CN115650224A - High-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film and preparation method thereof - Google Patents
High-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film and preparation method thereof Download PDFInfo
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Abstract
The application discloses a high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite membrane and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Uniformly stirring and mixing the graphene oxide solution, the acidified carbon nano tube and the water-soluble amine cross-linking agent to obtain slurry; (2) Coating the slurry to form a film, and drying to obtain an amino crosslinked graphene oxide-carbon nanotube composite film; (3) Carrying out graphitization heat treatment on the amino-crosslinked graphene oxide-carbon nanotube composite membrane under the protection of an inert atmosphere to obtain a nitrogen-doped graphene-carbon nanotube composite membrane; (4) And (3) rolling the nitrogen-doped graphene-carbon nanotube composite membrane to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite membrane. The raw materials of the invention have wide sources and low cost; the amino-group-enhanced graphene oxide film can be assembled by one-step solidification, and then the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film with excellent thermal conductivity and electrical conductivity is obtained by thermal treatment.
Description
Technical Field
The invention relates to the field of graphene films, in particular to a high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film and a preparation method thereof.
Background
Graphene is used as the most basic structural unit of all carbon materials, has a real monoatomic layer thickness and a strict two-dimensional structure, and has high mechanical strength, elasticity, thermal conductivity, electrical conductivity, quantum Hall effect and the like. Since 2010 UK scientists (Andre Geim) Anddelejem and (Konstantin Novoseov) Kesta Novovoronol discovered graphene and gained Nobel prize, the research of graphene reaches unprecedented climax, and more researches discover that the graphene has great application prospect in special fields such as energy storage, electrical devices, catalysis and biomedicine. From the practical application point of view, the transformation of nano graphene materials into macro structure materials is undoubtedly a very valuable research direction. However, the preparation of the macroscopic graphene-carbon nanotube composite material by compounding the one-dimensional carbon nanotube and the two-dimensional graphene structure will undoubtedly bring great beneficial values to the industry. Carbon nanotubes include multi-walled carbon nanotubes and single-walled carbon nanotubes. The carbon nano tube has the characteristics of excellent optical, electric and magnetic properties, extremely large specific surface area, quite strong conductivity and reactivity, many surface active sites and the like, is an excellent nano material for electric analysis and electrocatalysis, and can be widely applied to various fields such as chemistry, biology and the like.
The macro-assembled graphene membrane is a main form of the macro-fabrication of nano-scale graphene sheets, and common methods include a suction filtration method, a film scraping method, a spin coating method, a spraying method and the like, but the methods limit the large-scale and continuous preparation of the graphene membrane. Chinese invention patent CN201410457039.6 discloses two methods of preparing graphene films: firstly, a wet spinning method is adopted to precipitate in coagulating liquid such as inorganic metal salt solution and the like to form a film, the film is dried, and then a reducing agent is used to perform a reduction two-step method to prepare the ion-enhanced graphene film; and secondly, the graphene solution is used as a raw material, stays in a solidification solution containing coordination ions for solidification to form a film, and is dried to obtain the ion-reinforced graphene film. Therefore, it is an urgent need to solve the problem of developing a simple and convenient preparation method for continuously preparing a high-strength and high-performance graphene film without inorganic salt ions in a one-step method.
Disclosure of Invention
Aiming at the problems, the invention provides a high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film comprises the following steps:
(1) Uniformly stirring and mixing the graphene oxide solution, the acidified carbon nano tube and the water-soluble amine cross-linking agent to obtain slurry;
wherein the mass ratio of the graphene oxide to the acidified carbon nanotubes in the slurry is (1;
the acidified carbon nano tube is an acidified multi-wall carbon nano tube and/or an acidified single-wall carbon nano tube;
the water-soluble amine cross-linking agent is one or more of ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ammonia, polyallylamine, hydrazine hydrate and p-phenylenediamine;
(2) Coating the slurry obtained in the step (1) to form a film, and drying to obtain an amino crosslinked graphene oxide-carbon nanotube composite film;
(3) Carrying out graphitization heat treatment on the amino cross-linked graphene oxide-carbon nanotube composite membrane prepared in the step (2) under the protection of inert atmosphere to obtain a nitrogen-doped graphene-carbon nanotube composite membrane;
(4) And (4) calendering the nitrogen-doped graphene-carbon nanotube composite film obtained in the step (3) to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film.
