CN112174114B - Mixed carbon nanotube film and preparation method thereof - Google Patents
Mixed carbon nanotube film and preparation method thereof Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention discloses a mixed carbon nanotube film and a preparation method thereof, wherein catalysts and promoters with different amounts are dissolved in an organic carbon source to form uniform solutions with different concentrations, then the solutions are injected into a plurality of atomizers to form tiny liquid drops with uniform sizes, the tiny liquid drops respectively enter different reaction tubes of a multi-tube parallel CVD reactor under the drive of carrier gas, barrel-shaped aerogel consisting of different carbon nanotubes is continuously generated in a high-temperature area of a tube furnace, the aerogel is twisted and mixed and then is guided to a roller which rotates and horizontally reciprocates, and the mixed carbon nanotube film can be obtained after a period of time; the invention utilizes a floating chemical vapor deposition method, and finally obtains the mixed carbon nanotube film by changing the types and the dosage of the catalyst, the accelerant and the carbon source; the mixed carbon nanotube film prepared by the invention has the advantages of low cost, high yield, high purity, less impurities, high conductivity, high mechanical strength and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a mixed carbon nanotube film and a preparation method thereof.
Background
In 1991, the first formal report of carbon nanotubes has brought attention to this hollow tubular structure in the nanoscale range. Although the carbon nano tube has excellent mechanical property, electric conduction and heat conduction capability and outstanding physical and chemical stability under extreme conditions of high temperature, acid, alkali and the like, the carbon nano tube powder is difficult to show the performance advantage on the micro scale in the macroscopic view.
In 2004, the floating catalytic CVD method for preparing carbon nanotube films was realized. The carbon nanotube film prepared by the method has no adhesive or dispersant inside, and the carbon nanotubes are connected together by chemical bonds and Van der Waals force, so that the carbon nanotube film inherits various excellent properties of the carbon nanotubes, is very light, thin and flexible, and has extremely high application value in high-end fields such as national defense, military industry, aerospace and the like.
Each key performance index of the carbon nano tube film is determined by the tube wall structure of the carbon nano tube and a conductive network formed by the tube wall structure.
Analysis shows that, in general conditions, when a carbon nanotube film is prepared by a floating catalytic CVD method, a reaction system needs very stable dynamic balance, wherein the pipe diameter and the pipe wall structure of the carbon nanotube change very little, so that the improvement of the performance of the carbon nanotube film can only be realized by reducing the diameter and the thickness of the carbon nanotube and increasing the number of the carbon nanotubes on the premise that the total amount of a carbon source is fixed. However, the pipe diameter of the carbon nano tube is reduced, the wall of the tube is thinned to a limit, and when the number of lattice layers of the tube wall is two, the conductivity of the carbon nano tube film reaches the maximum value; continuing to reduce the number of lattice layers in the walls of the tube results in 2/3 carbon nanotubes becoming semiconducting and the overall conductivity of the film decreases. Moreover, the cost of the double-walled carbon nanotube film is high, which is an obstacle to large-scale popularization.
Since carbon nanotubes have been formally reported in 1991, the carbon nanotubes prepared by CVD method generally tend to agglomerate with each other to reduce surface energy, and the agglomerates of carbon nanotubes with uniform tube diameter size usually appear in the form of hexagonal close-packed bundles, in which a large number of structural voids are left. The gap can not be eliminated in the rolling process at the later stage of the film production, and the existence of the gap causes a series of problems that the contact between the carbon nanotubes in the film is not tight enough, the integral density of the film is reduced, the contact resistance between the tubes is increased, the integral resistivity of the film is improved, and the like.
Disclosure of Invention
The invention aims to solve the technical problem that the existing preparation method causes the defect of structural gaps in the carbon nanotube film, and provides a mixed carbon nanotube film and a preparation method thereof.
In order to solve the above technical problems, the present invention provides a mixed carbon nanotube film, which is composed of carbon nanotubes having different tube diameters and different tube wall structures.
