CN114572963B - High-yield and good-conductivity carbon nanotube synthesis method - Google Patents
High-yield and good-conductivity carbon nanotube synthesis method Download PDFInfo
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- CN114572963B CN114572963B CN202210264963.7A CN202210264963A CN114572963B CN 114572963 B CN114572963 B CN 114572963B CN 202210264963 A CN202210264963 A CN 202210264963A CN 114572963 B CN114572963 B CN 114572963B
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Abstract
The invention discloses a synthesis method of a carbon nano tube with high yield and good conductivity, belonging to the technical field of chemistry. The method for synthesizing the carbon nano tube comprises the following steps: (1) Uniformly mixing water, ferric nitrate hexahydrate, cobalt nitrate hexahydrate, aluminum nitrate hexahydrate and magnesium nitrate hexahydrate, and heating, evaporating and concentrating until the solution density is 1.33g/ml to obtain a solution; roasting the solution for 180min at 640 ℃ by using an air atmosphere continuous pusher kiln, and crushing and sieving to obtain a catalyst; (2) Adding the catalyst into a fluidized bed reactor, and introducing hydrogen at 660 ℃ for reduction for 10min; stopping introducing hydrogen, then introducing nitrogen and propylene, and reacting for 40min at 660 ℃; stopping propylene introduction, introducing nitrogen and carbon dioxide, and heating to 760-800 ℃ for 30 min; stopping introducing nitrogen and carbon dioxide, and changing into methane and hydrogen, and reacting for 40min at 760-800 ℃; stopping ventilation, and outputting the product to obtain the carbon nano tube. The carbon nano tube has high yield and good conductivity, thereby being applied to lithium batteries.
Description
Technical Field
The invention relates to a synthesis method of a carbon nano tube with high yield and good conductivity, belonging to the technical field of chemistry.
Background
In recent years, power cells have been developed in a jump-type manner to achieve the goals of peak-to-peak carbon and neutral carbon. The lithium battery has the advantages of environment friendliness, high temperature difference change adaptability, long service life, low self-discharge rate and the like. The lithium ion battery active material is granular, and the conductive agent is required to fill the gaps of the active material, so that the conductive agent can be fully contacted with the active material, thereby improving the conductive performance.
The conductive agent is used as a key auxiliary material of the lithium ion battery and plays a role in enhancing the conductive contact of the active substance. Carbon nanotubes, which are excellent conductive materials, have potential application values in the fields of electronics, energy sources, communication and the like, and in recent years, have been used as a main component of a conductive agent in the production of lithium batteries, thereby greatly enhancing the application performance of the lithium batteries.
Currently, the synthesis method of multi-walled carbon nanotubes for lithium ion batteries in the market is mainly Chemical Vapor Deposition (CVD). CVD is further subdivided according to the carbon raw material used in the reaction process, and can be roughly divided into two types, namely, CVD-pyrolysis of methane to synthesize carbon nanotubes and CVD-pyrolysis of olefins (e.g., ethylene, propylene, etc.) to synthesize carbon nanotubes. Synthesizing carbon nano tube by CVD cracking methane, wherein the proper reaction temperature is 700-1000 ℃; the graphitization degree of the synthesized carbon nano tube is higher and the conductivity is better, but the catalyst is easy to be deactivated by the pyrolysis reaction, and the yield of the carbon nano tube is generally lower. CVD cracking olefin to synthesize carbon nano tube, and the proper reaction temperature is 650-700 ℃; the reactivity of the olefin is high, the yield of the synthesized carbon nano tube is generally higher, but the graphitization degree of the synthesized carbon nano tube is lower due to the lower reaction temperature, and the conductivity is obviously poorer.
Disclosure of Invention
[ technical problem ]
The carbon nano tube prepared at present cannot simultaneously achieve good conductivity and high yield.
Technical scheme
In order to solve the problems, the invention uses a two-step CVD reaction to synthesize the carbon nano tube with higher yield and higher graphitization degree.