The raw materials of the invention have wide sources and low cost; the preparation method takes the graphene oxide solution as a raw material, can assemble the amino-enhanced graphene oxide film by one-step solidification, and then obtains the high-heat-conductivity nitrogen-doped graphene-carbon nanotube composite film by heat treatment, so that the reaction temperature is low, the operation is simple, the environment is protected, and large-scale continuous preparation can be realized; the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film prepared by the invention has good strength and toughness, excellent thermal conductivity and electric conductivity, and widens the range of subsequent application.
In practical use, the stirring in step (1) may be performed by mechanical stirring for uniform mixing.
The application also provides the amino crosslinked graphene oxide-carbon nanotube composite membrane prepared by the steps (1) to (2), and the amino crosslinked graphene oxide-carbon nanotube composite membrane has a good application prospect in the fields of heat conduction and heat dissipation, battery shielding and the like.
In the invention, the dosage of the water-soluble amine cross-linking agent is conventional in the field, and is generally 1 to 35%, wherein the percentage is the mass percentage of the water-soluble amine cross-linking agent relative to the mixed solution.
In one embodiment of the present invention, in the step (2), the thickness of the coating film ranges from 1 μm to 10mm, preferably from 10 μm to 6mm.
In one embodiment of the present invention, the preparation of the acidified carbon nanotube comprises the following steps:
mixing a carbon nano tube and an acidifying substance according to a set proportion, and stirring for 1 to 24h at 50 to 95 ℃ to obtain a mixture, wherein the carbon nano tube is a multi-wall carbon nano tube and/or a single-wall carbon nano tube, and the acidifying substance is sulfuric acid and/or sulfuric acid;
and pouring the mixture into water, filtering and collecting solid, and washing and drying the solid to obtain the acidified carbon nano tube.
In one embodiment of the invention, in the slurry in the step (1), the content of the graphene oxide is 1 to 80mg/mL of the slurry;
or, in the slurry in the step (1), the content of the graphene oxide is 31 to 80mg/mL of slurry.
In one embodiment of the present invention, in the slurry, the mass ratio of the graphene oxide to the water-soluble amine crosslinking agent is (1.
In the present invention, the graphene oxide solution is prepared by a method conventional in the art, preferably by an oxidation exfoliated graphite method (i.e., hummers method), more preferably by the following steps: (1) pre-oxidation: pouring graphite, concentrated sulfuric acid and nitric acid into water, filtering and drying to obtain pre-oxidized graphite; (2) thermal expansion: thermally expanding the pre-oxidized graphite in the step (1) for 5-30s at 950-1300 ℃ to obtain thermally expanded graphite oxide; (3) heating the thermal expansion graphite oxide obtained in the step (2) with a mixture of concentrated sulfuric acid, potassium persulfate and phosphorus pentoxide at 80-90 ℃, adding water, filtering, washing and drying to obtain pre-oxidized thermal expansion graphite; (4) and (3) mixing the pre-oxidized thermal expansion graphite in the step (3) with concentrated sulfuric acid at 0-5 ℃, adding potassium permanganate, reacting, adding hydrogen peroxide, standing, filtering, centrifugally washing, adding water, and stirring to obtain a graphene oxide solution.
In one embodiment of the invention, in the step (2), the drying temperature is 60 to 95 ℃, and the drying time is 0.5 to 200 hours;
or in the step (2), the drying temperature is 65 to 95 ℃, and the drying time is 2 to 50 hours.