The invention also designs a preparation method of the mixed carbon nanotube film, which comprises the following steps:
s1 mixing and stirring: adding carbon sources, catalysts and promoters in different proportions into a plurality of beakers, and fully stirring until the carbon sources, the catalysts and the promoters are completely dissolved;
s2, heating and ventilating: placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, heating, introducing inert gas into the reactor and a collecting box body, and introducing hydrogen into the system after the tube furnace is heated to a target temperature;
s3 pipe making: respectively injecting the solution prepared in the step S1 into a plurality of different atomizers, atomizing the solution to form tiny droplets with uniform sizes, adjusting the hydrogen flow, and respectively bringing the tiny droplets into different reaction tubes of the multi-tube parallel CVD reactor in the step S2 at a constant flow rate to obtain the barrel-shaped aerogel consisting of carbon nano tubes with different tube wall structures;
s4 film preparation: and (3) twisting and mixing the different barrel-shaped carbon nanotube aerogels prepared in the step S3, collecting the mixture on a roller which horizontally moves back and forth and rotates, and taking down the aerogels from the roller and rolling when the thickness of the aerogels reaches 6-15 cm to obtain the mixed carbon nanotube film.
The invention further defines the technical scheme that:
further, in the preparation method of the mixed carbon nanotube film, the mass ratio of the carbon source, the catalyst and the accelerator in the step S1 is (93-99.79): (4.5-0.2): (2.5-0.01);
preferably, the mass ratio of the carbon source, the catalyst and the promoter in the step S1 is (94.2-99.74): (4.1-0.24): 1.7-0.02).
In the preparation method of the mixed carbon nanotube film, the carbon source in step S1 is one or more of methanol, ethanol, isopropanol, mannitol, acetone, benzene, and toluene;
preferably, the carbon source in step S1 is one or more of methanol, ethanol, isopropanol, mannitol, and toluene.
In the preparation method of the mixed carbon nanotube film, the catalyst in step S1 is one or a combination of more of cyclopentadienyl compounds of iron, cobalt and nickel, acetylacetone compounds, nitrates, sulfates, chlorides, and acetates and oxalates;
preferably, the catalyst in step S1 is a combination of cyclopentadienyl compounds of iron, cobalt and nickel, acetylacetone compounds, nitrates and one or more of acetates and oxalates.
In the preparation method of the mixed carbon nanotube film, the accelerator in step S1 is one or a combination of more of thiophene, thiophene- α -sulfonamide, sulfur powder, ethanethiol, carbon disulfide, thiourea, 2-mercaptopyridine, and thioacetamide;
preferably, the accelerator in step S1 is one or more of thiophene, carbon disulfide, and sulfur powder.
In the preparation method of the mixed carbon nanotube film, the target temperature in the step S2 is 1100-1500 ℃;
preferably, the target temperature in step S2 is 1150-1450 ℃.
In the preparation method of the mixed carbon nanotube film, the introduction speed of the hydrogen in the step S2 is 0.5-16L/min.
In the preparation method of the mixed carbon nanotube film, the inert gas introducing speed in the step S2 is 1-2L/min, and the hydrogen introducing speed is 1-14L/min.
The invention has the beneficial effects that:
the invention uses a floating catalytic chemical vapor deposition method to obtain the mixed carbon nanotube film. Compared with the traditional floating gas phase catalytic chemical deposition method, in the reaction process, catalyst precursors and auxiliaries in different proportions are firstly dissolved in a carbon source to form uniform solutions with different concentrations, and then the solutions with different concentrations are respectively injected into a plurality of atomizers to be atomized to form tiny droplets with uniform sizes. The tiny droplets are respectively carried into different reaction tubes of the multi-tube row CVD reactor by hydrogen carrier gas, and the carbon source, the catalyst precursor and the auxiliary agent are all vaporized along with the rise of the furnace temperature. And the carbon source is cracked at high temperature to provide the carbon source, so that the continuous growth of the carbon nano tube is ensured. In the whole reaction process, the hydrogen is used as a carrier gas, provides a reducing environment for the production of the carbon nano tube and participates in the generation of the carbon nano tube. Twisting and mixing the carbon nanotube barrel-shaped aerogel with different tube wall structures generated by the multi-tube row CVD reactor, collecting the carbon nanotube barrel-shaped aerogel on a roller which horizontally moves back and forth and rotates, and taking off and rolling the carbon nanotube barrel-shaped aerogel from the surface of the roller when the thickness of the carbon nanotube barrel-shaped aerogel reaches the required thickness. The carbon nanotubes are connected with each other through intermolecular force and van der waals force, and the carbon nanotubes with small diameter can be embedded into the gaps of the carbon nanotube bundles with large diameter, so that a high-density mixed carbon nanotube film can be formed.
