CN115101762A - Preparation method of carbon nano tube/metal selenide material - Google Patents
Preparation method of carbon nano tube/metal selenide material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 111
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 46
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000005284 excitation Effects 0.000 claims abstract description 20
- 238000010891 electric arc Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 21
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- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
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- 238000001704 evaporation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The embodiment of the application provides a preparation method of a carbon nano tube/metal selenide material, which adopts the following method: mixing the carbon nano tube with the prepared metal salt solution according to a preset proportion to obtain a micro-wet carbon nano tube mixed system; filling a micro-wet carbon nano tube mixed system in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, enabling a tungsten filament negative electrode to be close to the carbon nano tube mixed system of a positive electrode, and switching on a power supply to prepare an intermediate material of carbon nano tubes/metal salt particles; roasting the intermediate material of the carbon nano tube/metal salt particles for ion exchange treatment to obtain a carbon nano tube/metal selenide material; firstly, the dispersion of the carbon nano tube and the uniform solid loading of the metal can be realized by one step through the arc excitation, and no toxic gas is generated in the process; and then the prepared carbon nano tube/metal salt particle intermediate material is placed in a tube furnace for ion exchange treatment to prepare the carbon nano tube/metal selenide, the operation is simple, and the industrialization is easy to realize.
Description
Technical Field
The application belongs to the technical field of catalyst material preparation, and particularly relates to a preparation method of a carbon nano tube/metal selenide material.
Background
The hydrogen fuel proton exchange membrane fuel cell is widely concerned due to the advantages of high efficiency, zero emission and the like. The catalyst in the fuel cell is the most critical component determining its catalytic performance, wherein the Oxygen Reduction Reaction (ORR) catalyst at the cathode of the fuel cell is responsible for reducing oxygen to lower oxygen for combination with the positive hydrogen produced at the anode to produce water molecules, and thus the ORR catalyst is an important part in determining the catalytic rate. The composite material of the carbon nano material and the transition metal is a kind of material with prominent performance in the ORR catalyst, and the carbon nano tube in the carbon nano material has the characteristics of high electrical conductivity, stable structure and the like and is often used as a carrier of the transition metal.
Researchers often adopt a hydrothermal method, an electrochemical deposition method, a vapor phase chemical deposition method and the like to prepare a metal catalyst with carbon nanotubes as a carrier, however, the above methods cannot disperse the aggregated carbon nanotubes, which results in that uniform dispersion of metal particles on the carbon nanotubes and small particle size are difficult to realize, and in addition, the method has the disadvantages of tedious operation, high risk and strong pollution; in order to increase the dispersibility of the carrier, application No. 201510959784.5 discloses an underwater arc discharge preparation method of a graphene supported Pt catalyst, which comprises the steps of using a spectral pure graphite rod as an electrode, evaporating an anode by arc discharge to provide a carbon source for growth of a graphene structure, and reducing metal cations in a salt solution to generate Pt metal particles which are loaded on the surface of the graphene structure; however, the patent has the problems that harmful gases such as chlorine gas are generated by reducing the salt solution, the recovery and the treatment are difficult, the operation steps are complicated, the reduction reaction is generated, the energy consumption of graphite evaporation is high and the like.
In view of this, the present application is specifically made.
Disclosure of Invention
In order to solve one of the technical defects, the embodiment of the present application provides a method for preparing a carbon nanotube/metal selenide material.
According to a first aspect of embodiments of the present application, there is provided a method for preparing a carbon nanotube/metal selenide material, comprising:
mixing the carbon nano tube with the prepared metal salt solution according to a preset proportion to obtain a micro-wet carbon nano tube mixed system;
filling a micro-wet carbon nano tube mixed system in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, enabling a tungsten filament negative electrode to be close to the carbon nano tube mixed system of a positive electrode, and switching on a power supply to prepare an intermediate material of carbon nano tubes/metal salt particles;
and roasting the intermediate material of the carbon nano tube/metal salt particles for ion exchange treatment to obtain the carbon nano tube/metal selenide material.
Preferably, the dosage ratio of the metal salt to the liquid phase working medium is 0.2g-1.0 g: 10 ml.