A first object of the present invention is to provide a method for synthesizing carbon nanotubes having high yield and good electrical conductivity, comprising the steps of:
(1) The synthesis catalyst comprises the following components:
uniformly mixing water, ferric nitrate hexahydrate, cobalt nitrate hexahydrate, aluminum nitrate hexahydrate and magnesium nitrate hexahydrate, and heating, evaporating and concentrating until the solution density is 1.33g/ml to obtain a solution; roasting the solution for 180min at 640 ℃ by using an air atmosphere continuous pusher kiln, and crushing and sieving to obtain a catalyst;
(2) Synthesizing carbon nano tubes:
adding the catalyst into a fluidized bed reactor, and introducing hydrogen at 660 ℃ for reduction for 10min;
stopping introducing hydrogen, then introducing nitrogen and propylene, and reacting for 40min at 660 ℃;
stopping propylene introduction, introducing nitrogen and carbon dioxide, and heating to 760-800 ℃ for 30 min;
stopping introducing nitrogen and carbon dioxide, and changing into methane and hydrogen, and reacting for 40min at 760-800 ℃;
stopping ventilation, and outputting the product to obtain the carbon nanotube.
In one embodiment of the invention, in the step (1), the mass ratio of water, ferric nitrate nonahydrate, cobalt nitrate hexahydrate, aluminum nitrate nonahydrate and magnesium nitrate hexahydrate is 80:4.85:2.99:1.35:15.69:22.18.
in one embodiment of the invention, the uniform mixing in step (1) is dissolution using mechanical stirring with paddles at 130rpm.
In one embodiment of the present invention, the heating evaporation concentration in step (1) is performed at 85 ℃.
In one embodiment of the present invention, the parameters of the air atmosphere continuous pusher kiln in step (1) are: the length of the hearth is 10 meters, the size of the square sagger is 380mm, and the feeding speed is 10 min/time.
In one embodiment of the invention, the sieving in step (1) is a 80 mesh sieve.
In one embodiment of the invention, the catalyst addition in step (2) is 800g, and the parameters of the fluidized bed reactor are: 500mm in diameter and 6000mm in height.
In one embodiment of the present invention, the flow rate of hydrogen in step (2) is 30slm.
In one embodiment of the present invention, the flow rates of nitrogen and propylene in step (2) are 400slm, 700slm.
In one embodiment of the present invention, the flow rates of nitrogen and carbon dioxide in step (2) are 400slm, 100slm.
In one embodiment of the present invention, the flow rates of methane and hydrogen in step (2) are 1200slm, 50slm.
In one embodiment of the invention, the product output in step (2) is a positive nitrogen pressure feed.
The second purpose of the invention is to prepare the carbon nano tube with high yield and good conductivity by the method.
The third object of the present invention is to use the carbon nanotubes of high yield and good conductivity in the fields of electronics, energy and communications.
In one embodiment of the invention, the use includes use in the preparation of lithium ion batteries.
[ advantageous effects ]
According to the invention, the carbon nano tube is synthesized through two-step CVD reaction by utilizing the reaction characteristics of different carbon sources, so that the yield of the carbon nano tube is improved, the graphitization degree and the conductivity of the carbon nano tube are improved, and the comprehensive performance of the carbon nano tube is improved, so that the carbon nano tube can be better applied to a lithium battery.
Drawings
Fig. 1 is a scanning electron micrograph and a raman spectrum of the carbon nanotube of example 1.
