CN115353094B - Solid phase purification method of carbon nano tube - Google Patents
Solid phase purification method of carbon nano tube Download PDFInfo
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Abstract
The invention discloses a solid phase purification method of carbon nanotubes, which comprises the following steps: premixing the carbon nano tube and the nitrogen-containing organic matters through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere. The solid phase purification method of the carbon nano tube can remove the residual transition metal impurities in the production process of the crude carbon nano tube with high selectivity, avoid damaging the tube wall of the carbon nano tube, simultaneously maintain the excellent mechanical and electrical properties of the carbon nano tube, and has the advantages of simple process, high purification efficiency, low cost and environmental protection.
Description
Technical Field
The invention belongs to the technical field of purification of carbon nanotubes, and particularly relates to a solid phase purification method of carbon nanotubes.
Background
The carbon nano tube is a one-dimensional quantum material based on a hexagonal lattice formed by carbon atoms, has excellent mechanical, electrical, chemical and biological characteristics, and has wide application prospect. The conventional method for preparing the carbon nanotubes comprises the following steps: arc discharge, glow discharge, laser ablation, solid phase pyrolysis, chemical vapor deposition, gas combustion, etc., wherein chemical vapor deposition is currently widely used. However, the chemical vapor deposition method prepares carbon nanotubes using transition metals (Fe, co, ni, etc.) as catalysts, and the prepared carbon nanotubes generally remain with transition metal nanoparticle impurities, affecting the performance and application of the carbon nanotubes, and thus, purification treatment of the crude carbon nanotubes is required. At present, the carbon nano tube generally adopts a liquid phase pickling method to remove the transition metal nano particle impurities in the carbon nano tube, but the liquid phase pickling method has the defects of low purification degree, reduced performance, acid-containing wastewater generation and the like of the carbon nano tube. Therefore, development of a more efficient, green and clean carbon nanotube purification method is urgently needed.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: at present, the carbon nano tube generally adopts a liquid phase pickling method to remove the transition metal nano particle impurities in the carbon nano tube, uses one or more mixed acids of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid and the like to react with the transition metal nano particles in the crude carbon nano tube under the conditions of ultrasound, H 2O2, potassium permanganate or heating to generate soluble salt, and then filters and washes to remove the soluble salt, thereby achieving the aim of purifying the carbon nano tube. However, the liquid phase pickling method can only remove the transition metal nano particles exposed on the surface of the carbon nano tube, and is difficult to obtain the high-purity carbon nano tube; the liquid phase pickling method has poor reaction selectivity, can damage the tube wall structure of the carbon nano tube, and reduces the mechanical and electrical properties of the carbon nano tube; the liquid-phase pickling method has complicated process flow and generates a large amount of acid-containing wastewater in the treatment process. Therefore, development of a more efficient, green and clean carbon nanotube purification method is urgently needed.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a solid-phase purification method of carbon nanotubes, which can remove the residual transition metal impurities in the production process of the crude carbon nanotubes with high selectivity, avoid damaging the walls of the carbon nanotubes, and simultaneously maintain the excellent mechanical and electrical properties of the carbon nanotubes, and has the advantages of simple process, high purification efficiency, low cost and environmental protection.
The solid phase purification method of the carbon nano tube comprises the following steps: premixing the carbon nano tube and the nitrogen-containing organic matters through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere.
The solid phase purification method of the carbon nano tube according to the embodiment of the invention has the advantages and technical effects that: according to the method, the crude carbon nano tube with transition metal impurities left in the production process is purified, firstly, nitrogen-containing organic matters and the crude carbon nano tube are selected to be premixed through ball milling, the nitrogen-containing organic matters and the carbon nano tube are fully and uniformly mixed, and a part of tail end of the carbon nano tube is opened to seal a port through mechanical force, so that the residual transition metal nano particles are exposed, the nitrogen-containing organic matters are fully contacted with the metal nano particles in the carbon nano tube, and the removal of the metal nano particles is facilitated; then roasting the premix under inert atmosphere, wherein nitrogen-containing organic matters can generate volatile matters such as CN x and the like in the high-temperature decomposition process, the volatile matters react with fully exposed transition metal nano particles to generate transition metal volatile matters, and then the transition metal volatile matters are carried out of the carbon nano tube along with inert gas, so that the purposes of removing transition metal impurities and purifying the carbon nano tube are achieved, the removal rate of the transition metal impurities can exceed 90%, and meanwhile, the method can avoid damage of acid treatment to the wall of the carbon nano tube and can keep excellent mechanical and electrical properties of the carbon nano tube.
