CN112158827B - Preparation method of carbon nano tube with controllable shape - Google Patents
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
Abstract
The invention belongs to the field of inorganic nano materials, and mainly relates to a preparation method of a carbon nano tube with controllable appearance. The lamellar catalyst containing the transition metal active center is prepared by adopting a one-step synthesis method, and the growth of the carbon nano tubes with different shapes, such as aggregation state, array beam shape and horizontal growth, is realized in a fixed bed or fluidized bed reactor by regulating and controlling the growth conditions of the carbon nano tubes. The array-bundled carbon nano tubes and the horizontally-grown carbon nano tubes prepared by the method are not wound, are easy to purify and disperse, can be used for large-scale mass production of the carbon nano tubes, have good application prospects in the aspect of positive conductive additives, can be applied to the fields of composite materials, lithium batteries, super capacitors, biosensors and the like, and have wide application prospects. The preparation method is beneficial to producing a novel lithium battery with high energy density, accelerates the industrialization of the pure electric vehicle taking the lithium battery as power, and promotes the industrial upgrading of the whole lithium battery industry.
Description
Technical Field
The invention relates to a preparation method of a carbon nano tube with controllable appearance, belonging to the field of inorganic nano materials.
Technical Field
The carbon nanotube has a typical one-dimensional tubular structure, is stable in performance, and has excellent mechanical, electrical and chemical properties, for example, the strength is 16 times that of stainless steel, and the thermal conductivity is 5 times that of copper. Therefore, the carbon nano tube has wide application prospect in various fields of composite materials, micro machinery, information storage, nano electronic devices, batteries and the like. For example, after carbon nanotubes are added into a polymer, ceramic or metal matrix, the electrical conductivity, the thermal conductivity and other physical properties of the main body material can be obviously improved, and the effect of the carbon nanotube-based composite material is far better than that of the traditional additives such as carbon black, carbon fiber or glass fiber. The structure of the carbon nano tube is the same as the lamellar structure of graphite, so the carbon nano tube has good conductive performance, at present, multiwalled carbon nano tube conductive slurry is widely applied to the field of lithium batteries as a positive conductive additive, the charging and discharging efficiency and the multiplying power of the lithium batteries can be effectively improved, the service life of the batteries is prolonged, the production of novel lithium batteries with high energy density is facilitated, the industrialization of pure electric vehicles taking the lithium batteries as power is greatly accelerated, and the industrial upgrading of the whole lithium battery industry is promoted.
In summary, based on the application requirements of the carbon nanotubes, it is of great significance to realize large-scale mass production of carbon nanotubes with different morphologies. The invention realizes the preparation of the lamellar catalyst containing the transition metal active center by a one-step synthesis method, and the carbon nanotubes with different shapes, aggregation states, array beam shapes and horizontal growth can grow in a fixed bed or a fluidized bed reactor by regulating and controlling the catalyst composition, the proportion of the carbon nanotube growth carrier gas and other factors. The array beam-shaped carbon nano tube is a carbon nano tube which is vertical to the catalyst lamellar structure and grows between the lamellae; the horizontally grown carbon nano tube is a carbon nano tube horizontally grown along the direction of carbon source airflow, the carbon nano tubes with the two shapes are not wound, and large-scale batch production can be realized. It is worth mentioning that the catalyst lamellar structure is composed of magnesium oxide, aluminum oxide or a mixture of magnesium oxide and aluminum oxide, the lamellar structure is easy to remove after the carbon nano tube grows, the obtained high-purity carbon nano tube is free from winding and easy to disperse, and the catalyst lamellar structure has wide application market in the field of lithium battery positive conductive additives.
Disclosure of Invention
The invention aims to provide a preparation method capable of realizing the controllable growth of carbon nanotubes with different shapes.
A method for preparing carbon nanotubes with controllable morphology is characterized in that a one-step synthesis method is adopted to prepare a lamellar catalyst containing a transition metal active center, and the growth of carbon nanotubes with different morphologies, such as aggregation state, array beam shape and horizontal growth, is realized in a fixed bed or fluidized bed reactor by regulating and controlling the growth conditions of the carbon nanotubes; the method comprises the following specific steps:
(1) adding purified water and ethylene glycol into a reaction kettle according to a fixed volume ratio, and stirring uniformly to obtain a solution A;
(2) adding nitrate containing active components into the solution A, and continuously stirring to completely dissolve the nitrate to obtain a solution B;
(3) weighing a certain amount of ammonia water, adding the ammonia water into the solution B, and uniformly stirring to obtain a solution C;
(4) adding molybdate completely dissolved in the purified water into the solution C to obtain a mixed solution;
(5) stirring and heating the reaction kettle to a set temperature, and reacting for a certain time;
(6) after the reaction time is reached, cooling to room temperature, filtering, washing a filter cake twice by absolute ethyl alcohol and purified water respectively to obtain a precipitate, drying the precipitate, and cooling to room temperature to obtain a solid;
(7) calcining the solid in a muffle furnace to obtain a lamellar catalyst;
(8) the lamellar catalyst is put into a reactor, and the growth of the carbon nano tubes with different shapes, such as aggregation state, array beam shape and horizontal growth, is realized by regulating and controlling the growth conditions of the carbon nano tubes.