According to the invention, by accurately controlling reaction parameters, each reaction tube of the multi-tube row CVD reactor is always in different dynamic equilibrium states, so that a stable environment is provided for the generation of continuous barrel-shaped carbon nanotube aerogel with different structures; tests prove that the density of the mixed carbon nanotube film prepared by the method is improved by 30 percent compared with that of a multi-wall carbon nanotube film prepared by the traditional CVD method, the conductivity of the film with the same thickness is doubled, and the mechanical strength is improved by 60 percent. And because the catalyst particles are reduced, the catalytic efficiency is improved, the dosage of the catalyst is correspondingly reduced, the manufacturing cost is further reduced, and the impurity content in the product is reduced. Therefore, the method has very high popularization value.
Drawings
FIG. 1 is a schematic structural diagram of a hybrid carbon nanotube film according to an embodiment of the present invention;
FIG. 2 is a Raman spectrum of a mixed carbon nanotube film A1 according to example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the mixed carbon nanotube film A1 magnified 2 ten thousand times in example 1 of the present invention;
FIG. 4 is a high resolution TEM image of the mixed CNT film A1 in example 1 of the present invention;
FIG. 5 is a Raman spectrum of the mixed carbon nanotube film A2-A5 according to example 2-5 of the present invention;
FIG. 6 is a scanning electron microscope image of the mixed carbon nanotube film A2 magnified 5 ten thousand times in example 2 of the present invention;
FIG. 7 is a high resolution TEM image of the mixed CNT film A2 in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
This example provides a mixed carbon nanotube film consisting of single-walled and multi-walled carbon nanotubes.
The preparation method specifically comprises the following steps:
s1 mixing and stirring:
according to the mass ratio of 99.6: 0.38: respectively weighing 100 g of ethanol, ferrocene and thiophene according to the proportion of 0.02, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
according to the mass ratio of 97: 1.5: 1.5, respectively weighing 100 g of ethanol, ferrocene and thiophene, adding the weighed substances into another beaker, and stirring until the substances are completely dissolved;
s2 heating and ventilating:
placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, starting the tube furnace to heat, introducing inert gas into the reactor and a collecting box body at the flow rate of 1L/min, and introducing hydrogen into the multi-tube row CVD reactor at the speed of 10L/min after the tube furnace is heated to 1200 ℃, so as to provide a stable environment for the subsequent generation of the carbon nano tube film;
S3 pipe making:
respectively injecting the solutions prepared in the step S1 into two atomizers, atomizing the solutions to form tiny droplets with uniform sizes, adjusting hydrogen flow, respectively carrying the tiny droplets into two different reaction tubes of the multi-tube parallel CVD reactor in the step S2 by hydrogen flow at a constant flow rate, and collecting at the other end of the tube furnace to obtain continuous barrel-shaped aerogel formed by mixing multi-wall carbon nanotubes and single-wall carbon nanotubes;
s4 film making:
and (3) twisting and mixing the aerogel prepared in the S3, embedding single-walled carbon nanotubes into gaps of a multi-walled carbon nanotube bundle in the process, collecting the mixture on a roller which rotates and slowly moves horizontally as shown in figure 1, taking the mixture off the roller and rolling when the thickness of the aerogel reaches 10 cm, and testing the thickness of the mixture to be 25 microns and the surface resistivity to be 0.13 +/-0.05 ohm/SQ to obtain a mixed carbon nanotube film A1.
The mixed carbon nanotube film A1 prepared in the example was analyzed and tested by Raman spectroscopy, scanning electron microscopy and high resolution transmission electron microscopy, respectively, and the characterization results of Raman spectroscopy shown in FIG. 2 indicated that the thickness was 195 cm-1And 213 cm-1Two characteristic respiration peaks are respectively provided, which indicates that the carbon nanotube film contains single-walled carbon nanotubes and is arranged from 1322 cm -1D-band peak intensity of (2) and 1591 cm-1The G-band peak of the carbon nanotube film is not split, so that the carbon nanotube film can be judged to contain a large amount of multi-wall carbon nanotubes.