In some embodiments, the nitrogen-containing organic comprises at least one of dicyandiamide, melamine, urea, and melem.
In some embodiments, the weight ratio of the nitrogen-containing organic matter to the carbon nanotubes is 0.1:1 to 300:1.
In some embodiments, the rotational speed of the ball milling process is 200 to 350rpm.
In some embodiments, the ball milling process is for a period of time ranging from 5 to 50 hours.
In some embodiments, the inert atmosphere comprises at least one of nitrogen, argon, helium.
In some embodiments, the firing temperature is 500 to 1200 ℃.
In some embodiments, the firing rate is from 1 to 20 ℃ min -1.
In some embodiments, the firing time is 1 to 50 hours.
In some embodiments, the carbon nanotubes are crude carbon nanotubes produced by chemical vapor deposition.
Drawings
FIG. 1 is an X-ray diffraction pattern of crude carbon nanotubes of example 2 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the carbon nanotube treated by the solid phase purification method of example 2 of the present invention.
FIG. 3 is an electrochemical impedance spectrum of the purified Carbon Nanotubes (CNTs) of example 6 and the purified carbon nanotubes (A-CNTs) of comparative example 1 according to the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The solid phase purification method of the carbon nano tube comprises the following steps: premixing the carbon nano tube and the nitrogen-containing organic matters through ball milling treatment to obtain a premix; the pre-mixture is calcined under an inert atmosphere.
According to the solid-phase purification method of the carbon nano tube, the crude carbon nano tube with transition metal impurities left in the production process is purified, firstly, nitrogen-containing organic matters and the crude carbon nano tube are selected to be premixed through ball milling, the nitrogen-containing organic matters and the carbon nano tube are fully and uniformly mixed, and a part of tail end of the carbon nano tube is opened through mechanical force to seal a port, so that the residual transition metal nano particles are exposed, the full contact of the nitrogen-containing organic matters and the metal nano particles in the carbon nano tube is facilitated, and the removal of the metal nano particles is facilitated; then roasting the premix under inert atmosphere, wherein nitrogen-containing organic matters can generate volatile matters such as CN x and the like in the high-temperature decomposition process, the volatile matters react with fully exposed transition metal nano particles to generate transition metal volatile matters, and then the transition metal volatile matters are carried out of the carbon nano tube along with inert gas, so that the purposes of removing transition metal impurities and purifying the carbon nano tube are achieved, the removal rate of the transition metal impurities can exceed 90%, and meanwhile, the method can avoid damage of acid treatment to the wall of the carbon nano tube and can keep excellent mechanical and electrical properties of the carbon nano tube.
In some embodiments, the nitrogen-containing organic comprises at least one of dicyandiamide, melamine, urea, and melem. In the embodiment of the invention, the nitrogen-containing organic matters are optimized, the nitrogen content of the nitrogen-containing organic matters is high, more volatile CN x substances can be generated, the purification effect of the carbon nano tube is improved, and the impurity content is reduced.
In some embodiments, the nitrogen-containing organic is preferably dicyandiamide. In the embodiment of the invention, the types of CN x generated in the high-temperature decomposition process of different nitrogen-containing organic matters are slightly different, and CN x generated in dicyandiamide decomposition is easier to combine with the surface atoms of the transition metal nano particles in the crude carbon nano tube, so that the removal effect of metal impurities is improved.
In some embodiments, the nitrogen-containing organic is further preferably a combination of dicyandiamide and melem, optionally in a mass ratio of 2:1. in the embodiment of the invention, a synergistic effect exists between CN x generated by decomposing two different nitrogen-containing organic matters of dicyandiamide and miller amine, which is beneficial to improving the removal effect of metal impurity nano particles.
In some embodiments, the weight ratio of the nitrogen-containing organic matter to the carbon nanotubes is 0.1:1 to 300:1, preferably 1:1 to 300:1. In the embodiment of the invention, the addition amount of the nitrogen-containing organic matters is optimized, and if the addition amount of the nitrogen-containing organic matters is too high, the surface of the carbon nano tube is wrapped by carbon nitride, so that the conductivity of the carbon nano tube is reduced; if the amount of the nitrogen-containing organic matter is too low, the metal nano particles are not completely removed, and the purpose of removing the metal impurities cannot be achieved.
