CN110723724A - Three-dimensional graphene-carbon nanotube network structure and preparation method thereof - Google Patents
Three-dimensional graphene-carbon nanotube network structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional graphene-carbon nanotube network structure and a preparation method thereof, wherein the three-dimensional graphene-carbon nanotube network structure comprises the following steps: the three-dimensional graphene-carbon nanotube network structure is prepared by selecting a chlorine-containing benzene ring structure as a carbon source, growing a carbon nanotube sponge body by a chemical vapor deposition method, preparing polyamic acid, putting the carbon nanotube sponge body into the polyamic acid solution, performing thermal imidization treatment, and then performing carbonization and graphitization processes. The three-dimensional graphene-carbon nanotube network structure composite material has better heat-conducting property and mechanical property, provides a new method for preparing a carbon functional material, and also widens the application range of the carbon composite material.
Description
Technical Field
The invention belongs to the field of carbon functional composite materials, and particularly relates to a three-dimensional graphene-carbon nanotube network structure and a preparation method thereof, in particular to a three-dimensional graphene-carbon nanotube sponge and a preparation method thereof.
Background
Carbon Nanotubes (CNTs) and Graphene (Graphene) were discovered in 1991 and 2004, respectively, and have been of interest since the day they were discovered. Despite the numerous enthusiasms raised, it is still the focus of developers in many fields, and graphene and carbon nanotubes have been widely used in many fields due to their many unique and excellent characteristics. Carbon nanotubes and graphene are excellent one-dimensional and two-dimensional carbon materials, respectively, which exhibit one-dimensional and two-dimensional anisotropy, such as electrical conductivity, mechanical properties, thermal conductivity, and the like. In order to combine the advantages of both, graphene and carbon nanotubes have been used together in composite materials. The graphene and carbon nanotube composite material forms a three-dimensional network structure, and the graphene and carbon nanotube composite material shows more excellent performance than any single material, such as better isotropic thermal conductivity, isotropic electrical conductivity, three-dimensional space microporous network and the like, through a synergistic effect between the graphene and carbon nanotube composite material. Based on the properties, the graphene/carbon nanotube composite material has a good application prospect in the aspects of super capacitors, solar cells, displays, biological detection, fuel cells and the like.
The carbon nano tube sponge is a novel three-dimensional integral functional material, and has a developed pore structure, an ultra-large specific surface area and an ultra-light density. At present, the main methods for preparing the graphene sponge body include an electric arc method, a chemical vapor deposition method, a laser evaporation method, a floating catalysis method and the like. The material has the properties of low density, high heat conduction, high temperature resistance, chemical corrosion resistance and the like, is greatly applied to the fields of aerospace, satellites, navigation and the like, and is considered to be one of the most potential materials in the future.
The graphene has extremely high thermal conductivity and mechanical strength, and the conjugated molecular surface structure of the graphene can provide an ideal two-dimensional channel for phonon conduction. The micron-sized graphene increases contact with a polymer matrix due to the large surface area. Based on this, graphene is regarded as an excellent filler for achieving high thermal conductivity, and thus has received extensive attention from researchers. Meanwhile, the carbon nano tube also has good heat conductivity, so that a novel carbon composite material which is lighter in mass, higher in heat conductivity, better in heat dissipation capability and good in rebound resilience can be prepared by combining the advantages of the carbon nano tube and the carbon nano tube, the preparation of the carbon-based high-heat-conductivity material by using the expanded graphite is also a research focus of people, and similar patent authorization or publication also appears. The invention patents of the national intellectual property office of the people's republic of China with the grant numbers of CN101407322B, CN100368342C, CN101458049A and the like disclose the technology of preparing a heat conducting plate by utilizing compressed expanded graphite, but the existing technology compounds a graphene sponge body and a carbon nano tube and does not relate to the technical content of preparing the carbon nano tube sponge body.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a three-dimensional graphene-carbon nanotube network structure and a preparation method thereof, which can realize the uniform compounding of a carbon nanotube sponge and graphene and have good performance.