In one embodiment of the present invention, in the step (3), the graphitization heat treatment can be performed in a conventional apparatus in the art, preferably in a muffle furnace, wherein the graphitization heat treatment temperature is 50-3000 ℃, and the heat treatment time is 0.5-200 hours; or the heat treatment temperature is 1000-3000 ℃, and the heat treatment time is 2-10 hours.
In one embodiment of the present invention, the graphitization heat treatment includes two stages:
in the first stage, the graphene oxide is reduced by heat treatment for 1 to 10 hours at the temperature of between 200 and 1500 ℃ under a vacuum condition;
in the second stage, the temperature is kept at 2300-3300 ℃ for 0.5-20 hours under the protection of inert atmosphere, or in the second stage, the temperature is kept at 3001-3300 ℃ for 3-10 hours under the protection of inert atmosphere.
After graphitization heat treatment, the thermal conductivity and strength of the obtained nitrogen-doped graphene-carbon nanotube composite membrane are improved.
In one embodiment of the present invention, in the step (3), the inert atmosphere is one or more of nitrogen, argon and helium.
In one embodiment of the present invention, the diameter of the acidified carbon nanotube is 10 to 200nm.
The application also discloses a high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film prepared by the preparation method of the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film, wherein the thermal conductivity of the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film is 700-1500W/mk or 1600-2000W/mk.
In one embodiment of the present invention, the thickness of the nitrogen-doped graphene-carbon nanotube composite film with high thermal conductivity is preferably 0.1 to 400 μm.
The invention has the beneficial effects that:
(1) In the mixed solution of polyamine water-soluble crosslinking coagulants and graphene oxide, the invention adopts a graphene oxide solution coating method, can realize self-assembly of amino crosslinking graphene oxide-carbon nanotube composite films by solidification in one step, and has the advantages of low reaction temperature, simple operation, environmental protection, large-scale preparation, simplicity, controllability and easy operation under single condition.
(2) The raw materials used in the invention are graphene oxide, low-cost polyamine water-soluble crosslinking coagulator and water-dispersible acidified carbon nanotubes, the source is very wide, and the method can be widely applied in a large scale; the prepared nitrogen-doped graphene-carbon nanotube composite membrane has good strength and toughness and excellent thermal conductivity, and widens the range for subsequent application.
(3) If the carbon nanotubes are directly blended with graphene oxide to form the composite aerogel, the carbon nanotubes cannot be dispersed in water, are seriously agglomerated and have poor dispersibility, and cannot be uniformly mixed with the graphene oxide, so that the carbon nanotubes have excellent mechanical, heat-conducting and electrical properties, and the utilization efficiency of the carbon nanotubes is limited due to agglomeration. The graphene-carbon nanotube composite membrane prepared by the invention is completely different from the graphene-carbon nanotube composite membrane. The water-dispersible acidified carbon nanotube can be dispersed in water, the acidified carbon nanotube containing carboxylic acid groups and graphene oxide are self-assembled and gelatinized by the polyamine water-soluble crosslinking coagulant to obtain uniform dispersion liquid, and the acidified carbon nanotube is uniformly loaded on a graphene film, so that the carbon nanotube has better dispersibility, is adhered on a graphene sheet layer by the polyamine water-soluble crosslinking coagulant and slowly formed, is tightly combined without agglomeration, is favorable for fully exerting the good mechanical, heat conduction, electrical properties and other beneficial characteristics of the carbon nanotube, and has great potential application value.
(4) The high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite membrane subjected to calendaring treatment is obviously improved in thermal conductivity and tensile strength, and has potential application value.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
In the following examples, the starting materials used are all commercially available. The film thickness of the graphene film is measured by a scanning electron microscope or a vernier caliper, the thermal conductivity is measured by a laser thermal conductivity meter, and the mechanical property is measured by a universal tensile testing machine.
In the following examples, the graphite used was a flake graphite having an average particle diameter of 50 to 500. Mu.m, and was obtained from Sigma Aldrich (Sigma-Aldrich). Carbon nanotubes were derived from shenzhen nano gang ltd, multi-walled carbon nanotubes and single-walled carbon nanotubes. The rest raw materials are all from chemical reagents of national drug group, inc.