Preferably, the method comprises the following specific steps:
s1: mixing metal salt and a liquid-phase working medium according to a preset proportion to obtain a metal salt solution;
s2: mixing the carbon nano tube with the metal salt solution prepared in the step S1 according to a preset proportion to obtain a micro-wet carbon nano tube mixed system;
s3: filling the micro-wet carbon nanotube mixed system prepared in the step S2 in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, connecting a power supply to the carbon nanotube mixed system with the tungsten filament cathode close to the anode, and preparing a carbon nanotube/metal salt particle intermediate material;
s4: and (4) placing the porcelain boat containing the selenium powder at an upper air inlet of the tube furnace, placing the porcelain boat containing the carbon nano tube/metal salt particle intermediate material prepared in the step S3 at a lower air inlet of the tube furnace, introducing protective gas, heating to 400 ℃, and maintaining for 3 hours to obtain the carbon nano tube/metal selenide catalyst.
Preferably, the mass ratio of the metal salt solution to the carbon nanotubes is 4-10: 1.
preferably, in step S3, after the power is turned on, one drop of the metal salt solution prepared in step S1 is added dropwise into the mixed system collector every 3-5min during the preparation process.
Preferably, the distance between the cathode and the anode of the tungsten wire is kept between 0.5 and 1.0 mm.
Preferably, the liquid phase working medium is a mixed solution of any one or two or more of water, ethanol and glycol.
Preferably, the metal salt solution is a chloride of a metal.
The beneficial effect of this application:
1. firstly, mixing metal salt and a liquid phase working medium to prepare a micro-wet carbon nanotube mixed system, then exciting the carbon nanotube mixed system by adopting electric arc discharge, leading the liquid phase working medium to be excited by electric arc high-energy particle beams to generate phase change, vaporizing and rising so as to lead the carbon nanotube to obtain kinetic energy of dispersion and rising, condensing the metal salt into nano particles from an ionic state to be immobilized on the carbon nanotube, further realizing the dispersion of the carbon nanotube and the uniform immobilization of metal by electric arc excitation, and then carrying out ion exchange treatment to prepare a catalyst of the carbon nanotube/metal selenide; the arc excitation can realize the dispersion of the carbon nano tube and the uniform immobilization of the metal in one step without generating toxic gas, and the method has the characteristics of environmental protection; the arc excitation does not need long-time operation such as high temperature and high pressure, and the like, and the operation is simple and easy to realize industrialization.
2. In the traditional method, electric arc excitation is carried out in a solution, and the solution is excessive, so that the agglomeration phenomenon is easy to occur in the preparation process, and the energy consumption is high; the method has the advantages that the carbon nano tube and the metal salt solution are innovatively mixed to be in a micro-wet state and then are subjected to arc excitation treatment; at the moment, the carbon nano tube is fully mixed with the metal salt solution, so that massive crystallization is prevented from being generated after subsequent electric arc treatment; the metal salt solution is fully soaked in the carbon nano tube gaps, and in the process of electric arc excitation, the carbon nano tubes are driven to disperse and rise by the vaporization force of the liquid phase working medium, so that the dispersity of the carbon nano tubes is improved.
3. The carbon nano tube dispersion and the metal uniform solid-carrying can be realized by one step by using the electric arc excitation, and no toxic gas is generated in the process; then placing the prepared carbon nano tube/metal salt particle intermediate material in a tube furnace for ion exchange treatment to prepare the carbon nano tube/metal selenide, wherein in the process, the metal salt loaded on the carbon nano tube is replaced by the metal selenide, and the replaced chlorine or other gases can be intensively subjected to subsequent treatment so as to avoid volatilization of toxic gases in the whole preparation process; preventing gas pollution in the preparation process.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 SEM images of the material;
FIG. 2 is an SEM image of the CNTs raw material of the present application;
FIG. 3 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 A TEM image of the material;
FIG. 4 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 LSV plot at material 400-;
FIG. 5 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 I-t cycle stability plot of the material, compared to commercial catalyst Pt/C.
