CN115924890A

CN115924890A - Preparation method of three-dimensional carbon nano tube

Info

Publication number: CN115924890A
Application number: CN202211357411.7A
Authority: CN
Inventors: 王彬彬; 杨金富; 陈安然; 林俊达; 张雨轩; 王静宜
Original assignee: Yunnan Iridium Biotechnology Co ltd
Current assignee: Yunnan Iridium Biotechnology Co ltd
Priority date: 2022-11-01
Filing date: 2022-11-01
Publication date: 2023-04-07

Abstract

The invention relates to a preparation method of a three-dimensional carbon nanotube, belonging to the technical field of electrode material preparation. Dissolving hydroxyl multi-walled carbon nanotubes, cobalt acetate and melamine in methanol to obtain a mixture solution; evaporating the mixture solution to remove methanol to obtain an evaporated mixture; and (3) carrying out two-stage high-temperature treatment on the evaporated mixture: cooling the high-temperature treatment product to room temperature to obtain a precursor; and soaking the obtained precursor in a sulfuric acid solution with the concentration of 0.5-0.8mol/L for 24-36h to obtain the three-dimensional carbon nano tube after soaking. The method is simple and easy to control, and the three-dimensional carbon nano tube with excellent performance can be prepared.

Description

Preparation method of three-dimensional carbon nanotube

Technical Field

The invention relates to a preparation method of a three-dimensional carbon nanotube, belonging to the technical field of electrode material preparation.

Background

The carbon nano tube is used as a one-dimensional nano material, has light weight, perfect connection of a hexagonal structure and a plurality of abnormal mechanical, electrical and chemical properties, but with the deepening of the carbon nano tube and the nano material, the three-dimensional carbon nano tube has a wider application scene in the future, and compared with the one-dimensional carbon nano tube, the three-dimensional carbon nano tube has multi-dimensional conductive capability and more excellent mechanical properties.

The current preparation methods of carbon nanotubes mainly comprise: arc discharge, laser ablation, chemical vapor deposition, and the like.

The patent application number is 2014103441241, and the method for preparing the three-dimensional carbon nanotube network. The method comprises the following steps of (1) mixing active metals: sodium, potassium, magnesium, calcium or carbon dioxide is used as a raw material, a metal net is used as a template, the active metal and the metal net are placed into a high-temperature furnace and heated under the protection of argon or nitrogen, then carbon dioxide or mixed gas of carbon dioxide and nitrogen or argon is introduced, and the redox reaction between the active metal and the carbon dioxide is utilized to directly prepare the three-dimensional carbon nanotube net on the metal net. The size of the carbon nanotubes can be controlled by adjusting the reaction temperature, the reaction time and the flow rate of the introduced gas. The invention has the advantages of cheap and easily obtained raw materials, low cost and simple synthesis process, and takes greenhouse gas carbon dioxide as the raw material, thereby being environment-friendly. The obtained carbon nanotube network has good conductivity and mechanical properties, and can be widely applied to preparation of electrode materials of super capacitors or lithium ions. However, this method requires a metal mesh as a template, and is complicated.

The patent application number is 2017108182957, and a three-dimensional configuration carbon nanotube and a preparation method thereof. In the method, ferrocene and thiophene are dissolved in benzene, the benzene is heated under the protection of nitrogen, and then a reaction solution is introduced into a high-temperature reaction furnace by adopting a pulse pump under the atmosphere of nitrogen and hydrogen, and is subjected to high-temperature catalytic cracking to form the carbon nano tube. The three-dimensional carbon nano tube with the stereo structure prepared by the method is formed by connecting linear or bent carbon nano tubes in a three-dimensional structure, and even forms a closed-loop structure. However, the method must rely on certain equipment, such as a pulse pump and the like, in the preparation process.

The preparation method of the three-dimensional carbon nano tube is simple, and the three-dimensional carbon nano tube with excellent performance is prepared and obtained, which is a technical problem.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method of a three-dimensional carbon nanotube. The method is simple and easy to control, and the three-dimensional carbon nano tube with excellent performance can be prepared. The invention is realized by the following technical scheme.