Example 1
The preparation method of the graphene oxide solution comprises the following steps:
adding 10g of graphite, 150ml of sulfuric acid with the concentration of 98% and 30ml of nitric acid with the concentration of 69% into a 500ml conical flask, stirring for 24 hours at room temperature, slowly pouring into 1L of water, filtering, collecting solids, washing for 3 times, and drying for 4 hours at 80 ℃ to obtain pre-oxidized graphite.
The pre-oxidation process was repeated twice.
And (3) putting the dried pre-oxidized graphite into a box type furnace, and thermally expanding for 20s at 900 ℃ to obtain the thermally expanded graphite oxide.
In a 500ml wide-mouth conical flask, 5g of thermally expandable graphite oxide was mixed with 300ml of sulfuric acid (concentration: 98%), 5g of potassium persulfate, and 7g of phosphorus pentoxide, and then heated at 80 ℃ for 4 hours, diluted with 2L of water, filtered, washed, and air-dried for 3 days to obtain pre-oxidized thermally expandable graphite.
Mixing the dried pre-oxidized thermal expansion graphite with 200ml of sulfuric acid (with the concentration of 98%) at the low temperature of 0-5 ℃, slowly adding 20g of potassium permanganate, stirring at the temperature of 35 ℃ for 1h, adding 2L of water to dilute and stand for 1h, adding 10ml of 30% hydrogen peroxide, standing for 2 days, pouring off the supernatant, centrifuging and washing, and stirring mildly to obtain a well-dispersed graphene oxide solution.
The preparation method of the acidified carbon nanotube comprises the following steps:
5g of carbon nano tube, 150ml of sulfuric acid with the concentration of 98 percent and 30ml of nitric acid with the concentration of 69 percent are taken and added into a 500ml conical flask to be stirred for 24 hours at the temperature of 50 ℃, and then the mixture is slowly poured into 1L of water to be filtered and collected into solid, and the solid is washed for 3 times and dried for 4 hours at the temperature of 80 ℃ to obtain the acidified carbon nano tube.
Stirring and mixing the prepared graphene oxide solution, the acidified carbon nanotube and the ethylenediamine uniformly to obtain slurry; the content of the graphene oxide is 31mg/mL of slurry, and the mass ratio of the graphene oxide to an acidified carbon nanotube (the carbon nanotube is a multi-walled carbon nanotube, the pipe diameter is 10 to 20 nanometers, and the length is less than 2 micrometers) is 1:1, the mass fraction of ethylenediamine with respect to the slurry was 1%. And coating the slurry to form a film, drying at 95 ℃ for 2h to obtain an amino-crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 3000 ℃ and the time is 2 h). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, the thermal conductivity and the mechanical properties of the obtained high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Example 2
The graphene oxide solution was prepared as in example 1.
The preparation method of the acidified carbon nano tube comprises the following steps:
5g of carbon nano tube, 150ml of sulfuric acid with the concentration of 98 percent and 30ml of nitric acid with the concentration of 69 percent are taken and added into a 500ml conical flask to be stirred for 10 hours at 70 ℃, and then the mixture is slowly poured into 1L of water to be filtered and collected into solid, and the solid is washed for 3 times and dried for 4 hours at 80 ℃ to obtain the acidified carbon nano tube.
Stirring and mixing the prepared graphene oxide solution, the acidified carbon nano tube and the ethylenediamine uniformly to obtain slurry; wherein the content of the graphene oxide is 1mg/mL of slurry, and the mass ratio of the graphene oxide to the acidified carbon nanotube is 1:0.05, the carbon nanotube comprises a multi-wall carbon nanotube and a single-wall carbon nanotube with a mass ratio of 1 to 1, wherein the multi-wall carbon nanotube has a pipe diameter of 40 to 60 nanometers and a length of 2 to 5 micrometers, and the single-wall carbon nanotube has a pipe diameter of 1 to 3 nanometers and a length of 2 to 5 micrometers; the mass fraction of ethylenediamine with respect to the slurry was 20%. Coating the slurry to form a film, drying at 85 ℃ for 4h to obtain an amino-crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 2000 ℃, and the time is 3 h). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, thermal conductivity and mechanical properties of the obtained high thermal conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Example 3
The graphene oxide solution was prepared as in example 1.