The technical purpose of the invention is realized by the following technical scheme:
a three-dimensional graphene-carbon nanotube network structure and a preparation method thereof are prepared according to the following steps:
in the step 1, vacuum impregnation is adopted for 0.5-3 h, preferably 1-3 h.
In step 1, the thermal imidization treatment is carried out for 1 to 5 hours, preferably 1 to 3 hours.
In step 1, the temperature for thermal imidization is 320 to 360 ℃.
In step 1, p-phenylenediamine and biphenyltetracarboxylic dianhydride are reacted in an equimolar ratio in dimethylacetamide for a period of 1 to 10 hours, preferably 5 to 8 hours.
In step 1, the structure of the benzene ring containing chlorine is chlorobenzene, dichlorobenzene, trichlorobenzene, or dichlorobenzene and trichlorobenzene with equal mass.
In the step 1, the concentration of ferrocene is 0.02-0.06 g/ml, and the mass-to-volume ratio of the carbon source to the absolute ethyl alcohol is (0.5-5): 50, the unit of the mass of the carbon source is g, and the unit of the volume of the absolute ethyl alcohol is ml.
In the step 1, the injection speed of the mixed solution is 10-25 ml/h.
In step 1, the temperature is raised from room temperature 20-25 ℃ to 800-900 ℃ at a constant speed at a temperature rise rate of 1-10 ℃ per minute, and the carbon nanotube sponge is grown for 1-10 hours, preferably 6-10 hours.
Step 2, carbonizing the structure of the polyimide-coated carbon nanotube sponge obtained in the step 1, and then graphitizing to obtain a three-dimensional graphene-carbon nanotube composite network material, wherein the carbonizing treatment is carried out by heating from room temperature of 20-25 ℃ to 900-1200 ℃ at a heating rate of 1-10 ℃ per minute in an inert protective gas atmosphere; and continuously carrying out graphitization treatment on the sample subjected to carbonization treatment at the high temperature of 2500-2800 ℃ in the atmosphere of inert protective gas.
In step 2, the carbonization treatment time is 1 to 5 hours, preferably 1 to 3 hours.
In step 2, the carbonization temperature is 1000-1200 ℃.
In the step 2, the graphitization treatment temperature is 2600-2800 ℃.
In step 2, the graphitization treatment time is 1 to 5 hours, preferably 1 to 3 hours.
In the step 2, after carbonization, the temperature is continuously increased to graphitization treatment at the temperature increasing speed of 1-10 ℃ per minute, heat is preserved for graphitization treatment, and furnace cooling is carried out to room temperature.
In the technical scheme of the invention, the inert protective gas is nitrogen, helium or argon.
Compared with the prior art, the invention discloses a three-dimensional graphene-carbon nanotube network structure and a preparation method thereof. The three-dimensional graphene-carbon nanotube network structure composite material obtained by the invention has better mechanical properties, provides a new method for preparing carbon functional materials, and also widens the application range of the carbon composite material.
Drawings
Fig. 1 is a scanning electron micrograph (1) of the three-dimensional network structure of the graphene-carbon nanotube sponge prepared according to the present invention.
Fig. 2 is a scanning electron micrograph (2) of the three-dimensional network structure of the graphene-carbon nanotube sponge prepared according to the present invention.
Fig. 3 is a transmission electron microscope photograph (1) of the graphene-carbon nanotube sponge with a three-dimensional network structure prepared by the present invention.
Fig. 4 is a transmission electron microscope photograph (2) of the graphene-carbon nanotube sponge with a three-dimensional network structure prepared by the present invention.
FIG. 5 is a Raman spectrum diagram of the carbon nanotube sponge processed by different processes.
FIG. 6 is a graph showing the cyclic compression curve of the carbon nanotube sponge according to the present invention.
Fig. 7 is a cyclic compression curve diagram of the three-dimensional network structure of the graphene-carbon nanotube sponge prepared by the present invention.
Detailed Description
The following is a further description of the invention and is not intended to limit the scope of the invention.
