CN116947025A - Preparation method of high-conductivity double-wall carbon nanotube and double-wall carbon nanotube aqueous slurry - Google Patents
Preparation method of high-conductivity double-wall carbon nanotube and double-wall carbon nanotube aqueous slurry Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/04—Nanotubes with a specific amount of walls
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
Abstract
The application belongs to the technical field of nano material and slurry preparation, and relates to a preparation method of a high-conductivity double-wall carbon nano tube and double-wall carbon nano tube aqueous slurry. The preparation method of the application obtains a larger high-temperature reaction zone by controlling the formation of a static arc column, introduces a template agent to regulate and control the size of the evaporated main catalyst particles, prolongs the reaction time of the main catalyst in the high-temperature zone, adopts measures such as mixed carbon sources and the like, and finally prepares the metal type high-conductivity double-wall carbon nano tube. Raman characterization of the same I G /I D The initial purity of the product is more than 80, the yield reaches 30-100 g/h, and the highest powder conductivity can reach 1.56 multiplied by 10 5 S/m. The double-walled carbon nanotube has higher purity and yield, and simultaneously has excellent conductivity and dispersion stability. The high-conductivity aqueous slurry can be prepared by using a small amount of dispersing agent under the same process. Thin coated PET filmThe layer resistance is 50-350 omega/sq (the light transmittance is 80% -95%), and has better commercial application value compared with similar products.
Description
Technical Field
The application belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a high-conductivity double-wall carbon nano tube and double-wall carbon nano tube aqueous slurry.
Background
Conventionally, double-walled carbon nanotubes (DWCNTs) are tubular structural materials formed by crimping two graphene sheets. The double-layer structure is a special carbon tube between the multi-wall carbon nano tube (multi-layer graphene sheet curl) and the single-wall carbon nano tube (single-layer graphene sheet curl), so that the double-wall carbon nano tube has a plurality of advantages of the single-wall carbon nano tube and the multi-wall carbon nano tube. The good mechanical property and the excellent electrical property lead the double-wall carbon nano tube to have important application value in the fields of composite material enhancement, conductive additives, field effect transistors and the like. However, the preparation of high-purity double-walled carbon nanotubes in large quantities still has great challenges at present due to the special condition limitations of double-walled carbon nanotubes in the synthesis process.
The preparation method of the double-wall carbon nano tube is the same as that of the traditional carbon nano tube, but the control of the process conditions is more strict. The prior art has also been able to produce double walled carbon nanotubes by Chemical Vapor Deposition (CVD). However, the initial purity of the double-walled carbon nanotubes prepared by the powder catalyst with a large amount of load is very low, more than 90% of the initial product is a catalyst matrix, and the high-purity double-walled carbon nanotubes can be obtained through a later complicated purification process. The complex purification treatment of concentrated hydrochloric acid, sodium hydroxide, hydrofluoric acid and the like increases the risk of great environmental pollution. In addition, the preparation of the double-wall carbon nano tube can be also carried out by a floating catalytic chemical vapor deposition method, and the addition amounts of the catalyst, the auxiliary agent and the liquid carbon source are precisely controlled by the method, so that the high-conductivity double-wall carbon nano tube film is prepared. According to the consensus in the industry, the yield of carbon tubes prepared by the floating catalytic method is limited by the concentration of the introduced catalyst, and the yield is difficult to improve. The unit volume yield of the carbon nano tube prepared by most floating catalysis is difficult to break through 1g/h. In the 90 s, many scientific institutions can also perform the preparation of carbon nanotubes, particularly single-walled carbon nanotubes, by an arc discharge method, and this conventional arc discharge method has been considered as a method capable of performing mass production of single-walled carbon nanotubes. The double-wall carbon nano tube is prepared by adopting the traditional arc discharge method, taking a carbon rod containing a catalyst and solid carbon source graphite powder as an anode and performing arc discharge between the carbon rod and a cathode of the graphite rod. The carbon tube prepared by the arc discharge method of the traditional ablated graphite carbon source often contains more fullerene, carbon coated iron and other carbon products.
