CN111732743A - Preparation method of carbon nanotube/graphene flexible film - Google Patents
Preparation method of carbon nanotube/graphene flexible film Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 244
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims description 50
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- 238000001035 drying Methods 0.000 claims description 21
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- 239000002952 polymeric resin Substances 0.000 claims description 19
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229940037003 alum Drugs 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
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- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
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- 239000010408 film Substances 0.000 description 64
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 5
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a carbon nano tube/graphene flexible film, which comprises the steps of dispersing carbon nano tubes and graphene in an aqueous solution of a surfactant at low concentration respectively, and then carrying out flocculation, filtration molding and the like to obtain the flexible film containing a graphene layer and a carbon nano tube layer. The film carbon nano material has high content, excellent conductivity (less than or equal to 10 omega/sq), resistance to kneading and soaking and good flexibility.
Description
Technical Field
The invention relates to the technical field of nano conductive materials, in particular to a preparation method of a carbon nano tube/graphene flexible film.
Background
Carbon nanotubes and graphene are hot spots for research and industrial application as carbon nanomaterials with excellent properties. The carbon nano tube has the characteristics of light weight, high strength, high modulus, functionalized surface and the like, and is an ideal reinforcing material for developing light-weight, high-strength and impact-resistant composite materials. As a conductive material, the composite material has various performances such as antistatic property, electromagnetic shielding property and the like.
Graphene is a two-dimensional crystal composed of carbon atoms only one layer of atomic thickness. Graphene has distinctive optical, electrical, magnetic, thermal, mechanical, and other properties. Due to the special conducting structure, the flake graphene has great advantages in the aspects of electricity and heat conduction; with the research, the properties and application range of graphene are continuously expanded, and the graphene can be widely applied to different fields such as transistors, sensors, photovoltaic cells, transparent conductors, composites, touch screens and high-frequency electronic equipment. The mode of preparing the powdery nano material into the film layer gives full play to the excellent performance of the powdery nano material, and is an important application and research direction. At present, the methods for preparing the carbon material conductive film on a large scale mainly comprise the following steps:
(1) the transparent graphene electrothermal film is prepared by using a chemical vapor deposition method, but the process is complex, and the product is not resistant to bending and kneading.
(2) And mixing the carbon nano tube/graphene powder with the high polymer resin mixed slurry by using a printing or coating method, coating, drying and forming a film. The electrothermal film prepared by the process is thicker and has higher resistance.
(3) And depositing the electrophoresis slurry containing the graphene on a metal substrate by using an electrophoresis process to obtain a graphene conductive polymer film, and then etching and laminating to obtain the graphene electrothermal film. The process is complex, the efficiency is low, and the preparation process is not environment-friendly. Therefore, it is desirable to provide a carbon nanotube/graphene composite film with good electrical and thermal conductivity.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon nanotube/graphene flexible film.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of a carbon nano tube/graphene flexible film, which comprises the following steps:
(1) dispersing carbon nanotubes in an aqueous solution of a surfactant to obtain a carbon nanotube dispersion liquid;
dispersing graphene in an aqueous solution of a surfactant to obtain a graphene dispersion liquid;
preferably, the carbon nanotube powder is dispersed by a horizontal grinder, and the graphene is dispersed by a cell disruptor.
Preferably, the surfactant is selected from at least one of sodium dodecyl sulfate, polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, betaine-type amphoteric surfactant.
Preferably, the mass concentration of the aqueous solution of the surfactant is 0.5-2.5 per mill.
Preferably, in the carbon nanotube dispersion liquid, the mass ratio of the carbon nanotubes to the surfactant aqueous solution is 1 (150-800).
Preferably, in the graphene dispersion liquid, the mass ratio of graphene to the aqueous solution of the surfactant is 1 (150-800).
(2) Mixing the graphene dispersion liquid with a high-molecular resin emulsion to obtain a graphene mixed liquid, adding a water solution of a flocculating agent into the graphene mixed liquid, and mixing to obtain a graphene suspension;
mixing the carbon nanotube dispersion liquid with a high molecular resin emulsion to obtain a carbon nanotube mixed liquid, adding a water solution of a flocculating agent into the carbon nanotube mixed liquid, and mixing to obtain a carbon nanotube suspension;
preferably, the graphene dispersion liquid or the carbon nanotube dispersion liquid is mixed with the polymer resin emulsion, and then stirred for 0.5-1 h.