Fig. 2 is a scanning electron micrograph and a raman spectrum of the carbon nanotube of example 2.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
Example 1
A method for producing high yield and good conductivity carbon nanotubes, comprising the steps of:
(1) The synthesis catalyst comprises the following components:
sequentially weighing 80kg of pure water, 4.85kg of ferric nitrate hexahydrate, 2.99kg of cobalt nitrate hexahydrate, 1.35kg of aluminum nitrate hexahydrate, 15.69kg of magnesium nitrate hexahydrate and 22.18kg of anhydrous citric acid, sequentially adding into a reaction kettle, mechanically stirring and dissolving by using a blade, and rotating at 130rpm; heating at 85 ℃, evaporating and concentrating until the density of the solution reaches 1.33g/ml to obtain a solution;
discharging the solution from the reaction kettle; roasting the solution by using an air atmosphere continuous pusher kiln; wherein the length of the hearth is 10 meters, the size of the square sagger is 380 x 380mm, the feeding speed is 10 min/time, the roasting temperature is set to 640 ℃, and the effective roasting time is 180min;
sieving and crushing the discharged material through a 80-mesh sieve to obtain a catalyst;
(2) Synthesizing carbon nano tubes:
weighing 800g of catalyst, adding the catalyst into the bottom of a fluidized bed reactor with the diameter of 500mm and the height of 6000mm through a catalyst adding tank, keeping the temperature at 660 ℃, and introducing hydrogen with the flow rate of 30slm from a bottom feeding nozzle for reduction for 10min;
stopping introducing hydrogen, then introducing 400slm of nitrogen and 700slm of propylene, and reacting at 660 ℃ for 40min;
stopping propylene feeding, then feeding 400slm of nitrogen and 100slm of carbon dioxide, and heating to 760 ℃ for 30 min;
stopping introducing nitrogen and carbon dioxide, changing into 1200slm methane and 50slm hydrogen, and reacting at 760 ℃ for 60min;
stopping introducing the reaction gas, and conveying the product to a finished product storage tank by positive pressure of nitrogen to cool to obtain the carbon nano tube.
Example 2
A method for synthesizing carbon nanotubes with high yield and good conductivity, comprising the following steps:
(1) The synthesis catalyst comprises the following components:
sequentially weighing 80kg of pure water, 4.85kg of ferric nitrate hexahydrate, 2.99kg of cobalt nitrate hexahydrate, 1.35kg of aluminum nitrate hexahydrate, 15.69kg of magnesium nitrate hexahydrate and 22.18kg of anhydrous citric acid, sequentially adding into a reaction kettle, mechanically stirring and dissolving by using a blade, and rotating at 130rpm; heating at 85 ℃, evaporating and concentrating until the density of the solution reaches 1.33g/ml to obtain a solution;
discharging the solution from the reaction kettle; roasting the solution by using an air atmosphere continuous pusher kiln; wherein the length of the hearth is 10 meters, the size of the square sagger is 380 x 380mm, the feeding speed is 10 min/time, the roasting temperature is set to 640 ℃, and the effective roasting time is 180min;
sieving and crushing the discharged material through a 80-mesh sieve to obtain a catalyst;
(2) Synthesizing carbon nano tubes:
weighing 800g of catalyst, adding the catalyst into the bottom of a fluidized bed reactor with the diameter of 500mm and the height of 6000mm through a catalyst adding tank, keeping the temperature at 660 ℃, and introducing hydrogen with the flow rate of 30slm from a bottom feeding nozzle for reduction for 10min;
stopping introducing hydrogen, then introducing 400slm of nitrogen and 700slm of propylene, and reacting at 660 ℃ for 40min;
stopping propylene feeding, then feeding 400slm of nitrogen and 100slm of carbon dioxide, and heating to 800 ℃ for 30 min;
stopping introducing nitrogen and carbon dioxide, changing into 1200slm methane and 50slm hydrogen, and reacting at 800 ℃ for 60min;
stopping introducing the reaction gas, and conveying the product to a finished product storage tank by positive pressure of nitrogen to cool to obtain the carbon nano tube.
Comparative example 1
The synthetic carbon nanotubes of example 1 (2) were adjusted to:
weighing 800g of catalyst, adding the catalyst into the bottom of a fluidized bed reactor with the diameter of 500mm and the height of 6000mm through a catalyst adding tank, keeping the temperature at 660 ℃, and introducing hydrogen with the flow rate of 30slm from a bottom feeding nozzle for reduction for 10min;
stopping introducing hydrogen, then introducing 400slm of nitrogen and 700slm of propylene, and reacting at 660 ℃ for 40min;
stopping introducing propylene, and conveying the product to a finished product storage tank by positive pressure of nitrogen for cooling to obtain the carbon nanotube.