Disclosure of Invention
The application discloses a preparation method of a high-conductivity double-wall carbon nano tube and double-wall carbon nano tube aqueous slurry, which are used for solving the above and other potential problems in the prior art.
In order to solve the problems, the technical scheme of the application is as follows: the preparation method of the high-conductivity double-wall carbon nano tube specifically comprises the following steps:
s1) forming a static arc in a hearth by adopting an improved arc discharge method to obtain an arc ultrahigh temperature reaction zone with a large area, and controlling the arc ultrahigh temperature reaction zone to a set temperature;
s2) introducing the mixed main catalyst, template agent and cocatalyst according to a certain proportion into an electric arc ultra-high temperature reaction zone through carrier gas to evaporate the main catalyst, so as to obtain main catalyst nano particles with a certain particle size;
s3) passing a certain flow of inert gas into the hearth to form vortex in the hearth, and adjusting the air outlet quantity of the hearth to keep a certain positive pressure value in the hearth and ensure that the catalyst nano particles stay in the hearth for a certain time;
s4) introducing a mixed carbon source into the hearth at a certain flow, and reacting the introduced mixed carbon source with main catalyst nano particles in an electric arc ultrahigh temperature reaction zone to grow so as to prepare the double-wall carbon nano tube;
s5) carrying out post-treatment on the double-wall carbon nano tube in the step S4) to obtain the high-purity high-conductivity double-wall carbon nano tube powder.
Further, the improved arc discharge method in S1) specifically includes: firstly, controlling the diameter of an arc column to be maintained at 3-15 cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, and maintaining the arc length of the arc to be unchanged between 8 cm and 25cm through constant voltage; the set temperature is 5000-18000 ℃.
Further, the procatalyst in S2): template agent: the mass ratio of the cocatalyst is 45% -95%: 1-30%: 25% -4%;
the particle size of the main catalyst nano particles is 0.2 nm-5 nm.
Further, the template agent is one or more of silicon, aluminum, silicon oxide, aluminum oxide, magnesium carbonate, calcium oxide, calcium carbonate, graphite, carbon black or basic magnesium carbonate.
Further, the flow rate of the inert gas in S2) is: 10-50L/min;
prolonging the residence time of the catalyst and enabling the catalyst particles to be fully contacted with a carbon source; 10-50L/min;
the positive pressure value is 0.001 MPa-0.1 MPa;
the residence time is 0.01s to 5s.
Further, the mixed carbon source in S4) includes a main carbon source component and an auxiliary carbon source component, and the mass ratio of the main carbon source component to the auxiliary carbon source component is: 70% -99.9%: 30 to 0.1 percent.
Further, the main carbon source component is methane;
the auxiliary carbon source component comprises one or a combination of more of ethylene, acetylene, propane, propylene, butadiene, ethanol, toluene and graphite;
further, the post-treatment in S4) includes a purification process and a pulverization process;
wherein, the purification process is as follows:
air-firing at 300-600 deg.C, pickling with 1-10 mol/L hydrochloric acid, washing, drying, and heat-treating at 1500-3000 deg.C in vacuum high-temperature furnace;
the crushing process comprises the following steps:
and shearing and cutting the carbon tube by using an airflow pulverizer or a mechanical blade pulverizer to finally obtain the high-purity high-conductivity double-wall carbon nanotube powder.
Further, the purity of the high-purity high-conductivity double-wall carbon nano tube powder is 85% -99.99%;
the conductivity of the high-purity high-conductivity double-wall carbon nano tube powder is 1.0 multiplied by 10 5 S/m～8.0×10 5 S/m；
The granularity of the high-purity high-conductivity double-wall carbon nano tube powder is 10-500 mu m.
The double-wall carbon nano tube aqueous slurry comprises a dispersing agent and double-wall carbon nano tubes, wherein the double-wall carbon nano tubes are high-purity high-conductivity double-wall carbon nano tube powder prepared by the preparation method.
The preparation process comprises the following steps: performing sand mill dispersion treatment on a small amount of dispersing agent and water, and then preparing double-wall carbon nano tube aqueous slurry by adopting a high-pressure homogenizer;
the small amount of dispersing agent is that the dispersing agent is reduced by 20-50% compared with other carbon tube products, and the sheet resistance of the PET film coated with the dispersing agent can reach 50-350 omega/sq (light transmittance 80-95%).