Preferably, in the graphene mixed solution, the mass ratio of the polymer resin to the graphene is (0.2-1.5): 1; in the carbon nanotube mixed solution, the mass ratio of the polymer resin to the carbon nanotubes is (0.2-1.5): 1.
Preferably, the polymer resin is at least one of polyurethane and acrylic resin.
Preferably, the flocculant is an inorganic flocculant and is selected from at least one of alum, aluminum sulfate, aluminum chloride, ferric sulfate and ferric chloride.
Preferably, the mass concentration of the aqueous solution of the flocculant is 0.1-3%.
Preferably, the mass ratio of the aqueous solution of the flocculant to the graphene is (50-300): 1.
(3) Placing a filter screen in the graphene suspension or the carbon nano tube suspension, performing suction filtration, drying, and removing the filter screen to obtain a graphene film or a carbon nano tube film;
preferably, the filter screen is a polyester filter screen or a stainless steel filter screen, and the aperture is 150-600 meshes.
Preferably, vacuum filtration is adopted, and the filtration time is 2-4 min.
Preferably, infrared drying is adopted, the drying temperature is 80-120 ℃, and the drying time is more than 30 min.
(4) Placing the graphene film obtained in the step (3) into a carbon nano tube suspension, centrifuging, taking out and drying to obtain a carbon nano tube/graphene/carbon nano tube flexible film;
and (4) putting the carbon nano tube film obtained in the step (3) into a graphene suspension, centrifuging, taking out and drying to obtain the graphene/carbon nano tube/graphene flexible film.
Preferably, the thickness of the flexible film is 50-150 μm, the surface square resistance is 2-30 Ω/sq, and the tensile strength is 1-10 Mpa.
The invention has the beneficial effects that:
the invention provides a preparation method of a carbon nano tube/graphene flexible film, which comprises the steps of dispersing carbon nano tubes and graphene in an aqueous solution of a surfactant at low concentration respectively, and then carrying out flocculation, filtration molding and the like to obtain the flexible film containing a graphene layer and a carbon nano tube layer. The film carbon nano material has high content, excellent conductivity (less than or equal to 10 omega/sq), resistance to kneading and soaking and good flexibility.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a preparation method of a carbon nanotube/graphene flexible film, which comprises the following steps:
(1) dispersing carbon nanotubes in an aqueous solution of a surfactant to obtain a carbon nanotube dispersion liquid; and dispersing graphene in an aqueous solution of a surfactant to obtain a graphene dispersion liquid. The preparation of the carbon nanotube dispersion and the graphene dispersion may be performed separately or simultaneously.
In one embodiment of the present invention, since the carbon nanotubes are nano-sized powder, the carbon nanotubes are usually available in the form of bulk or crushed aggregates, which cannot meet the requirement of film-forming particle size when used directly. Therefore, the carbon nano tube aggregated powder can be ground and depolymerized into primary particles by using equipment such as a sand mill, a bead membrane machine, a vibration mill, a dense medium mill and the like, so as to be beneficial to dispersion and film formation. In the invention, the carbon nanotube powder is dispersed by a horizontal grinder.
Graphene is a carbon atom in sp2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. Common powder production methods of graphene include a mechanical stripping method, an oxidation-reduction method, and the like. Since the graphene powder sold in the market is also aggregated and stacked, graphene sheets cannot be thoroughly separated by grinding, and thus, the graphene is dispersed by a cell disruptor.
In one embodiment of the present invention, the surfactant is selected from at least one of sodium lauryl sulfate, polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, betaine-type amphoteric surfactants. The function of the surfactant is as follows: the carbon nano tube, the graphene and the subsequently added resin emulsion and other nano particles or liquid drops are coated, so that the nano particles or liquid drops are uniformly dispersed and stably exist in water, and the carbon nano tube and the graphene are prevented from settling.
In one embodiment of the present invention, the mass concentration of the aqueous solution of the surfactant is 0.5 to 2.5%. The mass concentration of the surfactant is too low, so that effective coating on the carbon nano tube and the graphene cannot be formed, the carbon nano tube and the graphene are settled before film forming, and the stability and uniformity of the film are influenced. Too high a mass concentration of the surfactant causes the dispersion to foam, and uniform film formation is still impossible.
In one embodiment of the invention, the mass ratio of the carbon nanotubes to the surfactant aqueous solution in the carbon nanotube dispersion is 1 (150-800). In the graphene dispersion liquid, the mass ratio of graphene to the aqueous solution of the surfactant is also 1 (150-800).