The preparation method of the acidified carbon nanotube comprises the following steps:
adding 5g of carbon nano tube, 150ml of sulfuric acid with the concentration of 98% and 30ml of nitric acid with the concentration of 69% into a 500ml conical flask, stirring for 1h at 95 ℃, slowly pouring into 1L of water, filtering, collecting solid, washing for 3 times, and drying for 4 hours at 80 ℃ to obtain the acidified carbon nano tube.
Stirring and mixing the prepared graphene oxide solution, the acidified carbon nano tube, ammonia water and triethylene tetramine uniformly to obtain slurry; the content of the graphene oxide is 55mg/mL slurry, and the mass ratio of the graphene oxide to an acidified carbon nanotube (the carbon nanotube is a multi-walled carbon nanotube, the pipe diameter is 60-100 nanometers, and the length is 5-15 micrometers) is 1:0.01; the mass fraction of the ammonia water relative to the slurry was 30%, and the mass fraction of the triethylene tetramine relative to the slurry was 5%. And coating the slurry to form a film, drying at 75 ℃ for 8 hours to obtain an amino crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 1500 ℃, and the time is 4 hours). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, thermal conductivity and mechanical properties of the obtained high thermal conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Example 4
The graphene oxide solution was prepared as in example 1.
The acidified carbon nanotubes were prepared as in example 1.
Stirring and mixing the prepared graphene oxide solution, the acidified carbon nano tube, the propane diamine and the butane diamine uniformly to obtain slurry; the content of the graphene oxide is 80mg/mL of slurry, and the mass ratio of the graphene oxide to an acidified carbon nanotube (the carbon nanotube is a single-walled carbon nanotube, the pipe diameter is 1 to 3 nanometers, and the length is 5 to 15 micrometers) is 1:0.5; the mass fractions of propylenediamine and butylenediamine relative to the slurry were both 8%. And coating the slurry to form a film, drying the film at 55 ℃ for 24h to obtain an amino-crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 1000 ℃ and the time is 8 h). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, the thermal conductivity and the mechanical properties of the obtained high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Example 5
The graphene oxide solution was prepared as in example 1.
The acidified carbon nanotubes were prepared as in example 1.
Stirring and uniformly mixing the prepared graphene oxide solution, the acidified carbon nanotube and diethylenetriamine to obtain slurry; the content of the graphene oxide is 31mg/mL of slurry, and the mass ratio of the graphene oxide to the acidified carbon nanotube is 1: the carbon nano tube comprises a multi-wall carbon nano tube and a single-wall carbon nano tube with the mass ratio of 1 to 1, wherein the single-wall carbon nano tube has the tube diameter of 1 to 3 nanometers and the length of 5 to 15 micrometers, and the multi-wall carbon nano tube has the tube diameter of 1 to 3 nanometers and the length of 5 to 15 micrometers; the mass fraction of diethylenetriamine to the slurry was 5%. And coating the slurry to form a film, drying the film at 55 ℃ for 24h to obtain an amino-crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 50-1000 ℃, the heating rate is 20 ℃/min, the temperature is kept at 1000 ℃, and the total time is 200 h). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, the thermal conductivity and the mechanical properties of the obtained high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Example 6
The graphene oxide solution was prepared as in example 1.
The acidified carbon nanotubes were prepared as in example 1.