The scanning electron microscope characterization result of the finished mixed carbon nanotube film a1 prepared in the example is shown in fig. 3, and the scanning electron microscope analysis result shows that the film is composed of carbon nanotubes with different thicknesses, and a small amount of particles exist, the particles are divided into two types, one is catalyst nanoparticle aggregates suspended in the high-temperature tube furnace, and the other is amorphous carbon nanoparticles.
The high resolution transmission electron microscopy analysis of the finished mixed carbon nanotube film a1 prepared in the example is shown in fig. 4, and the analysis result shows that the wall of the carbon nanotube constituting the carbon nanotube film has a multi-layer and single-layer lattice composition.
Example 2
The embodiment provides a mixed carbon nanotube film, which is composed of carbon nanotubes with single-wall, double-wall and multi-wall tube wall structures, and the preparation method specifically comprises the following steps:
s1 mixing and stirring:
according to the mass ratio of 99.7: 0.28: 0.02 weighing 100 g of a mixture of methanol and ethanol (methanol: ethanol = 5: 95 by volume), nickel acetylacetonate and carbon disulfide, adding the weighed materials into a beaker, and stirring until the materials are completely dissolved;
According to the mass ratio of 99.7: 0.24: 0.06 weight methanol and ethanol (methanol: ethanol = 5: 95 by volume ratio) mixture, nickel acetylacetonate and carbon disulfide total 100 grams, and add the weighed material into a beaker, stir until completely dissolved;
according to the mass ratio of 97: 1.5: 1.5 weighing 100 g of a mixture of methanol and ethanol (methanol: ethanol = 5: 95 by volume), nickel acetylacetonate and carbon disulfide, adding the weighed materials into a beaker, and stirring until the materials are completely dissolved;
s2 heating and ventilating:
placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, starting the tube furnace to heat, introducing inert gas into the reactor and a collecting box body at the flow rate of 1L/min, and introducing hydrogen into the multi-tube row CVD reactor at the speed of 9L/min after the tube furnace is heated to 1400 ℃, so as to provide a stable environment for the subsequent generation of the carbon nano tube film;
s3 pipe making:
respectively injecting the solutions prepared in the step S1 into three atomizers, atomizing the solutions to form tiny droplets with uniform sizes, adjusting hydrogen flow, respectively bringing the tiny droplets into three different reaction tubes of the multi-tube parallel CVD reactor in the step S2 by hydrogen flow at a constant flow rate, and collecting and obtaining continuous barrel-shaped aerogel formed by mixing multi-wall, double-wall and single-wall carbon nano tubes at the other end of the tube furnace;
S4 film preparation:
and (3) twisting and mixing the aerogel prepared in the S3, collecting the aerogel on a roller which rotates and slowly moves horizontally, taking down the aerogel from the roller and rolling when the thickness of the aerogel reaches 10cm, and testing the thickness of the aerogel A2 to be 22 microns and the surface resistivity to be 0.22 +/-0.05 ohm/SQ.
A scanning electron microscope is performed on the finished mixed carbon nanotube film a2 prepared in the example, as shown in fig. 6, and the scanning electron microscope analysis result shows that the surface of the film is relatively flat and smooth, a small amount of particles exist, the particles are divided into two types, one is catalyst nanoparticle aggregates suspended inside a high-temperature tubular furnace, and the other is amorphous carbon nanoparticles.
The high resolution transmission electron microscopy analysis of the finished mixed carbon nanotube film a2 obtained in the example is shown in fig. 7, and the analysis results show that the carbon nanotube walls constituting the carbon nanotube film have multi-layer, double-layer and single-layer lattice compositions.
The Raman spectrum of the finished mixed carbon nanotube film A2 prepared in the example is shown in FIG. 5, and the Raman spectrum characterization result shows that the Raman spectrum is 192 cm-1，214 cm-1And 252 cm-1Three respiration peaks respectively indicate that the carbon nanotube film contains single-wall and double-wall carbon nanotubes and is from 1332 cm -1Peak intensity of (2) and (2) of (3)-1The carbon nanotube film can be judged to contain a large amount of multi-walled carbon nanotubes without splitting the peak.