(2) Mixing the graphene dispersion liquid prepared in the step (1) with a high polymer resin emulsion to obtain a graphene mixed liquid, adding a water solution of a flocculating agent into the graphene mixed liquid to obtain a graphene suspension liquid, wherein the flocculating particles appear in the mixed liquid;
and (2) mixing the carbon nanotube dispersion liquid prepared in the step (1) with a high-molecular resin emulsion to obtain a carbon nanotube mixed liquid, adding a water solution of a flocculating agent into the carbon nanotube mixed liquid, and mixing to obtain a carbon nanotube suspension. The preparation of the carbon nanotube suspension and the graphene suspension can be performed separately or simultaneously.
In one embodiment of the invention, the graphene dispersion liquid or the carbon nanotube dispersion liquid is mixed with the polymer resin emulsion, and then stirred for 0.5-1 h. The stirring function is to fully mix the flocculating agent with the substances in the dispersion liquid so that the flocculating agent can play a role.
In one embodiment of the invention, the high molecular resin is selected from at least one of polyurethane emulsion and acrylic resin emulsion, and the particle size of the emulsion is less than or equal to 500 nm. The polymer resin is a water-based polymer, has good bonding strength and chemical resistance, provides the bonding force between the carbon nanotube and the graphene powder, and further improves the flexibility and the mechanical property of the film. Anionic resins are preferred in the present invention and are not used because epoxy resins require curing agents, increasing the number of other species in the film.
In one embodiment of the invention, in the graphene mixed solution, the mass ratio of the polymer resin to the graphene is (0.2-1.5): 1; the mass ratio of the polymer resin to the carbon nanotubes in the carbon nanotube mixture is also (0.2-1.5): 1. The addition amount of the polymer resin is too small, so that the adhesive force provided for the nano powder is insufficient; if the addition amount is too large, the graphene and the carbon nano tube in the unit area of the film are reduced as impurities, and the electrical property of the film is influenced.
In one embodiment of the invention, the flocculant is an inorganic flocculant selected from at least one of alum, aluminum sulfate, aluminum chloride, ferric sulfate, and ferric chloride. The function of the flocculating agent is to destroy the charge balance in the emulsifying agent after the graphene, the carbon nano tube and the resin emulsion are uniformly and stably mixed, so as to influence the dispersion effect of the emulsifying agent, break the stable state of the mixed solution and flocculate small particles into large particles. The method has a key effect on the uniform deposition of graphene and carbon nanotubes at the bottom of the suspension to form a wet film.
In one embodiment of the invention, the mass concentration of the aqueous solution of the flocculant is 0.1-3%. The mass concentration of the flocculating agent is too low, so that the carbon nano tubes and the graphene cannot be fully settled, the quality of the graphene and the carbon nano tubes in unit area of the film is reduced, and the stability and the uniformity of the film are influenced. The mass concentration of the flocculant is too high, and the carbon nano tube and the graphene settle too fast, so that the uniformity of the film is influenced.
In one embodiment of the invention, the mass ratio of the aqueous solution of the flocculating agent to the graphene is (50-300): 1.
(3) And (3) placing the filter screen in the graphene suspension or the carbon nano tube suspension prepared in the step (2), performing suction filtration, drying, and manually stripping the filter screen from the surface of the film to obtain the graphene film or the carbon nano tube film. The graphene film or the carbon nanotube film is a wet film.
In one embodiment of the present invention, the filter screen is a polyester filter screen or a stainless steel filter screen, and the aperture is 150 to 600 mesh.
In one embodiment of the invention, in order to fully attach the graphene or the carbon nanotubes in the suspension to the surface of the filter screen, vacuum filtration is adopted, and the filtration time is 2-4 min.
In one embodiment of the invention, the graphene film or the carbon nanotube film is placed in an infrared drying oven for drying. The reason is that the infrared drying environment is soft and gentle, and the non-air-blast drying is carried out under air flow, so that the film is disturbed. The infrared drying temperature is 80-120 ℃, and the drying time is more than 30 min.
(4) Placing the graphene film obtained in the step (3) into a carbon nano tube suspension, centrifuging, taking out and drying to obtain a carbon nano tube/graphene/carbon nano tube flexible film;
and (4) putting the carbon nano tube film obtained in the step (3) into a graphene suspension, centrifuging, taking out and drying to obtain the graphene/carbon nano tube/graphene flexible film.