In some embodiments, the rotational speed of the ball milling process is 200 to 350rpm; the ball milling treatment time is 5-50 hours, preferably 10-50 hours. In the embodiment of the invention, the ball milling treatment process opens the end seal of the carbon nano tube by mechanical force, which is favorable for the contact of the nitrogen-containing organic matters and the metal nano particles in the carbon nano tube and the removal of the metal nano particles.
In some embodiments, the inert atmosphere comprises at least one of nitrogen, argon, helium. The roasting is carried out in an inert atmosphere, no vacuumizing is needed, and the requirement on equipment is low.
In some embodiments, the firing temperature is 500 to 1200 ℃, preferably 500 to 1000 ℃; the temperature rising rate of the roasting is 1-20 ℃ min -1, preferably 5-20 ℃ min -1; the roasting time is 1 to 50 hours, preferably 3 to 30 hours. In the embodiment of the invention, the roasting temperature and time are optimized, which is favorable for generating the volatile CN x substance and volatilizing and removing the generated transition metal volatile substance and is favorable for improving the purification effect of the carbon nano tube.
In some embodiments, the carbon nanotubes are crude carbon nanotubes produced by chemical vapor deposition.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
After 0.3g of crude carbon nanotube and 5g of cyanamide were uniformly mixed, the mixture was transferred to a ball mill pot, and the rotational speed of the ball mill was set at 300rpm, followed by grinding for 24 hours. Transferring the ground mixture into a quartz boat, putting into a tube furnace, introducing argon, heating to 800 ℃ according to the heating rate of 10 ℃ min -1, and keeping the temperature for 8 hours. Cooling to room temperature to obtain purified carbon nanotube.
Example 2
2G of crude carbon nanotubes and 6g of dicyandiamide are uniformly mixed and then transferred into a ball milling tank, the rotating speed of the ball milling tank is set to 250rpm, and the grinding is carried out for 12 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing nitrogen, heating to 500 ℃ according to the heating rate of 20 ℃ min -1, and keeping the temperature for 30 hours. Cooling to room temperature to obtain purified carbon nanotube.
As can be seen from fig. 1, in addition to the diffraction peaks (26.3 °, 43.1 °, 54.2 °) of the carbon nanotubes, the diffraction peaks (44.5 °, 51.9 °) of metallic Ni were also detected in the XRD spectrum of the crude carbon nanotubes, indicating that the crude carbon nanotubes contained a certain amount of residual metallic Ni impurities.
From fig. 2, it can be seen that the diffraction peaks (44.5 ° and 51.9 °) of the metal Ni disappear after the crude carbon nanotubes are purified by the solid phase method, and only the diffraction peaks (26.3 ° and 43.1 ° and 54.2 °) of the carbon nanotubes are detected, which indicates that the metal Ni impurities are effectively removed after the crude carbon nanotubes are purified by the solid phase method.
Example 3
After 0.15g of crude carbon nanotube and 15g of melamine were mixed uniformly, the mixture was transferred to a ball mill pot, and the rotational speed of the ball mill was set at 350rpm, followed by grinding for 24 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing helium, heating to 1000 ℃ according to the heating rate of 5 ℃ min -1, and keeping the temperature for 3 hours. Cooling to room temperature to obtain purified carbon nanotube.
Example 4
2G of crude carbon nano tube and 6g of urea are uniformly mixed and then transferred into a ball milling tank, the rotating speed of the ball milling tank is set to 250rpm, and the grinding is carried out for 12 hours. Transferring the ground mixture into a quartz boat, putting into a tube furnace, introducing helium, heating to 500 ℃ according to the heating rate of 20 ℃ min -1, and keeping the temperature for 30 hours. Cooling to room temperature to obtain purified carbon nanotube.
Example 5
After 0.4g of crude carbon nanotube and 0.6g of dicyandiamide were uniformly mixed, the mixture was transferred to a ball mill pot, the rotation speed of the ball mill was set to 280rpm, and the mixture was milled for 50 hours. Transferring the ground mixture into a quartz boat, putting into a tube furnace, introducing argon, heating to 1000 ℃ according to the heating rate of 10 ℃ min -1, and keeping the temperature for 5 hours. Cooling to room temperature to obtain purified carbon nanotube.