The beneficial effects of the application are as follows:
(1) The diameter of the air inlet hole in the cathode electrode rod is adjusted to control the arc column to be kept at a large diameter, and the arc length is maintained and kept unchanged by constant voltage, so that a static arc is controlled and formed, and a large-area arc high-temperature reaction area is obtained. The large-area high-temperature reaction zone can provide more carbon tube growth space and can effectively improve the yield. Meanwhile, the higher reaction temperature can effectively improve the crystallinity and graphitization degree of the carbon tube;
(2) Through the design of adding back-flow carrier gas in the hearth and keeping positive pressure in the hearth, the passing time of a carbon source in the hearth can be effectively delayed, and the growth reaction time of the carbon tube is prolonged. The double-wall carbon nano tube generated by long-time high-temperature reaction effectively improves crystallinity and graphitization degree, and has higher conductivity;
(3) A template agent is introduced into the catalyst proportion for the first time, and can enable the molten and evaporated iron particles to adhere and nucleate to form stable nano particles. The nano particles not only have specific size, but also can be maintained for a long time at high temperature without melting, and the service life of the catalyst is greatly prolonged. The method provides a guarantee for continuously synthesizing a large amount of double-wall carbon nanotubes with uniform tube diameters;
(4) By using the mode of mixing carbon sources, the introduced second carbon source can play a good role in cooperative growth, and is beneficial to improving the yield and quality of the double-wall carbon nano tube;
(5) In the purification process, the proposed acid-washed product adopts a high-temperature furnace heat treatment process, so that the catalyst iron particles coated by carbon can be effectively removed, and the final purity of the product is greatly improved. In the pulverizing process, a shearing pulverizing process is added in the early stage, so that the filamentous carbon tube primary product can be effectively cut, and the subsequent dispersion preparation of the slurry product is facilitated.
Drawings
Fig. 1 is a scanning electron micrograph of a double-walled carbon nanotube prepared in example 1 of the present application.
Fig. 2 is a transmission electron micrograph of a double-walled carbon nanotube prepared in example 1 of the present application.
FIG. 3 is a graph showing the Raman spectrum of the double-walled carbon nanotube prepared in example 1 of the present application.
FIG. 4 is a thermogravimetric analysis of the initial product of double walled carbon nanotubes prepared in example 1 of the present application.
FIG. 5 is a thermogravimetric analysis curve of the double-walled carbon nanotube prepared in example 1 of the present application after purification.
Fig. 6 is a graph showing a powder resistivity test of the double-walled carbon nanotube prepared in example 1 of the present application.
Fig. 7 is a transmission electron micrograph of the aqueous slurry of double walled carbon nanotubes prepared in example 1 of the present application.
Fig. 8 is a scanning electron micrograph of the double-walled carbon nanotube prepared in comparative example 1 of the present application.
Fig. 9 is a graph showing raman spectra of the double-walled carbon nanotube prepared in comparative example 1 of the present application.
Fig. 10 is a scanning electron micrograph of a double-walled carbon nanotube prepared in example 2 of the present application.
Fig. 11 is a transmission electron micrograph of a double-walled carbon nanotube prepared in example 2 of the present application.
Fig. 12 is a graph showing raman spectra of the double-walled carbon nanotubes prepared in example 2 of the present application.
Detailed Description
The application will be further described with reference to the accompanying drawings and specific examples.
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Example 1
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 15cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, calcium carbonate is used as a template agent, and ferrous sulfide is used as a cocatalyst to be added into a furnace body for experiment, wherein the main catalyst is as follows: template agent: the mass ratio of the cocatalyst is 70 percent: 10%:20% of a base; evaporating in a high temperature area to obtain catalyst particles with the granularity of 1.5 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, and after inert gas argon is introduced, vortex is formed in an arc reaction area in the hearth, meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is ethylene, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 99%:1, preparing a double-wall carbon nano tube;
(5) Collecting a double-wall carbon nano tube product, performing purification post-treatment, firstly calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1h, taking out a sample, then refluxing and stirring the sample for 12h through a hydrochloric acid solution with the concentration of 4mol/L, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1h to obtain the high-purity high-conductivity double-wall carbon nano tube sample.