Further, the volume ratio of the water to the ethylene glycol in the step (1) is 1: 1.
Further, the nitrate in the step (2) is two or more of ferric nitrate, cobalt nitrate, nickel nitrate, magnesium nitrate, aluminum nitrate and the like.
Further, in the step (5), the heating temperature is 90-200 ℃, the stirring speed is about 200r/min, and the reaction time is 3-8 hours.
Further, the drying temperature of the precipitate in the step (6) is 50-70 ℃, and the drying time is 3-7 hours.
Further, the calcination temperature in step (7) is 300-700 ℃ and the calcination time is 3-7 hours.
Further, the step (8) of regulating the growth conditions of the carbon nanotubes comprises regulating the carbon source, the carrier gas composition, the reactor, the reaction temperature and the like.
Further, the carbon source comprises methane, carbon monoxide, ethylene and propylene.
Further, the carrier gas composition comprises a carbon source, hydrogen and nitrogen.
Further, in the step (8), the reactor is a fixed bed or a fluidized bed, and the reaction temperature is 500-1000 ℃.
The catalyst with a lamellar structure is prepared by adopting a one-step synthesis method, the main component of the lamellar structure is magnesium oxide, aluminum oxide or a mixture of the magnesium oxide and the aluminum oxide, and one or more of transition metal active centers Fe, Co and Ni are uniformly dispersed in the lamellar structure. The growth rate of the carbon nano tube is controlled from the angle of reaction kinetics by regulating and controlling the growth process parameters of the carbon nano tube, thereby realizing the growth of the carbon nano tube with different shapes, such as aggregation state, array beam shape and horizontal growth. The array bunched carbon nano tube and the horizontally grown carbon nano tube prepared by the invention are not wound, are easy to purify and disperse, can be applied to the fields of composite materials, lithium batteries, supercapacitors, biosensors and the like, and have wide application prospects.
Drawings
FIG. 1 is a scanning electron micrograph of a horizontally grown carbon nanotube.
FIG. 2 is a scanning electron micrograph of bundled carbon nanotubes in an array at different magnifications (a is a 30-magnification photograph, b is a 500-magnification photograph, c is a 1000-magnification photograph, and d is a 2000-magnification photograph).
FIG. 3 is a scanning electron micrograph of horizontally grown carbon nanotubes at low magnification (a is a 2000-magnification photograph, and b is a 5000-magnification photograph).
FIG. 4 is a high-power scanning electron micrograph of horizontally grown carbon nanotubes.
FIG. 5 is a scanning electron micrograph of the agglomerated carbon nanotube at a low magnification (a is a 2000-magnification photograph, and b is a 5000-magnification photograph).
FIG. 6 is a high-power scanning electron micrograph of the agglomerated carbon nanotubes.
Detailed Description
The method takes nitrate and ammonia water as main raw materials, water and ethylene glycol as solvents, and adopts a one-step precipitation method to prepare a lamellar structure containing a transition metal active center, wherein active components account for 0.1-30% of the total components, and the raw materials react for 3-8 hours at the reaction temperature of 90-200 ℃. The catalyst with a lamellar structure is obtained by filtering, washing and calcining. The invention is further illustrated by the following examples:
example 1:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. 23.51g of ferric nitrate, 49.75g of magnesium nitrate and 1.04g of ammonium molybdate are respectively weighed and added into the mixed solution, 96g of ammonia water is added, and the mixture is continuously stirred and heated to the reaction temperature of 110 ℃ and the reaction time is 4 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain light yellow precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace at 400 ℃ for 3 hours.
Example 2:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. 23.51g of ferric nitrate, 72.79g of aluminum nitrate and 1.23g of ammonium molybdate are respectively weighed and added into the mixed solution, 96g of ammonia water is added, and the mixture is continuously stirred and heated to the reaction temperature of 140 ℃ and the reaction time is 5 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain light pink precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 3 hours at 450 ℃.
Example 3:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. Respectively weighing 20.02g of cobalt nitrate, 72.79g of aluminum nitrate and 1.23g of ammonium molybdate, adding into the mixed solution, adding 96g of ammonia water, continuously stirring and heating to the reaction temperature of 150 ℃, and reacting for 6 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain light pink precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 3 hours at 450 ℃.
