparation process, in which the powder is dispersed in the aqueous solution, and the aqueous solution is obtained by high-speed stirring and ultrasonic vibration), wherein the particle size of the silicon dioxide particles is 0.85 μm, and the concentration of the aqueous solution is 3%.
(3) Preparation of base film and overlay film
Selecting two polyethylene substrates (10cm by 0.5cm), cleaning and drying the substrates, and coating one surface of the substrates with 0.5 mu m of ethylene-vinyl acetate copolymer to obtain a pretreated substrate.
Respectively coating a certain amount of supporting material aqueous solution on one surface of two pretreated base material layers coated with ethylene-vinyl acetate copolymer (blade coating by using a wire rod), drying at 100 ℃, and then preparing a base film and a covering film. Wherein the thickness of the primary coating is 1 μm, and the thickness of the coating is 1 μm.
(4) Preparation of suspended graphene film
Coating a certain amount of graphene aqueous solution on one surface of the bottom film with the supporting material, and heating in a stepped manner, wherein the heating in the stepped manner is performed at 50 ℃ for 10min, at 80 ℃ for 10min, at 100 ℃ for 10min and at 150 ℃ for 10 min.
And covering a covering film on the surface coated with the graphene, wherein the surface coated with the supporting material is close to the surface of the base film with the graphene, and rolling the covering film at 150 ℃ and covering the covering film together to obtain the suspended graphene film. Wherein the thickness of the suspended graphene film is 3 μm.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：一种双层连续缠绕针刺筒形件及其制备方法