A preparation method of three-dimensional carbon nanotubes comprises the following specific steps:

step 1, dissolving hydroxyl multi-walled carbon nanotubes, cobalt acetate and melamine in methanol to obtain a mixture solution;

step 2, evaporating the mixture solution obtained in the step 1 to remove methanol to obtain an evaporated mixture;

and 3, performing two-stage high-temperature treatment on the evaporated mixture obtained in the step 2:

step 3.1, under the condition of continuously introducing nitrogen, heating the evaporated mixture to 600-700 ℃ at the heating rate of 2 ℃/min, and preserving heat for 3-4h;

3.2, continuously introducing nitrogen, heating to 800-900 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2-2.5h to obtain a high-temperature treatment product;

3.3, after the heat preservation in the step 3.2 is finished, continuously introducing nitrogen, and cooling the high-temperature treatment product to room temperature to obtain a precursor;

and 4, soaking the precursor obtained in the step 3.3 in a sulfuric acid solution with the concentration of 0.5-0.8mol/L for 24-36h to obtain the three-dimensional carbon nano tube after soaking.

In the step 1, the mass ratio of the hydroxyl multi-walled carbon nanotube to the cobalt acetate to the melamine is 3-15:60-298.9:64-320.

The evaporation process of the step 2 comprises the following steps: magnetically stirring and evaporating in water bath at 60-70 deg.c for 3-4 hr.

The introduction amount of nitrogen in the steps 3.1, 3.2 and 3.3 is 5-6L/min.

The invention has the beneficial effects that:

(1) The method is simple and easy to control;

(2) The three-dimensional carbon nano tube prepared by the invention is tightly connected with the tube and mutually overlapped, meanwhile, the large network framework is clear, the diameter of a single carbon nano tube is about 10 nanometers, and the length is different from several micrometers. The three-dimensional carbon nanotube prepared by the method has excellent performance and can be directly applied to the process of preparing electrode materials.

Drawings

FIG. 1 is a TEM image A of a three-dimensional carbon nanotube prepared in example 1 of the present invention;

FIG. 2 is a TEM image B of a three-dimensional carbon nanotube prepared in example 1 of the present invention;

FIG. 3 is a TEM image C of the three-dimensional carbon nanotube prepared in example 1 of the present invention.

Detailed Description

The invention is further described with reference to the following drawings and detailed description.

Example 1

The preparation method of the three-dimensional carbon nano tube comprises the following specific steps:

step 1, dissolving 0.015g of hydroxyl multi-walled carbon nanotube, 0.2989g of cobalt acetate and 0.32g of melamine in 50mL of methanol, and magnetically stirring for 1h to obtain a mixture solution;

step 2, magnetically stirring the mixture solution obtained in the step 1 in a water bath at 60 ℃ for 3 hours, and evaporating to remove methanol to obtain an evaporated mixture;

and 3, carrying out two-stage high-temperature treatment on the evaporated mixture obtained in the step 2:

step 3.1, under the condition of continuously introducing nitrogen (the introduction amount of the nitrogen is 5L/min), heating the mixture after evaporation to 600 ℃ at the heating rate of 2 ℃/min and preserving the heat for 3h;

3.2, continuously introducing nitrogen (the introduction amount of the nitrogen is 5L/min), heating to 800 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2h to obtain a high-temperature treatment product;

step 3.3, after the heat preservation in step 3.2 is finished, continuously introducing nitrogen (the introduction amount of the nitrogen is 5L/min), and cooling the high-temperature treatment product to room temperature to obtain a precursor;

and 4, soaking the precursor obtained in the step 3.3 in 20mL of sulfuric acid solution with the concentration of 0.5mol/L for 24h to obtain the three-dimensional carbon nanotube after soaking.

TEM images of the three-dimensional carbon nanotubes prepared in this example are shown in FIGS. 1 to 3. It can be seen from fig. 1 to 3 that the method obtains a large number of three-dimensional carbon nanotubes, the tubes are connected tightly and overlapped with each other, the large network skeleton is clear, the diameter of a single carbon nanotube is about 10 nanometers, and the lengths are different from one another.