Example 4:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. 17.33g of ferric nitrate, 4.45g of cobalt nitrate, 49.75g of magnesium nitrate and 1.04g of ammonium molybdate are respectively weighed and added into the mixed solution, 96g of ammonia water is added, and the mixture is continuously stirred and heated to the reaction temperature of 130 ℃ for 5 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 4 hours at the temperature of 400 ℃.
Example 5:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. 17.33g of ferric nitrate, 4.45g of cobalt nitrate, 72.79g of aluminum nitrate and 1.23g of ammonium molybdate are respectively weighed and added into the mixed solution, 96g of ammonia water is added, and the mixture is continuously stirred and heated to the reaction temperature of 140 ℃ for 6 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 4 hours at 450 ℃.
Example 6:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. Respectively weighing 13.35g of cobalt nitrate, 6.65g of nickel nitrate, 72.79g of aluminum nitrate and 1.23g of ammonium molybdate, adding the cobalt nitrate, the nickel nitrate, the aluminum nitrate and the ammonium molybdate into the mixed solution, adding 96g of ammonia water, continuously stirring and heating to the reaction temperature of 160 ℃, and reacting for 8 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 4 hours at 500 ℃.
Example 7:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. 15.68g of ferric nitrate, 6.65g of nickel nitrate, 49.75g of magnesium nitrate and 1.04g of ammonium molybdate are respectively weighed and added into the mixed solution, 96g of ammonia water is added, and the mixture is continuously stirred and heated to the reaction temperature of 150 ℃ for 8 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 4 hours at 500 ℃.
Example 8:
300mL of ethylene glycol and 300mL of purified water are mixed and poured into a reaction kettle, and the mixture is stirred uniformly at room temperature. 15.68g of ferric nitrate, 4.87g of cobalt nitrate, 33.17g of magnesium nitrate, 24.26g of aluminum nitrate and 1.11g of ammonium molybdate are respectively weighed and added into the mixed solution, 96g of ammonia water is added, and the mixture is continuously stirred and heated to the reaction temperature of 140 ℃ and the reaction time is 6 hours. Cooling, filtering, washing the filter cake twice with absolute ethyl alcohol and purified water, and drying at 70 deg.C for 5 hr to obtain precipitate. The catalyst is obtained by calcining the catalyst in a muffle furnace for 4 hours at 450 ℃.
Example 9:
0.5g of the catalyst prepared in example 1 was placed in a fixed bed reactor having a diameter of 100mm and a length of 1000mm, nitrogen as a carrier gas, hydrogen as a reducing gas, and ethylene as a carbon source. Heating to 650 ℃ under the nitrogen atmosphere, introducing hydrogen to reduce for 10min, closing a hydrogen valve, introducing ethylene, wherein the total flow is 1500sccm, and the reaction time is 30 min. The grown carbon nano tube is in a powder shape in a macroscopic view, and the microscopic appearance is the carbon nano tube horizontally grown along the surface of the catalyst lamellar structure. FIG. 1 shows a scanning electron micrograph of the carbon nanotubes grown in this example.
Example 10:
1g of the catalyst prepared in example 3 was placed in a fluidized bed reactor having a diameter of 50mm and a length of 1100mm, with nitrogen as a carrier gas, hydrogen as a reducing gas, and propylene as a carbon source. Heating to 680 ℃ under the nitrogen atmosphere, introducing hydrogen to reduce for 5min, and introducing propylene, wherein the flow ratio of the hydrogen to the ethylene is 1:5, the total flow is 2000sccm, and the reaction time is 30 min. The grown carbon nano tube is in a tea shape in a macroscopic view and is in an array state in a microscopic shape. FIG. 2 shows the SEM photographs of the carbon nanotubes grown in this example at different magnifications.
Example 11:
0.5g of the catalyst prepared in example 5 was placed in a fixed bed reactor having a diameter of 100mm and a length of 1000mm, with nitrogen as a carrier gas, hydrogen as a reducing gas, and propylene as a carbon source. Heating to 680 ℃ under the nitrogen atmosphere, introducing hydrogen, reducing for 5min, closing a hydrogen gas valve, introducing propylene, wherein the total flow is 1200sccm, and the reaction time is 60 min. The grown carbon nano tube is in a powder shape in a macroscopic view, and is in a horizontally grown carbon nano tube in a microscopic shape. FIG. 3 shows a scanning electron micrograph of the carbon nanotubes grown in this example. FIG. 4 shows a high-power scanning electron micrograph of the carbon nanotubes grown in this example.