Example 3
The embodiment provides a mixed carbon nanotube film, which is composed of carbon nanotubes with single-wall, double-wall and multi-wall tube wall structures, and the preparation method specifically comprises the following steps:
s1 mixing and stirring:
according to the mass ratio of 99.63: 0.34: 0.03 weighing 100 g of isopropanol, ferric nitrate and thiophene, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
according to the mass ratio of 99.7: 0.24: 0.06 weight 100 g of isopropanol, ferric nitrate and thiophene, and add the weighed materials into a beaker, stir until completely dissolved;
according to the mass ratio of 97: 1.5: 1.5 weighing 100 g of isopropanol, ferric nitrate and thiophene, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
s2 heating and ventilating:
placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, starting the tube furnace to heat, introducing inert gas into the reactor and a collecting box body at the flow rate of 1L/min, and introducing hydrogen into the multi-tube row CVD reactor at the speed of 8L/min after the tube furnace is heated to 1250 ℃ so as to provide a stable environment for the subsequent generation of the carbon nano tube film;
S3 pipe making:
respectively injecting the solutions prepared in the step S1 into three atomizers, atomizing the solutions to form tiny droplets with uniform sizes, adjusting hydrogen flow, respectively bringing the tiny droplets into three different reaction tubes of the multi-tube parallel CVD reactor in the step S2 by hydrogen flow at a constant flow rate, and collecting at the other end of the tube furnace to obtain continuous barrel-shaped aerogel formed by mixing multi-wall carbon nanotubes, double-wall carbon nanotubes and single-wall carbon nanotubes;
s4 film preparation:
and (3) twisting and mixing the aerogel prepared in the S3, collecting the aerogel on a roller which rotates and slowly moves horizontally, taking down the aerogel from the roller and rolling when the thickness of the aerogel reaches 10cm, and testing the thickness of the aerogel to be 20 microns and the surface resistivity to be 0.18 +/-0.05 ohm/SQ to obtain the mixed carbon nanotube film A3.
Example 4
The embodiment provides a mixed carbon nanotube film, which is composed of carbon nanotubes with single-wall, double-wall and multi-wall tube wall structures, and the preparation method specifically comprises the following steps:
s1 mixing and stirring:
according to the mass ratio of 99.67: 0.31: 0.02 total 100 g of ethanol, cobalt acetate and thiophene are weighed, the weighed substances are added into a beaker, and the mixture is stirred until the substances are completely dissolved;
According to the mass ratio of 99.7: 0.25: 0.05 weighing 100 g of ethanol, cobalt acetate and thiophene, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
according to the mass ratio of 97: 1.5: 1.5 weighing 100 g of ethanol, cobalt acetate and thiophene, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
s2 heating and ventilating:
placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, starting the tube furnace to heat, introducing inert gas into the reactor and a collecting box body at the flow rate of 1L/min, and introducing hydrogen into the multi-tube row CVD reactor at the speed of 10L/min after the tube furnace is heated to 1350 ℃, so as to provide a stable environment for the subsequent generation of the carbon nano tube film;
s3 pipe making:
respectively injecting the solutions prepared in the step S1 into three atomizers, atomizing the solutions to form tiny droplets with uniform sizes, adjusting hydrogen flow, respectively bringing the tiny droplets into three different reaction tubes of the multi-tube parallel CVD reactor in the step S2 by hydrogen flow at a constant flow rate, and collecting at the other end of the tube furnace to obtain continuous barrel-shaped aerogel formed by mixing multi-wall carbon nanotubes, double-wall carbon nanotubes and single-wall carbon nanotubes;
S4 film making:
and (3) twisting and mixing the aerogel prepared in the S3, collecting the aerogel on a roller which rotates and slowly moves horizontally, taking down the aerogel from the roller and rolling when the thickness of the aerogel reaches 15cm, and testing the thickness of the aerogel to be 20 microns and the surface resistivity to be 0.12 +/-0.05 ohm/SQ to obtain the mixed carbon nanotube film A4.