In order to further characterize the excellent conductivity of the double-walled carbon nanotube sample, subsequent dispersion treatment is carried out, and performance characterization is carried out after the carbon nanotube aqueous slurry is prepared. Placing the purified double-wall carbon nanotube sample into an airflow crusher to shear and cut the carbon nanotubes, so as to obtain double-wall carbon nanotube powder with the granularity of 50 mu m;
the double-wall carbon nano tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the double-wall carbon nano tube aqueous slurry; the prepared double-wall carbon nano tube aqueous slurry is coated on a PET film in a scraping mode, and after the PET film is dried at the temperature of 100 ℃, the light transmittance and the sheet resistance of the PET film are detected.
Fig. 1 is a scanning electron micrograph of double-walled carbon nanotubes prepared under the conditions of this example, and it can be seen that a large number of crimped bundle-like carbon tubes are closely arranged, and this coarser bundle-like morphology is formed by adhering a plurality of double-walled carbon nanotubes to each other, and the length can reach several micrometers to several tens micrometers. The transmission electron micrograph of FIG. 2 shows clearly that the diameter of a straight double-walled carbon nanotube is about 1.5 nm. A Raman spectrum detected at 532nm using a laser is shown in FIG. 3, which shows a spectrum at 120cm -1 -200cm -1 The characteristic peak-RBM peak appearing nearby is relatively weaker than that of single-wall carbon nano tube, and hasThe standard characteristic peaks of the two carbon materials of the obvious G peak and the obvious D peak can be calculated to obtain I G /I D The product had fewer defects and high crystallinity at 85. The initial and purified products were analyzed for thermal stability and purity, respectively, by heating to 900 ℃ in an oxygen atmosphere by a thermogravimetric analyzer. In FIG. 4, which is a thermogravimetric plot of the initial product, it can be seen that the sample stops decomposing at 800℃and the final residual amount is 17.5%, indicating that the purity of the initial product can reach 82.5%. After purification treatment, as shown in fig. 5, the residual amount was only 2.0%, indicating that the purity of the purified product could be as high as 98.0%. The purified sample is subjected to four-probe powder resistivity test, as shown in fig. 6, as the pressure is increased, the compaction contact of the sample is tighter, the resistivity is reduced, the pressure is closer to a true value when the pressure reaches 18MPa, and the conductivity of the powder can reach 1.56 multiplied by 10 through calculation 5 S/m, has high conductivity. According to the method in the embodiment, the aqueous slurry is prepared, and is subjected to transmission electron microscope characterization, as shown in fig. 7, the carbon tubes are very uniformly dispersed, black 'fusiform' objects with the size of hundreds of nanometers are inserted among straight carbon tubes in an irregular distribution, and the liquid aggregate formed in the slurry under the action of surface tension can play a role in better dispersing the carbon tubes.
Comparative example 1
On the basis of the embodiment 1, an experiment without adding a template agent into the catalyst is carried out, and the specific steps are as follows:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 15cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in a hearth, adding a catalyst with a specific ratio into the hearth after the reaction temperature is reached, carrying out a comparison experiment without adding a template agent, taking iron powder as a main catalyst, and adding ferrous sulfide as a cocatalyst into a furnace body for carrying out an experiment, wherein the main catalyst is as follows: the mass ratio of the cocatalyst is 70 percent: 30%; evaporating in a high temperature region to obtain catalyst particles with the granularity of 2 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, and after inert gas argon is introduced, vortex is formed in an arc reaction area in the hearth, meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is ethylene, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 99%:1, preparing a product;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1 hour, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 4mol/L for 12 hours, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1 hour to obtain a purified sample.