Comparative example 2
The synthetic carbon nanotubes of example 1 (2) were adjusted to:
weighing 800g of catalyst, adding the catalyst into the bottom of a fluidized bed reactor with the diameter of 500mm and the height of 6000mm through a catalyst adding tank, keeping the temperature of the reactor at 760 ℃, introducing 1200slm methane and 50slm hydrogen from a bottom feeding nozzle, and reacting for 60min at 760 ℃;
stopping introducing methane and hydrogen, and conveying the product to a finished product storage tank by positive pressure of nitrogen for cooling; obtaining the carbon nano tube.
Comparative example 3
The synthetic carbon nanotubes of example 1 (2) were adjusted to:
weighing 800g of catalyst, adding the catalyst into the bottom of a fluidized bed reactor with the diameter of 500mm and the height of 6000mm through a catalyst adding tank, and keeping the reactor constant at 760 ℃; 1200slm methane and 50slm hydrogen are introduced from a bottom feeding nozzle, and the reaction is carried out for 60min at 760 ℃;
stopping introducing methane and hydrogen, introducing 400slm of nitrogen and 100slm of carbon dioxide, purging and cooling to 660 ℃;
introducing nitrogen with flow rate of 400slm and propylene with flow rate of 700slm at 660 ℃ for reaction for 40min;
stopping introducing the reaction gas, and conveying the product to a finished product storage tank by positive pressure of nitrogen for cooling; obtaining the carbon nano tube.
The obtained carbon nanotubes were subjected to a test, and the test results are shown in table 1 below:
TABLE 1
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. A method for synthesizing carbon nanotubes with high yield and good conductivity, comprising the steps of:
(1) The synthesis catalyst comprises the following components:
uniformly mixing water, ferric nitrate hexahydrate, cobalt nitrate hexahydrate, aluminum nitrate hexahydrate and magnesium nitrate hexahydrate, and heating, evaporating and concentrating until the solution density is 1.33g/mL to obtain a solution; roasting the solution for 180min at 640 ℃ by using an air atmosphere continuous pusher kiln, and crushing and sieving to obtain a catalyst;
(2) Synthesizing carbon nano tubes:
adding the catalyst into a fluidized bed reactor, and introducing hydrogen at 660 ℃ for reduction for 10min;
stopping introducing hydrogen, then introducing nitrogen and propylene, and reacting for 40min at 660 ℃;
stopping propylene introduction, introducing nitrogen and carbon dioxide, and heating to 760-800 ℃ for 30 min;
stopping introducing nitrogen and carbon dioxide, and changing into methane and hydrogen, and reacting for 40min at 760-800 ℃;
stopping ventilation, and outputting a product to obtain the carbon nanotube, wherein the mass ratio of water to ferric nitrate nonahydrate to cobalt nitrate hexahydrate to aluminum nitrate nonahydrate to magnesium nitrate hexahydrate in the step (1) is 80:4.85:2.99:1.35:15.69, wherein the flow rate of the hydrogen in the step (2) is 30slm, the flow rates of the nitrogen and the propylene are 400slm and 700slm, the flow rates of the nitrogen and the carbon dioxide are 400slm and 100slm, and the flow rates of the methane and the hydrogen are 1200slm and 50slm.
2. The method of claim 1, wherein the parameters of the air atmosphere continuous pusher kiln in step (1) are: the length of the hearth is 10 meters, the size of the square sagger is 380mm, and the feeding speed is 10 min/time.
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| CN202210264963.7A CN114572963B (en) | 2022-03-17 | 2022-03-17 | High-yield and good-conductivity carbon nanotube synthesis method |
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Non-Patent Citations (1)
| Title |
|---|
| Direct growth of carbon nanotube junctions by a two-step chemical vapor deposition;Zhong Jin等;《Chemical Physics Letters》;20061014;第177–183页 * |
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