Example 1
1) Preparing a carbon nano tube sponge: taking a chlorine-containing benzene ring structure as a carbon source, preparing a solution from 0.5g of chlorobenzene and 50ml of absolute ethyl alcohol as the carbon source for growing the carbon nano tube, adding ferrocene into the solution and uniformly dispersing the ferrocene to ensure that the concentration of the ferrocene is 0.04g/ml, and taking the solution as a catalyst and a carbon source for growing the carbon nano tube sponge; injecting the carbon nano tube into a vacuum tube furnace at an injection speed of 15ml/h, introducing argon as a protective gas, and uniformly heating to 800 ℃ from the room temperature of 20-25 ℃ at a heating speed of 5 ℃ per minute to grow a carbon nano tube sponge;
2) respectively dissolving 0.061mol of p-Phenylenediamine (PDA) and 0.061mol of biphenyl tetracarboxylic dianhydride (BPDA) in 60ml of dimethylacetamide (DMAc) solution, stirring until the solutions are fully dissolved, then mixing the two solutions according to the volume ratio of 1:1, reacting for 5 hours under the ice bath condition, and obtaining a polyamic acid solution under the nitrogen protection condition;
3) dipping the carbon nano tube sponge (with the growth time of 6 hours) prepared in the step 1) in a polyamic acid solution, vacuum dipping for 1.5 hours, then carrying out solvent replacement by using tert-butyl alcohol to remove DMAc, then carrying out freeze drying treatment, and after the treatment, placing a sample in a tubular furnace to carry out thermal imidization treatment for 1 hour at 350 ℃ to prepare a polyimide-coated carbon nano tube sponge structure;
4) in the argon atmosphere, raising the temperature from the room temperature of 20-25 ℃ to 1000 ℃ at the temperature raising speed of 5 ℃ per minute, and carrying out heat preservation carbonization for 1 h; and then putting the carbonized sample into a graphitization furnace, performing graphitization treatment at the high temperature of 2600 ℃ in an argon atmosphere, preserving heat, performing graphitization treatment for 1h to obtain the three-dimensional graphene-carbon nanotube composite network material, and cooling to room temperature along with the furnace.
Example 2
1) Preparing a carbon nano tube sponge: taking a chlorine-containing benzene ring structure as a carbon source, preparing 1g of dichlorobenzene and 50ml of absolute ethyl alcohol into a solution serving as the carbon source for growing the carbon nano tube, adding ferrocene into the solution and uniformly dispersing the ferrocene to ensure that the concentration of the ferrocene is 0.04g/ml, and taking the solution as a catalyst and a carbon source for growing the carbon nano tube sponge; injecting the carbon nano tube into a vacuum tube furnace at an injection speed of 15ml/h, introducing argon as a protective gas, and uniformly heating to 800 ℃ from the room temperature of 20-25 ℃ at a heating speed of 5 ℃ per minute to grow a carbon nano tube sponge;
2) respectively dissolving 0.06mol of p-phenylenediamine and 0.06mol of biphenyl tetracarboxylic dianhydride in 60ml of DMAc solution, stirring until the p-phenylenediamine and the biphenyl tetracarboxylic dianhydride are fully dissolved, then mixing the two DMAc solutions according to the volume ratio of 1:1, reacting for 8 hours under the ice bath condition, and obtaining a polyamic acid solution under the nitrogen protection condition;
3) dipping the carbon nano tube sponge (with the growth time of 8 hours) prepared in the step 1) in a polyamic acid solution, carrying out vacuum dipping for 2 hours, then carrying out solvent replacement by using tert-butyl alcohol to remove DMAc, then carrying out freeze drying treatment, and after the treatment, placing a sample in a tubular furnace to carry out thermal imidization treatment for 5 hours at 330 ℃ to prepare a polyimide-coated carbon nano tube sponge structure;
4) in the argon atmosphere, raising the temperature from room temperature of 20-25 ℃ to 1050 ℃ at a temperature raising speed of 5 ℃ per minute, and carrying out carbonization treatment for 1 h; and then placing the carbonized sample into a graphitization furnace, performing graphitization treatment at the high temperature of 2700 ℃ in an argon atmosphere, performing graphitization treatment for 1h to finally obtain the three-dimensional graphene-carbon nanotube composite network material, and cooling the three-dimensional graphene-carbon nanotube composite network material to room temperature along with the furnace.