And (3) carrying out subsequent dispersion treatment, and carrying out performance characterization after preparing the carbon tube aqueous slurry. Placing the purified sample into an air flow pulverizer to shear and cut carbon tubes to obtain powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
As shown in FIG. 8, a scanning electron micrograph of a sample of comparative example 1, which also has partially crimped bundles of carbon tubes, but with a large number of particles or fine bulk impurities between the carbon tubes, is seen by comparing with FIG. 1 of example 1, probably due to the fact that the nano-sized iron particles are easily fused and form larger iron particles, grow to form a large number of carbon-coated iron structures, which produce a product of quality in the absence of a templating agent in the catalystGreat adverse effects. FIG. 9 is a Raman spectrum of the product, calculated to give I G /I D 35, the quality of the product was also reduced.
Example 2
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 15cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, graphite is used as a template agent, ferrous sulfide is used as a cocatalyst and added into a furnace body for experiment, wherein the main catalyst is as follows: template agent: the mass ratio of the cocatalyst is 90 percent: 5%:5%; evaporating in a high temperature area to obtain catalyst particles with the granularity of 1.5 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, and after inert gas argon is introduced, vortex is formed in an arc reaction area in the hearth, meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is ethylene, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 99.5%:0.5% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1 hour, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 4mol/L for 12 hours, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1 hour to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
FIG. 10 is a scanning electron micrograph of carbon tubes prepared under the conditions of this example, also having a plurality of tightly packed bundles of carbon tubes which may be as long as several microns to several tens of microns. In the transmission electron micrograph of FIG. 11, a plurality of straight double-walled carbon nanotubes can be seen, the tube diameter of which is about 1.2-2.0 nm. The Raman spectrum is shown in FIG. 12, and I can be obtained by calculation G /I D 80.
Comparative example 2
Based on the embodiment 2, a single carbon source comparison experiment is carried out, and the specific steps are as follows:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 15cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, graphite is used as a template agent, ferrous sulfide is used as a cocatalyst and added into a furnace body for experiment, wherein the main catalyst is as follows: template agent: the mass ratio of the cocatalyst is 90 percent: 5%:5%; evaporating in a high temperature area to obtain catalyst particles with the granularity of 1.5 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a carbon source into a hearth from an air inlet for growth, wherein the carbon source is methane, and preparing a product;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1 hour, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 4mol/L for 12 hours, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1 hour to obtain a purified sample.
And (3) carrying out subsequent dispersion treatment, and carrying out performance characterization after preparing the carbon tube aqueous slurry. Placing the purified sample into an air flow pulverizer to shear and cut carbon tubes to obtain powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
Example 3
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 13cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained to be constant at 20cm through constant voltage, and a static arc is formed through control, so that a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, silicon oxide is used as a template agent, and ferrous sulfide is used as a cocatalyst to be added into a furnace body for experiment, wherein the main catalyst is as follows: template agent: the mass ratio of the cocatalyst is 85 percent: 10%:5%; evaporating in a high temperature area to obtain catalyst particles with the granularity of 1.5 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.08MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is propylene, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 80.0%:20.0% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1 hour, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 4mol/L for 12 hours, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1 hour to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
TABLE 1 comparison of the product index of carbon nanotubes of examples 1-3 and comparative examples 1-2 with the performance index after coating to prepare transparent conductive films
Example 4
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 20cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, aluminum oxide is used as a template agent, and ferrous sulfide is used as a cocatalyst to be added into a furnace body for experiment, wherein the main catalyst is as follows: template agent: the mass ratio of the cocatalyst is 80 percent: 10%:10%; evaporating in a high temperature area to obtain catalyst particles with the granularity of 1.5 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is acetylene, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 90.0%:10.0% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1 hour, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 4mol/L for 12 hours, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1 hour to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
Example 5
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 20cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, calcium oxide is used as a template agent, ferrous sulfide is used as a cocatalyst, and the main catalyst is added into a furnace body for experiment: template agent: the mass ratio of the cocatalyst is 95 percent: 2.5%:2.5%; evaporating in a high temperature region to obtain catalyst particles with the granularity of 2 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is propane, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 90.0%:10.0% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 400 ℃ for 1 hour, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 4mol/L for 12 hours, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1 hour to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.2% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