Uniformly stirring and mixing the prepared graphene oxide solution, the acidified carbon nano tube, the polyallylamine, the hydroxylamine hydrochloride and the hydrazine hydrate to obtain slurry; wherein the content of the graphene oxide is 31mg/mL slurry, and the mass ratio of the graphene oxide to the acidified carbon nanotube is 1:1; the mass fractions of the polyallylamine and the hydroxylamine hydrochloride relative to the slurry are both 6%; the mass fraction of hydrazine hydrate relative to the mass fraction of the slurry is 20%; the carbon nanotube comprises a multi-wall carbon nanotube and a single-wall carbon nanotube with a mass ratio of 1. And coating the slurry to form a film, drying at 40 ℃ for 100 hours to obtain an amino crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 1000 ℃ and the time is 8 hours). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, thermal conductivity and mechanical properties of the obtained high thermal conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Example 7
The graphene oxide solution was prepared as in example 1.
The acidified carbon nanotubes were prepared as in example 1.
Stirring and mixing the prepared graphene oxide solution, the acidified carbon nano tube, the ethylenediamine and the hydrazine hydrate uniformly to obtain slurry; the content of the graphene oxide is 31mg/mL slurry, and the mass ratio of the graphene oxide to an acidified carbon nanotube (the carbon nanotube is a double-walled carbon nanotube, the pipe diameter is 1-3 nanometers, and the length is 5-15 micrometers) is 1:0.5; the mass fraction of ethylenediamine with respect to the slurry was 5%, and the mass fraction of hydrazine hydrate with respect to the slurry was 20%. And coating the slurry to form a film, drying at 20 ℃ for 200 hours to obtain an amino crosslinked graphene oxide-carbon nanotube composite film, and then performing heat treatment to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film (the heat treatment temperature is 1000 ℃ and the time is 8 hours). Wherein the percentage is the mass percentage of each component relative to the mixed solution. The thickness, thermal conductivity and mechanical properties of the obtained high thermal conductivity nitrogen-doped graphene-carbon nanotube composite film are shown in table 1.
Comparative example 1
Except for the graphene oxide with the concentration of 0.5mg/mL, the other control parameters are the same as those in the embodiment 1, and the graphene oxide with the concentration of 0.5mg/mL is too low, so that the film structure is easy to break and cannot be continuously formed, and a continuous nitrogen-doped graphene film cannot be obtained.
Comparative example 2
The control parameters are the same as those in example 1 except that no water-soluble amine cross-linking agent is added, and the amine cross-linking agent is not added, so that the amino cross-linked graphene oxide-carbon nanotube composite membrane cannot be continuously formed, and is easy to break, low in tensile strength and poor in thermal conductivity. The thickness, mechanical properties and thermal conductivity are shown in table 1.
Comparative example 3
The control parameters are the same as those in example 1 except that no acidified carbon nanotube is added, and the obtained amino-modified graphene film has seriously reduced mechanical properties and thermal conductivity because no carbon nanotube is introduced. The thickness, mechanical properties and thermal conductivity are shown in table 1.
TABLE 1 data for thickness and thermal conductivity test of graphene films of examples 1 to 7 and comparative examples 1 to 3
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all structural equivalents which may be directly or indirectly applied to other related technical fields using the contents of the present specification are included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film is characterized by comprising the following steps of:
(1) Uniformly stirring and mixing the graphene oxide solution, the acidified carbon nano tube and the water-soluble amine cross-linking agent to obtain slurry;
wherein the mass ratio of the graphene oxide to the acidified carbon nanotubes in the slurry is (1;
the acidified carbon nano tube is an acidified multi-wall carbon nano tube and/or an acidified single-wall carbon nano tube;
the water-soluble amine cross-linking agent is one or more of ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ammonia, polyallylamine, hydrazine hydrate and p-phenylenediamine;
(2) Coating the slurry obtained in the step (1) to form a film, and drying to obtain an amino crosslinked graphene oxide-carbon nanotube composite film;
(3) Carrying out graphitization heat treatment on the amino cross-linked graphene oxide-carbon nanotube composite membrane prepared in the step (2) under the protection of inert atmosphere to obtain a nitrogen-doped graphene-carbon nanotube composite membrane;
(4) And (4) calendering the nitrogen-doped graphene-carbon nanotube composite film obtained in the step (3) to obtain the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film.