Example 6
After 0.15g of crude carbon nanotube, 5g of Miller amine and 10g of dicyandiamide were mixed uniformly, the mixture was transferred to a ball mill pot, the rotation speed of the ball mill was set at 350rpm, and the mixture was milled for 24 hours. Transferring the ground mixture into a quartz boat, putting the quartz boat into a tube furnace, introducing helium, heating to 1000 ℃ according to the heating rate of 5 ℃ min -1, and keeping the temperature for 3 hours. After cooling to room temperature, purified Carbon Nanotubes (CNTs) were obtained.
Example 7
The same procedure as in example 6 was followed except that no Miller amine was added and 15g of dicyandiamide was used as the nitrogen-containing organic compound.
Example 8
The same procedure as in example 6 was followed except that dicyandiamide was not added, and 15g of Miller amine was added as the nitrogen-containing organic substance.
Comparative example 1
The same procedure as in example 6 was followed except that the purified carbon nanotubes of example 6 were subjected to acid washing, specifically: the purified Carbon Nanotubes (CNTs) are added into a single-mouth round bottom flask containing 100mL 5M HCl solution, a condensing tube is arranged, and the mixture is heated and stirred for reaction for 6 hours at 120 ℃. And cooling to room temperature, filtering, washing with water, washing with ethanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon nanotubes (A-CNTs) subjected to acid washing treatment.
The purified Carbon Nanotubes (CNTs) of example 6 and the acid-washed carbon nanotubes (A-CNTs) of comparative example 1 were tested by electrochemical impedance spectroscopy, and the test results are shown in FIG. 3. As can be seen from fig. 3, the charge transfer resistance of the carbon nanotubes (a-CNTs) obtained after the acid treatment was 165 Ω, while the charge transfer resistance of the Carbon Nanotubes (CNTs) obtained by the solid phase purification method was only 143 Ω, indicating that the carbon nanotubes obtained by the solid phase purification method had better conductivity. As can be seen from table 1, the residual content of Ni impurity in the carbon nanotubes after the 5M HCl acid washing treatment was reduced from 0.03wt% to 0.01wt%, but the high temperature acid washing treatment partially destroyed the conjugated structure of c=c of the carbon nanotube walls, resulting in poor conductivity of the acid washed carbon nanotubes (a-CNTs), increased contact resistance, and reduced performance of the purified carbon nanotubes.
Comparative example 2
The same procedure as in example 6 was repeated except that the carbon nanotubes, the miller amine and the dicyandiamide were uniformly mixed and then directly subjected to the calcination treatment without performing the ball milling treatment.
The measurement results of the Ni impurity contents in the carbon nanotubes before and after purification of examples 1 to 8 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (7)
1. A method for solid phase purification of carbon nanotubes, comprising: premixing the carbon nano tube and the nitrogen-containing organic matters through ball milling treatment to obtain a premix; the pre-mixture is roasted in inert atmosphere, wherein the carbon nano tube is a crude carbon nano tube prepared by chemical vapor deposition, the nitrogen-containing organic matter comprises dicyan diamine, the rotation speed of ball milling treatment is 200-350 rpm, the ball milling treatment time is 12-50 h, the roasting is carried out in a tube furnace, and inert gas is introduced into the tube furnace.
2. The method of claim 1, wherein the nitrogen-containing organic matter comprises dicyandiamide and melem.
3. The method for solid-phase purification of carbon nanotubes according to claim 1, wherein the weight ratio of the nitrogen-containing organic matter to the carbon nanotubes is 0.1:1 to 300:1.
4. The method of claim 1, wherein the inert atmosphere comprises at least one of nitrogen, argon, and helium.
5. The method for solid-phase purification of carbon nanotubes according to claim 1, wherein the firing temperature is 500 to 1200 ℃.
6. The method for solid-phase purification of carbon nanotubes according to claim 1, wherein the temperature rise rate of the calcination is 1 to 20 ℃ min -1.
7. The method for solid-phase purification of carbon nanotubes according to claim 1, wherein the calcination time is 1 to 50 hours.
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