The flexible film having a double-layer structure, that is, the flexible film having the graphene layer + the carbon nanotube layer, may also be prepared in another manner. The graphene film containing the filter screen prepared in the step (3) can be used as a substrate, then the carbon nanotube suspension prepared in the step (2) is poured on the surface of the substrate, then the substrate is directly filtered and dried, and the filter screen is manually peeled from the surface of the film before and after drying, so that the composite film with the double-layer structure is obtained.
The invention also relates to a flexible film prepared by the method, which has the thickness of 50-150 mu m, the surface square resistance of 2-10 omega/sq, the tensile strength of 1-10 Mpa, and good flexibility and conductivity.
Example 1
A preparation method of a carbon nanotube/graphene flexible film comprises the following steps:
(1) preparing a carbon nano tube dispersion liquid: dispersing the carbon nano tube in a surfactant aqueous solution with the mass concentration of 0.5 per mill by a horizontal grinder to obtain a carbon nano tube dispersion liquid. Wherein the mass ratio of the carbon nano tube to the aqueous solution of the surfactant is 1:150, the surfactant is the combination of sodium dodecyl sulfate and cocamidopropyl betaine (CAB35), and the mass ratio of the sodium dodecyl sulfate to the cocamidopropyl betaine is 1: 2.
Preparing a graphene dispersion liquid: and dispersing graphene in an aqueous solution of a surfactant with the mass concentration of 0.5 per mill by using a cell disruptor to obtain a graphene dispersion liquid. Wherein the mass ratio of the graphene to the aqueous solution of the surfactant is 1:250, the surfactant is the combination of sodium dodecyl sulfate and CAB35, and the mass ratio of the sodium dodecyl sulfate to the cocamidopropyl betaine is 1: 2.
(2) Preparing a graphene suspension: mixing the graphene dispersion liquid with the polyurethane resin emulsion, fully stirring for 30min to obtain a graphene mixed liquid, adding a water solution of a flocculating agent with the mass concentration of 0.1% into the graphene mixed liquid, and mixing to obtain flocculating particles to obtain the graphene suspension. Wherein the mass ratio of the polymer resin to the graphene is 0.5:1, and the polymer resin is polyurethane. The mass ratio of the aqueous solution of the flocculating agent to the graphene is 100: 1.
Preparing a carbon nanotube suspension: mixing the carbon nano tube dispersion liquid with the polymer resin emulsion, fully stirring for 30min to obtain a carbon nano tube mixed liquid, adding a water solution of a flocculating agent with the mass concentration of 0.1% into the carbon nano tube mixed liquid, and mixing to obtain flocculated particles to obtain a carbon nano tube suspension. Wherein the mass ratio of the high molecular resin to the carbon nano tube is 0.2:1, and the high molecular resin is anionic polyurethane emulsion. The mass ratio of the aqueous solution of the flocculating agent to the carbon nano tubes is 80: 1.
(3) Filtering and forming: placing a polyester filter screen or a steel mesh with the aperture of 300 meshes in the prepared graphene suspension, carrying out vacuum filtration for 2min, then placing in an infrared drying oven for drying, and drying at 100 ℃ for 30min to obtain a graphene film containing the filter screen;
(4) and (3) manually removing the filter screen from the graphene film containing the filter screen prepared in the step (3), placing the graphene film into the carbon nano tube suspension prepared in the step (2), then placing the graphene film into a centrifuge for centrifugation, taking out the film after the solution is clear and transparent, and drying the film to obtain the carbon nano tube/graphene/carbon nano tube flexible film. The film has a three-layer structure, namely, the upper surface and the lower surface of the graphene layer are respectively provided with a carbon nanotube layer.
Examples 2-6 and comparative examples the specific materials and ratios of the steps were changed, as shown in table 1.
TABLE 1
The four-probe method was used to test the sheet resistance, and the tensile properties of the films obtained in the examples and comparative examples were tested according to GB/T1040.3-2006, the results of which are shown in Table 2.
TABLE 2
| Examples/comparative examples | Film thickness (μm) | Surface square resistance (omega/sq) | Tensile strength (Mpa) |
| Example 1 | 80 | 3 | 8 |
| Example 2 | 70 | 6 | 5 |
| Example 3 | 85 | 5 | 4 |
| Example 4 | 80 | 10 | 7 |
| Example 5 | 80 | 5 | 6 |
| Example 6 | 75 | 5 | 5 |
| Comparative example 1 | 90 | 6 | 3 |
| Comparative example 2 | 90 | 4 | 1 |
| Comparative example 3 | 30 | 12 | 2 |
The data in table 2 show that the carbon nanotube/graphene/carbon nanotube flexible film prepared by the method of the present invention has excellent electrical conductivity and tensile strength. If a surfactant, a polymer resin emulsion or a flocculant is not added during the preparation process, the above properties are reduced.