2. The method for preparing the nitrogen-doped graphene-carbon nanotube composite film with high thermal conductivity according to claim 1, wherein the preparation steps of the acidified carbon nanotubes are as follows:
mixing a carbon nano tube and an acidifying substance according to a set proportion, and stirring for 1 to 24h at 50 to 95 ℃ to obtain a mixture, wherein the carbon nano tube is a multi-wall carbon nano tube and/or a single-wall carbon nano tube, and the acidifying substance is sulfuric acid and/or sulfuric acid;
and pouring the mixture into water, filtering and collecting solid, and washing and drying the solid to obtain the acidified carbon nano tube.
3. The method for preparing the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film according to claim 1, wherein in the slurry in the step (1), the content of the graphene oxide is 1-80mg/mL slurry;
or, in the slurry in the step (1), the content of the graphene oxide is 31 to 80mg/mL of slurry.
4. The method for preparing the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film according to claim 1, wherein the mass ratio of the graphene oxide to the water-soluble amine crosslinking agent in the slurry is (1.
5. The method for preparing the nitrogen-doped graphene-carbon nanotube composite film with high thermal conductivity according to claim 1, wherein the graphene oxide solution is prepared by the following steps: (1) pre-oxidation: pouring graphite, concentrated sulfuric acid and nitric acid into water, filtering and drying to obtain pre-oxidized graphite; (2) thermal expansion: thermally expanding the pre-oxidized graphite in the step (1) for 5-30s at 950-1300 ℃ to obtain thermally expanded graphite oxide; (3) heating the thermal expansion graphite oxide obtained in the step (2) and a mixture of concentrated sulfuric acid, potassium persulfate and phosphorus pentoxide at 80-90 ℃, adding water, filtering, washing and drying to obtain pre-oxidized thermal expansion graphite; (4) and (3) mixing the pre-oxidized thermal expansion graphite in the step (3) with concentrated sulfuric acid at 0-5 ℃, adding potassium permanganate, reacting, adding hydrogen peroxide, standing, filtering, centrifugally washing, adding water, and stirring to obtain a graphene oxide solution.
6. The preparation method of the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film according to claim 1, wherein in the step (2), the drying temperature is 60 to 95 ℃, and the drying time is 0.5 to 200 hours;
or in the step (2), the drying temperature is 65 to 95 ℃, and the drying time is 2 to 50 hours.
7. The method for preparing the nitrogen-doped graphene-carbon nanotube composite film with high thermal conductivity according to claim 1, wherein in the step (3), the temperature of the heat treatment is 50-3000 ℃, and the time of the heat treatment is 0.5-200 hours;
or, in the step (3), the temperature of the heat treatment is 1000-3000 ℃, and the time of the heat treatment is 2-10 hours.
8. The method for preparing the nitrogen-doped graphene-carbon nanotube composite film with high thermal conductivity according to claim 1 or 7, wherein in the step (3), the inert atmosphere is one or more of nitrogen, argon and helium.
9. The method for preparing the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film according to claim 1, wherein the diameter of the acidified carbon nanotube is 10 to 200nm.
10. The high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film prepared by the preparation method of the high-thermal-conductivity nitrogen-doped graphene-carbon nanotube composite film according to any one of claims 1 to 9, wherein the thermal conductivity is 700-1500W/mk or 1600-2000W/mk.
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| CN106861617A (en) * | 2017-01-25 | 2017-06-20 | 河北大学 | A kind of preparation method and applications of Graphene/carbon nanotube composite material |
| CN107686107A (en) * | 2017-08-28 | 2018-02-13 | 中国石油大学(华东) | The preparation method of the hydrophobic CNT graphene composite aerogel of elasticity |
| CN114212778A (en) * | 2021-12-29 | 2022-03-22 | 杭州嘉悦智能设备有限公司 | Preparation method of nitrogen-doped graphene film and nitrogen-doped graphene film |
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