Example 3
1) Preparing a carbon nano tube sponge: taking a chlorine-containing benzene ring structure as a carbon source, preparing a solution from 2g of trichlorobenzene and 50ml of absolute ethyl alcohol as the carbon source for growing the carbon nano tube, adding ferrocene into the solution and uniformly dispersing the ferrocene to ensure that the concentration of the ferrocene is 0.04g/ml, and taking the solution as a catalyst and a carbon source for growing the carbon nano tube sponge; injecting the carbon nano tube into a vacuum tube furnace at the injection speed of 25ml/h, introducing argon as a protective gas, and uniformly heating the carbon nano tube to 850 ℃ from the room temperature of 20-25 ℃ at the heating speed of 5 ℃ per minute to grow the carbon nano tube sponge;
2) respectively dissolving 0.065mol of p-phenylenediamine and 0.065mol of biphenyl tetracarboxylic dianhydride in 65ml of DMAc solution, stirring until the p-phenylenediamine and the biphenyl tetracarboxylic dianhydride are fully dissolved, then mixing the two DMAc solutions according to the volume ratio of 1:1, reacting for 5 hours under the ice bath condition, and obtaining a polyamic acid solution under the nitrogen protection condition;
3) dipping the carbon nano tube sponge (with the growth time of 10 hours) prepared in the step 1) in a polyamic acid solution, vacuum dipping for 1.5 hours, then carrying out solvent replacement by using tert-butyl alcohol to remove DMAc, then carrying out freeze drying treatment, and after the treatment, placing a sample in a tubular furnace to carry out thermal imidization treatment for 3 hours at 340 ℃ to prepare a polyimide-coated carbon nano tube sponge structure;
4) in the argon atmosphere, raising the temperature from the room temperature of 20-25 ℃ to 1100 ℃ at the temperature raising speed of 5 ℃ per minute, and carrying out heat preservation carbonization for 1 h; and then placing the carbonized sample into a graphitization furnace, performing graphitization treatment at the high temperature of 2700 ℃ in an argon atmosphere, performing graphitization treatment for 1h to finally obtain the three-dimensional graphene-carbon nanotube composite network material, and cooling the three-dimensional graphene-carbon nanotube composite network material to room temperature along with the furnace.
Example 4
1) Preparing a carbon nano tube sponge: taking a chlorine-containing benzene ring structure as a carbon source, preparing 3g of chlorobenzene (1.5 g of dichlorobenzene and trichlorobenzene respectively) and 30ml of absolute ethyl alcohol into a solution serving as the carbon source for growing the carbon nano tube, adding ferrocene into the solution and uniformly dispersing the ferrocene to ensure that the concentration of the ferrocene is 0.05g/ml, taking the solution as a catalyst and a carbon source for growing the carbon nano tube sponge, injecting the solution into a vacuum tube furnace at an injection speed of 15ml/h, introducing argon as a protective gas, and uniformly heating the solution to 900 ℃ from the room temperature of 20-25 ℃ at a heating speed of 5 ℃ per minute to grow the carbon nano tube sponge;
2) respectively dissolving 0.063mol of p-phenylenediamine and 0.063mol of biphenyl tetracarboxylic dianhydride in 63ml of DMAc solution, stirring until the p-phenylenediamine and the biphenyl tetracarboxylic dianhydride are fully dissolved, then mixing the two DMAc solutions according to the volume ratio of 1:1, reacting for 5 hours under the ice bath condition, and obtaining a polyamic acid solution under the nitrogen protection condition;
3) dipping the carbon nano tube sponge (with the growth time of 8 hours) prepared in the step 1) in a polyamic acid solution, carrying out vacuum dipping for 2.5 hours, then carrying out solvent replacement by using tert-butyl alcohol to remove DMAc, then carrying out freeze drying treatment, and after the treatment, placing a sample in a tubular furnace to carry out thermal imidization treatment for 1 hour at 360 ℃ to prepare a polyimide-coated carbon nano tube sponge structure;
4) in the argon atmosphere, raising the temperature from the room temperature of 20-25 ℃ to 1200 ℃ at the temperature raising speed of 5 ℃ per minute, and carrying out heat preservation carbonization for 1 h; (ii) a And then placing the carbonized sample into a graphitization furnace, performing graphitization treatment at the high temperature of 2800 ℃ in an argon atmosphere, performing graphitization treatment for 1h to obtain the three-dimensional graphene-carbon nanotube composite network material, and cooling to room temperature along with the furnace.