According to the invention, the surfactant is adopted to realize the dispersion of the carbon nano tubes and the graphene, so that the content of the graphene and the carbon nano tubes in the flexible film is higher than that of the carbon nano tube/graphene film prepared by a conventional method, and the surface resistance is lower than 5 omega/sq. If the graphene/carbon nanotube and the resin are mixed in the solvent, then the mixture is subjected to roller grinding, and then the mixture is coated on the substrate layer to prepare the thin film in the prior art, the low surface resistance cannot be obtained. The flexible film is not required to be attached by a base material after the preparation is finished, and is an independently formed flexible film.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a carbon nanotube/graphene flexible film is characterized by comprising the following steps:
(1) dispersing carbon nanotubes in an aqueous solution of a surfactant to obtain a carbon nanotube dispersion liquid; dispersing graphene in an aqueous solution of a surfactant to obtain a graphene dispersion liquid;
(2) mixing the graphene dispersion liquid with a high-molecular resin emulsion to obtain a graphene mixed liquid, adding a water solution of a flocculating agent into the graphene mixed liquid, and mixing to obtain a graphene suspension;
mixing the carbon nanotube dispersion liquid with a high molecular resin emulsion to obtain a carbon nanotube mixed liquid, adding a water solution of a flocculating agent into the carbon nanotube mixed liquid, and mixing to obtain a carbon nanotube suspension;
(3) placing a filter screen in the graphene suspension or the carbon nano tube suspension, performing suction filtration, drying, and removing the filter screen to obtain a graphene film or a carbon nano tube film;
(4) placing the graphene film obtained in the step (3) into a carbon nano tube suspension, centrifuging, taking out and drying to obtain a carbon nano tube/graphene/carbon nano tube flexible film;
and (4) putting the carbon nano tube film obtained in the step (3) into a graphene suspension, centrifuging, taking out and drying to obtain the graphene/carbon nano tube/graphene flexible film.
2. The method according to claim 1, wherein in the step (1), the carbon nanotube powder is dispersed by a horizontal grinder, and the graphene is dispersed by a cell disruptor.
3. The method according to claim 1, wherein in the step (1), the surfactant is at least one selected from the group consisting of sodium dodecyl sulfate, polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate and betaine-type amphoteric surfactants.
4. The method according to claim 1, wherein in the step (1), the mass concentration of the aqueous solution of the surfactant is 0.5-2.5 ‰;
and/or in the carbon nanotube dispersion liquid, the mass ratio of the carbon nanotubes to the surfactant aqueous solution is 1 (150-800);
and/or in the graphene dispersion liquid, the mass ratio of graphene to the water solution of the surfactant is 1 (150-800).
5. The method according to claim 1, wherein in the step (2), the graphene dispersion liquid or the carbon nanotube dispersion liquid is mixed with the polymer resin emulsion, and then stirred for 0.5-1 h.
6. The method according to claim 1, wherein in the step (2), the mass ratio of the polymer resin to the graphene in the graphene mixed solution is (0.2-1.5): 1;
and/or the mass ratio of the polymer resin to the carbon nano tubes in the carbon nano tube mixed solution is (0.2-1.5): 1.
7. The method according to claim 1, wherein in the step (2), the polymer resin is at least one of polyurethane and acrylic resin;
and/or the flocculating agent is an inorganic flocculating agent and is selected from at least one of alum, aluminum sulfate, aluminum chloride, ferric sulfate and ferric chloride.
8. The method according to claim 1, characterized in that in the step (2), the mass concentration of the aqueous solution of the flocculating agent is 0.1-3%;
and/or the mass ratio of the aqueous solution of the flocculant to the graphene is (50-300): 1.
9. The method according to claim 1, wherein in the step (3), the filter screen is a polyester filter screen or a stainless steel filter screen, and the aperture is 150-600 meshes;
and/or infrared drying is adopted, the drying temperature is 80-120 ℃, and the drying time is more than 30 min.
10. The flexible film according to any one of claims 1 to 9, wherein the flexible film has a thickness of 50 to 150 μm, a surface sheet resistance of 2 to 30 Ω/sq, and a tensile strength of 1 to 10 Mpa.
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