Detailed Description
In order to make the technical solutions and advantages of the embodiments of the present application more apparent, the following further detailed description of the exemplary embodiments of the present application with reference to the accompanying drawings makes it clear that the described embodiments are only a part of the embodiments of the present application, and are not exhaustive of all embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example one
A preparation method of a carbon nano tube/metal selenide material comprises the following specific steps:
s1: mixing 0.2g of cobalt chloride with 10ml of deionized water according to a preset proportion to obtain a metal salt solution;
s2: mixing the carbon nano tube with the metal salt solution prepared in the step S1 according to a ratio of 4:1 to obtain a micro-wet carbon nano tube mixed system;
s3: filling the micro-wet carbon nanotube mixed system prepared in the step S2 in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, enabling a tungsten filament negative electrode to be close to the carbon nanotube mixed system of the positive electrode, keeping the distance between the tungsten filament negative electrode and the carbon nanotube mixed system of the positive electrode at 0.5-1.0mm, switching on a power supply, dripping a drop of metal salt solution every 3-5min in the preparation process, and collecting to obtain a carbon nanotube/cobalt chloride particle intermediate material;
s4: placing the ceramic boat containing selenium powder in the upper wind port of a tube furnace, placing the ceramic boat containing the carbon nano tube/cobalt chloride particle intermediate material prepared in the step S3 in the lower wind port of the tube furnace, introducing protective gas, heating to 400 ℃ and maintaining for 3 hours to obtain the carbon nano tube/CoSe 2 The catalyst of (1).
Example two
A preparation method of a carbon nano tube/metal selenide material comprises the following specific steps:
s1: mixing 0.6g of cobalt chloride with 10ml of deionized water according to a preset proportion to obtain a metal salt solution;
s2: mixing the carbon nano tube with the metal salt solution prepared in the step S1 according to a ratio of 7:1 to obtain a micro-wet carbon nano tube mixed system;
s3: filling the micro-wet carbon nanotube mixed system prepared in the step S2 in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, enabling a tungsten filament negative electrode to be close to the carbon nanotube mixed system of the positive electrode, keeping the distance between the tungsten filament negative electrode and the carbon nanotube mixed system of the positive electrode at 0.5-1.0mm, switching on a power supply, dripping a drop of metal salt solution every 3-5min in the preparation process, and collecting to obtain a carbon nanotube/cobalt chloride particle intermediate material;
s4: placing the ceramic boat containing selenium powder in the upper wind port of a tube furnace, placing the ceramic boat containing the carbon nano tube/cobalt chloride particle intermediate material prepared in the step S3 in the lower wind port of the tube furnace, introducing protective gas, heating to 400 ℃ and maintaining for 3 hours to obtain the carbon nano tube/CoSe 2 The catalyst of (1).
EXAMPLE III
A preparation method of a carbon nano tube/metal selenide material comprises the following specific steps:
s1: mixing 1g of cobalt chloride with 10ml of deionized water according to a preset proportion to obtain a metal salt solution;
s2: mixing the carbon nano tube with the metal salt solution prepared in the step S1 according to the ratio of 10:1 to obtain a micro-wet carbon nano tube mixed system;
s3: filling the micro-wet carbon nanotube mixed system prepared in the step S2 in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, enabling a tungsten filament negative electrode to be close to the carbon nanotube mixed system of the positive electrode, keeping the distance between the tungsten filament negative electrode and the carbon nanotube mixed system of the positive electrode at 0.5-1.0mm, switching on a power supply, dripping a drop of metal salt solution every 3-5min in the preparation process, and collecting to obtain a carbon nanotube/cobalt chloride particle intermediate material;
s4: placing the ceramic boat containing selenium powder at the upper wind port of the tube furnace, placing the ceramic boat containing the carbon nanotube/cobalt chloride particle intermediate material prepared in the step S3 at the lower wind port of the tube furnace, introducing protective gas, heating to 400 ℃ and maintaining for 3h to obtain the carbon nanotube/CoSe 2 A catalyst.
FIG. 1 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 SEM images of the material; FIG. 2 is an SEM image of the CNTs raw material of the present application; FIG. 3 shows the CNTs Supported CoSe prepared in example 1 of the present application 2 A TEM image of the material; FIG. 4 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 LSV plot at material 400-; FIG. 5 shows CoSe loaded onto CNTs prepared in example 1 of the present application 2 I-t cycle stability plot of the material, compared to commercial catalyst Pt/C.
FIG. 1 shows carbon nanotubes/CoSe prepared after arc excitation 2 The catalyst is highly dispersed, and it can be seen from fig. 2 that the CNTs raw material is in an agglomerated state, and the carbon nanotubes are curled and wound into a cluster. Fig. 1 shows that the prepared catalytic material is dispersed into the overlapped single carbon nanotubes from the carbon nanotube spheres which are wound in a curled and agglomerated shape, and compared with fig. 2 and fig. 1, the catalytic material prepared by the present application has a particularly significant dispersion effect.