The prepared three-dimensional graphene-carbon nanotube composite network material is characterized as shown in attached figures 1-7. The graphene-carbon nanotube composite material presents a three-dimensional network structure; characteristic peaks existing in the Raman spectrum show that good crystalline carbon appears after the carbon nanotube sponge body is carbonized at high temperature, sp2 hybridization appears at nodes, so that the nodes of the carbon nanotubes are better connected, and potential heat conduction and electric conduction performance exist; the test of cyclic compression is carried out aiming at elasticity, under the stress of 100Kpa, the sample is cyclically compressed for 100 circles, the fact that the carbon nano tube sponge is soft and difficult to recover after deformation is found, the finally prepared graphene-carbon nano tube sponge has good elastic performance, and 80% of the graphite-carbon nano tube sponge can be recovered after 100 circles of compression.
The preparation of the three-dimensional graphene-carbon nanotube composite network material can be realized by adjusting the process parameters according to the content of the invention, and the performance of the three-dimensional graphene-carbon nanotube composite network material is basically consistent with that of the embodiment. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A three-dimensional graphene-carbon nanotube network structure is characterized by being prepared according to the following steps:
step 1, dipping a carbon nano tube sponge body in a dimethyl acetamide solution of polyamic acid, performing solvent replacement by using tert-butyl alcohol to remove dimethyl acetamide, performing freeze drying treatment, and performing thermal imidization treatment at 300-400 ℃ to obtain a polyimide-coated carbon nano tube sponge body structure, wherein: the dimethylacetamide solution of polyamic acid is obtained by reacting p-phenylenediamine and biphenyl tetracarboxylic dianhydride in an equimolar ratio in dimethylacetamide under ice bath and inert protective gas atmosphere; uniformly mixing and dispersing a chlorine-containing benzene ring structure serving as a carbon source, absolute ethyl alcohol and ferrocene, growing a carbon nanotube sponge by using the mixed solution, injecting the carbon nanotube sponge into a vacuum tube furnace, and raising the temperature to 800-900 ℃ at a constant speed by using inert protective gas as an atmosphere to grow the carbon nanotube sponge;
step 2, carbonizing the structure of the polyimide-coated carbon nanotube sponge obtained in the step 1, and then graphitizing to obtain a three-dimensional graphene-carbon nanotube composite network material, wherein the carbonizing treatment is carried out by heating from room temperature of 20-25 ℃ to 900-1200 ℃ at a heating rate of 1-10 ℃ per minute in an inert protective gas atmosphere; and continuously carrying out graphitization treatment on the sample subjected to carbonization treatment at the high temperature of 2500-2800 ℃ in the atmosphere of inert protective gas.
2. The three-dimensional graphene-carbon nanotube network structure according to claim 1, wherein in step 1, vacuum impregnation is adopted for 0.5-3 hours, preferably 1-3 hours; the time for the thermal imidization treatment is 1 to 5 hours, preferably 1 to 3 hours, and the temperature for the thermal imidization treatment is 320 to 360 ℃.
3. The three-dimensional graphene-carbon nanotube network according to claim 1, wherein in step 1, p-phenylenediamine and biphenyltetracarboxylic dianhydride are reacted in an equimolar ratio in dimethylacetamide for a period of 1 to 10 hours, preferably 5 to 8 hours.
4. The three-dimensional graphene-carbon nanotube network structure according to claim 1, wherein in step 1, the structure of the chlorine-containing benzene ring is chlorobenzene, dichlorobenzene, trichlorobenzene, or dichlorobenzene and trichlorobenzene with equal mass; the concentration of the ferrocene is 0.02-0.06 g/ml, and the mass-volume ratio of the carbon source to the absolute ethyl alcohol is (0.5-5): 50, preferably (1-5): 50; the injection speed of the mixed solution is 10-25 ml/h; the temperature is raised from room temperature of 20-25 ℃ to 800-900 ℃ at a constant speed at a temperature rise rate of 1-10 ℃ per minute, and the growth of the carbon nanotube sponge is carried out for 1-10 hours, preferably 6-10 hours.