Example 6
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 20cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, carbon black is used as a template agent, sulfur powder is used as a cocatalyst and added into a furnace body for experiment, wherein the main catalyst comprises the following components: template agent: the mass ratio of the cocatalyst is 90 percent: 5.0%:5.0%; evaporating in a high temperature region to obtain catalyst particles with the granularity of 2 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is ethanol, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 90.0%:10.0% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, firstly calcining a proper amount of the product in an air atmosphere at 450 ℃ for 1h, taking out a sample, then refluxing and stirring the sample for 12h through a hydrochloric acid solution with the concentration of 2mol/L, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1600 ℃ for 1h to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.1% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
Example 7
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 10cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 20cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, magnesium carbonate is used as a template agent, thiophene is used as a cocatalyst, and the main catalyst is added into a furnace body for experiment: template agent: the mass ratio of the cocatalyst is 90 percent: 5.0%:5.0%; evaporating in a high temperature region to obtain catalyst particles with the granularity of 2 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is graphite, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 80.0%:20.0% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 450 ℃ for 1h, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 2mol/L for 12h, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1h to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.05% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
Example 8
The preparation of the high-conductivity double-wall carbon nano tube and the slurry thereof comprises the following specific steps:
(1) The diameter of an arc column is controlled to be maintained at 13cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, the arc length is maintained at 25cm through constant voltage, a static arc is formed through control, and a large-area arc high-temperature area is obtained;
(2) Regulating the temperature in the hearth, and adding a catalyst with a specific proportion into the hearth after the temperature reaches the reaction temperature; iron powder is used as a main catalyst, graphite is used as a template agent, thiophene is used as a cocatalyst, and the main catalyst is added into a furnace body for experiment: template agent: the mass ratio of the cocatalyst is 90 percent: 5.0%:5.0%; evaporating in a high temperature region to obtain catalyst particles with the granularity of 2 nm;
(3) Different air inlets are distributed at symmetrical positions of the inner wall of the hearth, inert gas argon is introduced into the hearth to form reflux in an electric arc reaction area in the hearth, and meanwhile, the inside of the hearth is kept in a positive pressure state of 0.05MPa, so that the residence time of the catalyst can be prolonged to more than 2s, and catalyst particles can be fully contacted with a carbon source;
(4) Introducing a mixed carbon source into a hearth from an air inlet for growth, wherein a main carbon source of the mixed carbon source is methane, an auxiliary carbon source is toluene, and the mass ratio of the main carbon source component to the auxiliary carbon source component is as follows: 80.0%:20.0% of a carbon tube sample is prepared;
(5) Collecting a product, performing purification post-treatment, calcining a proper amount of the product in an air atmosphere at 450 ℃ for 1h, taking out a sample, refluxing and stirring the sample by using a hydrochloric acid solution with the concentration of 2mol/L for 12h, placing the washed and dried sample into a vacuum high-temperature furnace, and performing vacuum heat treatment at 1800 ℃ for 1h to obtain a purified carbon tube sample.
In order to further characterize the conductivity of the sample, subsequent dispersion treatment is performed, and performance characterization is performed after the carbon tube aqueous slurry is prepared. Placing the purified carbon tube sample into an airflow crusher to shear and cut the carbon tube, so as to obtain carbon tube powder with the granularity of 50 mu m;
the carbon tube powder and the dispersing agent sodium dodecyl benzene sulfonate are respectively mixed according to the mass fraction of 0.1 percent: adding 0.05% of the rest water into an emulsifying machine for emulsifying and dispersing for 1h to obtain primarily dispersed slurry, taking out the primarily dispersed slurry, putting the primarily dispersed slurry into a high-pressure homogenizer for further dispersing treatment, homogenizing for 30min under 800bar pressure, and preparing the carbon tube water-based slurry;
the prepared carbon tube aqueous slurry is coated on a PET film in a scraping way, and after the PET film is dried at 100 ℃, the light transmittance and sheet resistance of the PET film are detected.
The above description of embodiments is only for aiding in the understanding of the method of the present application and its core ideas; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a preset error range, substantially achieving the technical effect. The description hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description is given for the purpose of illustrating the general principles of the application. The scope of the application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of numerous other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, either as a result of the foregoing teachings or as a result of the knowledge or technology of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the application are intended to be within the scope of the appended claims.