FIG. 3 shows CoSe loaded on CNTs prepared in example 1 of the present application 2 A TEM image of the material; it also further shows that CoSe 2 The carbon nano tube is loaded on the surface, and the particle size is small and uniform.
FIG. 4 shows the carbon nanotubes prepared in example 2 of the present applicationtube/CoSe 2 LSV curve of the catalyst, with high half-wave potential and onset potential.
FIG. 5 shows carbon nanotubes/CoSe prepared in the present application after 150000s of service 2 The catalyst has higher cycle stability compared with the commercial catalyst Pt/C.
Based on the above, according to the application, firstly, metal salt and a liquid phase working medium are mixed to prepare a micro-wet carbon nanotube mixed system, then, arc discharge is adopted to excite the carbon nanotube mixed system, the liquid phase working medium is excited by an electric arc high-energy particle beam to generate phase change, and evaporation and rising are carried out, so that the carbon nanotube obtains kinetic energy for dispersion and rising, the metal salt is condensed into nanoparticles from an ionic state and is immobilized on the carbon nanotube, the carbon nanotube dispersion and metal uniform immobilization can be realized by one step through the arc excitation, and then, ion exchange treatment is carried out to prepare the carbon nanotube/metal selenide catalyst; the arc excitation can realize the dispersion of the carbon nano tube and the uniform immobilization of the metal in one step without generating toxic gas, and the method has the characteristics of environmental protection; the arc excitation does not need long-time operation such as high temperature and high pressure, and the like, and the operation is simple and easy to realize industrialization. In addition, the carbon nanotubes/CoSe prepared by the present application 2 The catalyst has higher cycle stability.
It is worth to be noted that the carbon nanotube/metal sulfide material can be prepared by adopting sulfur powder instead of selenium powder in the ion exchange stage. The carbon nanotubes may be replaced with other materials such as graphene.
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the present application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
Claims (8)
1. A preparation method of a carbon nano tube/metal selenide material is characterized by comprising the following steps:
mixing the carbon nano tube with the prepared metal salt solution according to a preset proportion to obtain a micro-wet carbon nano tube mixed system;
filling a micro-wet carbon nanotube mixed system in a mixed system collector, placing the mixed system on a positive plate of an electric arc excitation device, connecting a power supply with a tungsten filament negative electrode close to a carbon nanotube mixed system of a positive electrode, and preparing an intermediate material of carbon nanotubes/metal salt particles;
and roasting the intermediate material of the carbon nano tube/metal salt particles for ion exchange treatment to obtain the carbon nano tube/metal selenide material.
2. The method of claim 1, wherein the ratio of the amount of the metal salt to the amount of the liquid working medium is 0.2g to 1.0 g: 10 ml.
3. The method according to claim 1, comprising the following steps:
s1: mixing metal salt and a liquid phase working medium according to a preset proportion to obtain a metal salt solution;
s2: mixing the carbon nano tube with the metal salt solution prepared in the step S1 according to a preset proportion to obtain a micro-wet carbon nano tube mixed system;
s3: filling the micro-wet carbon nanotube mixed system prepared in the step S2 in a mixed system collector, placing the collector on a positive plate of an electric arc excitation device, connecting a power supply to the carbon nanotube mixed system with the tungsten filament negative electrode close to the positive electrode, and preparing a carbon nanotube/metal salt particle intermediate material;
s4: and (4) placing the ceramic boat containing the selenium powder at an upper air inlet of the tube furnace, placing the ceramic boat containing the carbon nano tube/metal salt particle intermediate material prepared in the step S3 at a lower air inlet of the tube furnace, introducing protective gas, heating to 400 ℃, and maintaining for 3 hours to obtain the carbon nano tube/metal selenide catalyst.
4. The method of claim 3, wherein the mass ratio of the metal salt solution to the carbon nanotubes is from 4 to 10: 1.
5. the preparation method of claim 3, wherein in the step S3, after the power is turned on, one drop of the metal salt solution prepared in the step S1 is added to the mixed system collector every 3-5min during the preparation process.
6. The method of claim 3, wherein the distance between the cathode and the anode of the tungsten wire is maintained at 0.5 to 1.0 mm.
7. The method according to claim 3, wherein the liquid phase working medium is a mixed solution of any one or two or more of water, ethanol and ethylene glycol.
8. The method of claim 1, wherein the metal salt solution is a chloride of a metal.
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Citations (6)
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