5. The three-dimensional graphene-carbon nanotube network structure according to claim 1, wherein in step 2, the carbonization time is 1 to 5 hours, preferably 1 to 3 hours, and the carbonization temperature is 1000 to 1200 ℃; the graphitization temperature is 2600-2800 ℃, and the graphitization time is 1-5 hours, preferably 1-3 hours.
6. A preparation method of a three-dimensional graphene-carbon nanotube network structure is characterized by comprising the following steps: step 1, dipping a carbon nano tube sponge body in a dimethyl acetamide solution of polyamic acid, performing solvent replacement by using tert-butyl alcohol to remove dimethyl acetamide, performing freeze drying treatment, and performing thermal imidization treatment at 300-400 ℃ to obtain a polyimide-coated carbon nano tube sponge body structure, wherein: the dimethylacetamide solution of polyamic acid is obtained by reacting p-phenylenediamine and biphenyl tetracarboxylic dianhydride in an equimolar ratio in dimethylacetamide under ice bath and inert protective gas atmosphere; uniformly mixing and dispersing a chlorine-containing benzene ring structure serving as a carbon source, absolute ethyl alcohol and ferrocene, growing a carbon nanotube sponge by using the mixed solution, injecting the carbon nanotube sponge into a vacuum tube furnace, and raising the temperature to 800-900 ℃ at a constant speed by using inert protective gas as an atmosphere to grow the carbon nanotube sponge;
step 2, carbonizing the structure of the polyimide-coated carbon nanotube sponge obtained in the step 1, and then graphitizing to obtain a three-dimensional graphene-carbon nanotube composite network material, wherein the carbonizing treatment is carried out by heating from room temperature of 20-25 ℃ to 900-1200 ℃ at a heating rate of 1-10 ℃ per minute in an inert protective gas atmosphere; and continuously carrying out graphitization treatment on the sample subjected to carbonization treatment at the high temperature of 2500-2800 ℃ in the atmosphere of inert protective gas.
7. The method for preparing the three-dimensional graphene-carbon nanotube network structure according to claim 6, wherein in the step 1, vacuum impregnation is adopted for the impregnation, and the time is 0.5-3 hours, preferably 1-3 hours; the time for the thermal imidization treatment is 1 to 5 hours, preferably 1 to 3 hours, and the temperature for the thermal imidization treatment is 320 to 360 ℃.
8. The method for preparing a three-dimensional graphene-carbon nanotube network structure according to claim 6, wherein in step 1, p-phenylenediamine and biphenyltetracarboxylic dianhydride are reacted in an equimolar ratio in dimethylacetamide for 1 to 10 hours, preferably 5 to 8 hours.
9. The method for preparing the three-dimensional graphene-carbon nanotube network structure according to claim 6, wherein in the step 1, the structure of the benzene ring containing chlorine is chlorobenzene, dichlorobenzene, trichlorobenzene, or dichlorobenzene and trichlorobenzene with equal mass; the concentration of the ferrocene is 0.02-0.06 g/ml, and the mass-volume ratio of the carbon source to the absolute ethyl alcohol is (0.5-5): 50, preferably (1-5): 50; the injection speed of the mixed solution is 10-25 ml/h; the temperature is raised from room temperature of 20-25 ℃ to 800-900 ℃ at a constant speed at a temperature rise rate of 1-10 ℃ per minute, and the growth of the carbon nanotube sponge is carried out for 1-10 hours, preferably 6-10 hours.
10. The method for preparing a three-dimensional graphene-carbon nanotube network structure according to claim 6, wherein in the step 2, the carbonization time is 1 to 5 hours, preferably 1 to 3 hours, and the carbonization temperature is 1000 to 1200 ℃; the graphitization temperature is 2600-2800 ℃, and the graphitization time is 1-5 hours, preferably 1-3 hours.
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