Claims (10)
1. The preparation method of the high-conductivity double-wall carbon nano tube is characterized by comprising the following steps of:
s1) forming a static arc in a hearth by adopting an improved arc discharge method to obtain an arc ultrahigh temperature reaction zone with a large area, and controlling the arc ultrahigh temperature reaction zone to a set temperature;
s2) introducing the mixed main catalyst, template agent and cocatalyst according to a certain proportion into an electric arc ultra-high temperature reaction zone through carrier gas to evaporate the main catalyst, so as to obtain catalyst nano particles with a certain particle size;
s3) passing a certain flow of inert gas into the hearth to form vortex in the hearth, and adjusting the air outlet quantity of the hearth to keep a certain positive pressure value in the hearth and ensure that the main catalyst nano particles stay in the hearth for a certain time;
s4) introducing a mixed carbon source into the hearth at a certain flow, and reacting the introduced mixed carbon source with main catalyst nano particles in an electric arc ultrahigh temperature reaction zone to grow so as to prepare the double-wall carbon nano tube;
s5) carrying out post-treatment on the double-wall carbon nano tube in the step S4) to obtain the high-purity high-conductivity double-wall carbon nano tube powder.
2. The preparation method according to claim 1, wherein the modified arc discharge method in S1) is specifically: firstly, controlling the diameter of an arc column to be maintained at 3-15 cm through the adjustment of the diameter of an air inlet hole in a cathode electrode rod, and maintaining the arc length of the arc to be unchanged between 8 cm and 25cm through constant voltage;
the set temperature is 5000-18000 ℃.
3. The process according to claim 1, wherein the procatalyst of S2): template agent: the mass ratio of the cocatalyst is 45% -95%: 1-30%: 25% -4%;
the particle size of the main catalyst nano particles is 0.2 nm-5 nm.
4. The method of claim 3, wherein the template is one or more of silicon, aluminum, silicon oxide, aluminum oxide, magnesium carbonate, calcium oxide, calcium carbonate, graphite, carbon black, or basic magnesium carbonate.
5. The method according to claim 1, wherein the flow rate of the inert gas in S2) is: 10-50L/min;
prolonging the residence time of the catalyst and enabling the catalyst particles to be fully contacted with a carbon source; 10-50L/min;
the positive pressure value is 0.001 MPa-0.1 MPa;
the residence time is 0.01s to 5s.
6. The method according to claim 1, wherein the mixed carbon source in S4) includes a main carbon source component and an auxiliary carbon source component, and the mass ratio of the main carbon source component to the auxiliary carbon source component is: 70% -99.9%: 30 to 0.1 percent.
7. The method according to claim 6, wherein the main carbon source component is methane;
the auxiliary carbon source component comprises one or a combination of several of ethylene, acetylene, propane, propylene, butadiene, ethanol, toluene or graphite.
8. The method of claim 1, wherein the post-treatment in S4) comprises a purification process and a pulverization process;
wherein, the purification process is as follows:
air-firing at 300-600 deg.C, pickling with 1-10 mol/L hydrochloric acid, washing, drying, and heat-treating at 1500-3000 deg.C in vacuum high-temperature furnace;
the crushing process comprises the following steps:
and shearing and cutting the carbon tube by using an airflow pulverizer or a mechanical blade pulverizer to finally obtain the high-purity high-conductivity double-wall carbon nanotube powder.
9. The method according to claim 1, wherein the purity of the high-purity high-conductivity double-walled carbon nanotube powder is 85% to 99.99%;
the conductivity of the high-purity high-conductivity double-wall carbon nano tube powder is 1.0 multiplied by 10 5 S/m～8.0×10 5 S/m；
The granularity of the high-purity high-conductivity double-wall carbon nano tube powder is 10-500 mu m.
10. The double-walled carbon nanotube aqueous slurry comprises a dispersing agent and double-walled carbon nanotubes, and is characterized in that the double-walled carbon nanotubes are high-purity high-conductivity double-walled carbon nanotube powder prepared by the preparation method of any one of claims 1-9.
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