Example 5
The embodiment provides a mixed carbon nanotube film, which is composed of carbon nanotubes with single-wall, double-wall and multi-wall tube wall structures, and the preparation method specifically comprises the following steps:
s1 mixing and stirring:
according to the mass ratio of 99.64: 0.31: 0.05 weighing 100 g of ethanol, nickel oxalate and carbon disulfide, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
according to the mass ratio of 99.55: 0.35: 0.1, weighing 100 g of ethanol, nickel oxalate and carbon disulfide, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
according to the mass ratio of 97: 1.5: 1.5 weighing 100 g of ethanol, nickel oxalate and carbon disulfide, adding the weighed substances into a beaker, and stirring until the substances are completely dissolved;
s2 heating and ventilating:
placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, starting the tube furnace to heat, introducing inert gas into the reactor and a collecting box body at the flow rate of 1L/min, and introducing hydrogen into the multi-tube row CVD reactor at the speed of 10L/min after the tube furnace is heated to 1400 ℃, so as to provide a stable environment for the subsequent generation of the carbon nano tube film;
S3 pipe making:
respectively injecting the solutions prepared in the step S1 into three atomizers, atomizing the solutions to form tiny droplets with uniform sizes, adjusting hydrogen flow, respectively bringing the tiny droplets into three different reaction tubes of the multi-tube parallel CVD reactor in the step S2 by hydrogen flow at a constant flow rate, and collecting at the other end of the tube furnace to obtain continuous barrel-shaped aerogel formed by mixing multi-wall carbon nanotubes, double-wall carbon nanotubes and single-wall carbon nanotubes;
s4 film preparation:
and (3) twisting and mixing the aerogel prepared in the S3, collecting the aerogel on a roller which rotates and slowly moves horizontally, taking down the aerogel from the roller and rolling when the thickness of the aerogel reaches 15cm, and testing the thickness of the aerogel to be 20 microns and the surface resistivity to be 0.08 +/-0.01 ohm/SQ to obtain the mixed carbon nanotube film A5.
The mixed carbon nanotube films A2-A5 prepared in examples 2-5 were subjected to Raman spectroscopy analysis and testing, as shown in FIG. 5, the Raman spectroscopy characterization results showed that the Raman spectra were measured at 100-500 cm-1All four samples in the region have three or more characteristic respiration peaks, such as: 192 cm-1，214 cm-1And 252 cm-1The carbon nanotube film contains single-wall carbon nanotubes and double-wall carbon nanotubes, and the thickness of the carbon nanotube film is 1325 cm -1Nearby D-band peak intensity and 1590 cm-1The carbon nanotube film can be judged to contain a large amount of multi-walled carbon nanotubes without splitting the nearby G-band peak.
In the case of S3 tube production in examples 1 to 5 of the present invention, the solution prepared in step S1 was injected into three atomizers, respectively, using a conventional atomizing apparatus, having application No. 201922229176.5 and having patent names: the special atomizing device for atomizing carbon nanotube material can control the size of catalyst grain for growing carbon nanotube precisely to regulate the microstructure of carbon nanotube precisely; s2 when heating and ventilating, the multi-tube row CVD reaction device adopts the prior art with the patent number of 201922228249.9, the patent name is a row CVD reaction device in the row CVD reaction device for producing the carbon nano tube film, and the device can realize the preparation of the carbon nano tube film composed of a plurality of paths of different structures; the process of the invention is combined with the two technologies, the raw material liquid atomization technology (atomization device) is respectively added to each pipeline of the multi-pipeline parallel CVD reaction equipment, and the preparation of the mixed carbon nanotube film can be realized by controlling the structure of the carbon nanotube generated by each reaction pipeline.