Example 12:
1g of the catalyst prepared in example 7 was placed in a fluidized bed reactor having a diameter of 50mm and a length of 1100mm, nitrogen as a carrier gas, hydrogen as a reducing gas, and ethylene as a carbon source. Raising the temperature to 650 ℃ under the nitrogen atmosphere, introducing hydrogen and ethylene, wherein the flow ratio is 1:3, the total flow is 2000sccm, and the reaction time is 40 min. The grown carbon nano tube is in a small granular shape in a macroscopic view, and is in an agglomerated state in a microscopic shape. FIG. 5 shows a scanning electron micrograph of the carbon nanotubes grown in this example. FIG. 6 shows a high-power scanning electron micrograph of the carbon nanotubes grown in this example.
Claims (3)
1. A preparation method of a carbon nano tube with controllable appearance is characterized by comprising the following steps:
mixing 300mL of ethylene glycol and 300mL of purified water, pouring the mixture into a reaction kettle, stirring the mixture uniformly at room temperature, respectively weighing 23.51g of ferric nitrate, 49.75g of magnesium nitrate and 1.04g of ammonium molybdate, adding the mixture into the mixed solution, adding 96g of ammonia water, continuously stirring and heating the mixture to a reaction temperature of 110 ℃, reacting for 4 hours, cooling and filtering the mixture, washing the obtained filter cake twice by using absolute ethyl alcohol and purified water respectively, drying the filter cake for 5 hours at 70 ℃ to obtain a light yellow precipitate, and calcining the light yellow precipitate for 3 hours at 400 ℃ in a muffle furnace to obtain a catalyst;
putting 0.5g of the catalyst in a fixed bed reactor with the diameter of 100mm and the length of 1000mm, taking nitrogen as carrier gas, hydrogen as reducing gas and ethylene as carbon source, heating to 650 ℃ in nitrogen atmosphere, introducing hydrogen for reduction for 10min, closing a hydrogen valve, introducing ethylene, controlling the total flow to be 1500sccm, reacting for 30min, and enabling the grown carbon nano tube to be in a powder shape in a macroscopic view and to be in a carbon nano tube horizontally grown along the surface of the catalyst lamellar structure in a microscopic shape.
2. A preparation method of a carbon nano tube with controllable appearance is characterized by comprising the following steps:
mixing 300mL of ethylene glycol and 300mL of purified water, pouring the mixture into a reaction kettle, stirring the mixture evenly at room temperature, respectively weighing 17.33g of ferric nitrate, 4.45g of cobalt nitrate, 72.79g of aluminum nitrate and 1.23g of ammonium molybdate, adding the mixture into the mixed solution, adding 96g of ammonia water, continuously stirring and heating the mixture to the reaction temperature of 140 ℃, reacting for 6 hours, cooling and filtering the mixture, washing the obtained filter cake twice by absolute ethyl alcohol and purified water respectively, drying the filter cake for 5 hours at 70 ℃ to obtain a precipitate, and calcining the precipitate for 4 hours at 450 ℃ in a muffle furnace to obtain a catalyst;
putting 0.5g of the obtained catalyst in a fixed bed reactor with the diameter of 100mm and the length of 1000mm, taking nitrogen as carrier gas, hydrogen as reducing gas and propylene as carbon source, heating to 680 ℃ in nitrogen atmosphere, introducing hydrogen, reducing for 5min, closing a hydrogen gas valve, introducing propylene, ensuring that the total flow is 1200sccm, the reaction time is 60min, and the grown carbon nano tube is in a powder shape in a macroscopic view and is in a horizontally grown carbon nano tube in a microscopic shape.
3. A preparation method of a carbon nano tube with controllable appearance is characterized by comprising the following steps:
mixing 300mL of ethylene glycol and 300mL of purified water, pouring the mixture into a reaction kettle, stirring the mixture evenly at room temperature, respectively weighing 15.68g of ferric nitrate, 6.65g of nickel nitrate, 49.75g of magnesium nitrate and 1.04g of ammonium molybdate, adding 96g of ammonia water into the mixed solution, continuously stirring and heating the mixture to the reaction temperature of 150 ℃, reacting for 8 hours, cooling and filtering the mixture, washing a filter cake twice by absolute ethyl alcohol and purified water respectively, drying the filter cake for 5 hours at 70 ℃ to obtain a precipitate, and calcining the precipitate for 4 hours at 500 ℃ in a muffle furnace to obtain a catalyst;
putting 1g of the obtained catalyst in a fluidized bed reactor with the diameter of 50mm and the length of 1100mm, wherein nitrogen is used as a carrier gas, hydrogen is used as a reducing gas, and ethylene is used as a carbon source; heating to 650 ℃ in the nitrogen atmosphere, introducing hydrogen and ethylene, wherein the flow ratio is 1:3, the total flow is 2000sccm, the reaction time is 40min, the grown carbon nano tube is in a macroscopic particle shape, and the microscopic morphology is an agglomerated carbon nano tube.
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