The specific capacitance value of the three-dimensional carbon nanotube prepared by the method can reach 80F/g, and the three-dimensional carbon nanotube has excellent conductivity and can be directly applied to the process of preparing an electrode material.

Example 2

step 1, dissolving 0.003g of hydroxyl multiwalled carbon nanotube, 0.06g of cobalt acetate and 0.064g of melamine in 30mL of methanol, and magnetically stirring for 1h to obtain a mixture solution;

step 2, magnetically stirring the mixture solution obtained in the step 1 in a water bath at 70 ℃ for 4 hours to evaporate and remove methanol to obtain an evaporated mixture;

step 3.1, under the condition of continuously introducing nitrogen (the introduction amount of the nitrogen is 6L/min), heating the mixture after evaporation to 700 ℃ at the heating rate of 2 ℃/min and keeping the temperature for 4h;

3.2, continuously introducing nitrogen (the introduction amount of the nitrogen is 6L/min), heating to 900 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2.5 hours to obtain a high-temperature treatment product;

step 3.3, after the heat preservation in step 3.2 is finished, continuously introducing nitrogen (the introduction amount of the nitrogen is 6L/min), and cooling the high-temperature treatment product to room temperature to obtain a precursor;

and 4, soaking the precursor obtained in the step 3.3 in 20mL of sulfuric acid solution with the concentration of 0.8mol/L for 36h to obtain the three-dimensional carbon nanotube after soaking.

The specific capacitance value of the three-dimensional carbon nanotube prepared by the method can reach 65F/g, and the three-dimensional carbon nanotube has excellent conductivity and can be directly applied to the process of preparing an electrode material.

Example 3

step 1, dissolving 0.003g of hydroxyl multiwalled carbon nanotube, 0.06g of cobalt acetate and 0.064g of melamine in 40mL of methanol, and magnetically stirring for 1h to obtain a mixture solution;

step 2, magnetically stirring the mixture solution obtained in the step 1 in a water bath at 65 ℃ for 3.5 hours, and evaporating to remove methanol to obtain an evaporated mixture;

step 3.1, under the condition of continuously introducing nitrogen (the introduction amount of the nitrogen is 5.5L/min), heating the evaporated mixture to 650 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 3.5h;

3.2, continuously introducing nitrogen (the introduction amount of the nitrogen is 5.5L/min), heating to 850 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2.2 hours to obtain a high-temperature treatment product;

step 3.3, after the heat preservation in step 3.2 is finished, continuously introducing nitrogen (the introduction amount of the nitrogen is 5.5L/min), and cooling the high-temperature treatment product to room temperature to obtain a precursor;

and 4, soaking the precursor obtained in the step 3.3 in 20mL of sulfuric acid solution with the concentration of 0.6mol/L for 30h to obtain the three-dimensional carbon nanotube after soaking.

The specific capacitance value of the three-dimensional carbon nano tube prepared by the method can reach 70F/g, and the three-dimensional carbon nano tube has excellent performance and can be directly applied to the process of preparing an electrode material.

While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims

1. A preparation method of three-dimensional carbon nano-tubes is characterized by comprising the following specific steps:

step 3.1, under the condition of continuously introducing nitrogen, heating the evaporated mixture to 600-700 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3-4h;

step 3.3, after the heat preservation in the step 3.2 is finished, continuously introducing nitrogen, and cooling the high-temperature treatment product to room temperature to obtain a precursor;

2. The method for producing three-dimensional carbon nanotubes according to claim 1, wherein: in the step 1, the mass ratio of the hydroxyl multi-walled carbon nanotube to the cobalt acetate to the melamine is 3-15:60-298.9:64-320.

3. The method for producing three-dimensional carbon nanotubes according to claim 1, wherein: the evaporation process of the step 2 comprises the following steps: magnetically stirring and evaporating in water bath at 60-70 deg.c for 3-4 hr.

4. The method for producing three-dimensional carbon nanotubes according to claim 1, wherein: the introduction amount of nitrogen in the steps 3.1, 3.2 and 3.3 is 5-6L/min.