The method utilizes a floating chemical vapor deposition method, controls the size of catalyst particles by changing the types and the dosage of a catalyst, a promoter and a carbon source, realizes the continuous preparation of carbon nanotube aerogel with different structures in different reaction tubes of a multi-tube row CVD reactor, and finally obtains a mixed carbon nanotube film; the method has the advantages of simple process, low cost and high yield, and the prepared mixed carbon nanotube film has the advantages of low cost, high purity, less impurities, high conductivity, high mechanical strength and the like.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of a mixed carbon nanotube film is characterized by comprising the following steps: the preparation method of the mixed carbon nanotube film comprises the following steps:
s1 mixing and stirring: adding carbon sources, catalysts and promoters in different proportions into a plurality of beakers, and fully stirring until the carbon sources, the catalysts and the promoters are completely dissolved;
s2, heating and ventilating: placing the multi-tube row CVD reactor in a high-temperature area of a horizontal tube furnace, heating, introducing inert gas into the reactor and a collecting box body, and introducing hydrogen into the system after the tube furnace is heated to a target temperature;
S3 pipe making: respectively injecting the solution prepared in the step S1 into a plurality of different atomizers, atomizing the solution to form tiny liquid drops with uniform size, adjusting hydrogen flow, and respectively carrying the tiny liquid drops into different reaction tubes of the multi-tube parallel CVD reactor in the step S2 at a constant flow rate to obtain barrel-shaped aerogel consisting of carbon nano tubes with different tube diameters and tube wall structures;
s4 film making: and (3) twisting and mixing the different barrel-shaped carbon nanotube aerogels prepared in the step S3, collecting the mixture on a roller which horizontally moves back and forth and rotates, and taking down the aerogels from the roller and rolling when the thickness of the aerogels reaches 6-15 cm to obtain the mixed carbon nanotube film.
2. The method for preparing a mixed carbon nanotube film according to claim 1, wherein: the mass ratio of the carbon source, the catalyst and the accelerator in the step S1 is (93-99.79): (4.5-0.2): 2.5-0.01).
3. The method for preparing a mixed carbon nanotube film according to claim 1, wherein: the carbon source in step S1 is one or more of methanol, ethanol, isopropanol, mannitol, acetone, benzene, and toluene.
4. The method for preparing a mixed carbon nanotube film according to claim 1, wherein: the catalyst in step S1 is a combination of cyclopentadienyl compounds of iron, cobalt and nickel, acetylacetone compounds, nitrates, sulfates, chlorides, and one or more of acetates and oxalates.
5. The method for preparing the mixed carbon nanotube film according to claim 1, wherein: the accelerator in step S1 is one or a combination of more of thiophene, thiophene- α -sulfonamide, sulfur powder, ethanethiol, carbon disulfide, thiourea, 2-mercaptopyridine, and thioacetamide.
6. The method for preparing the mixed carbon nanotube film according to claim 1, wherein: the target temperature described in step S2 is 1100-1500 ℃.
7. The method for preparing a mixed carbon nanotube film according to claim 1, wherein: the introduction speed of the hydrogen in the step S2 is 0.5-16L/min.
8. The method for preparing a mixed carbon nanotube film according to claim 7, wherein: in the step S2, the inert gas introducing speed is 1-2L/min, and the hydrogen introducing speed is 1-14L/min.
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| CN101497436A (en) * | 2008-02-01 | 2009-08-05 | 清华大学 | Carbon nano-tube thin-film structure and preparation method thereof |
| CN101830455A (en) * | 2010-04-30 | 2010-09-15 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN110155986A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院金属研究所 | With single or mini-tube bundle size single-walled carbon nanotube transparent conductive film preparation |
| CN110357072A (en) * | 2019-07-10 | 2019-10-22 | 中国科学院金属研究所 | Major diameter, the magnanimity of narrow diameter distribution single-walled carbon nanotube, controllable method for preparing |
| CN112250060A (en) * | 2020-09-22 | 2021-01-22 | 江西铜业技术研究院有限公司 | Device and method for continuously preparing single-walled carbon nanotubes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101497436A (en) * | 2008-02-01 | 2009-08-05 | 清华大学 | Carbon nano-tube thin-film structure and preparation method thereof |
| CN101830455A (en) * | 2010-04-30 | 2010-09-15 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN110155986A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院金属研究所 | With single or mini-tube bundle size single-walled carbon nanotube transparent conductive film preparation |
| CN110357072A (en) * | 2019-07-10 | 2019-10-22 | 中国科学院金属研究所 | Major diameter, the magnanimity of narrow diameter distribution single-walled carbon nanotube, controllable method for preparing |
| CN112250060A (en) * | 2020-09-22 | 2021-01-22 | 江西铜业技术研究院有限公司 | Device and method for continuously preparing single-walled carbon nanotubes |
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