CN113192762B - Carbon nanotube composite material with hierarchical structure and preparation method thereof - Google Patents
Carbon nanotube composite material with hierarchical structure and preparation method thereof Download PDFInfo
- Publication number
- CN113192762B CN113192762B CN202110534272.XA CN202110534272A CN113192762B CN 113192762 B CN113192762 B CN 113192762B CN 202110534272 A CN202110534272 A CN 202110534272A CN 113192762 B CN113192762 B CN 113192762B
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- nano tube
- composite material
- hierarchical structure
- gas flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A carbon nanotube composite having a hierarchical structure, characterized in that: carbon of the hierarchical structureThe nano tube is composed of a thin carbon nano tube with the tube diameter of 5-10 nm and a thick carbon nano tube with the tube diameter of about 200nm, the thick carbon nano tube has a branch structure, and the thin carbon nano tube is spirally wound on the surface of the thick carbon nano tube. The carbon nano tube composite material with the hierarchical structure improves the electrochemical performance of the material, and the power density of the material reaches 73.2 Wh.kg‑1When the current density is 1A/g, the specific capacitance is 252.6F/g, which is 1.4 times of that of a single branch carbon nano tube with a large tube diameter, so that the high-capacitance carbon nano tube has excellent cycling stability, and still keeps extremely high capacitance retention rate after being cycled for 10000 times.
Description
Technical Field
The invention relates to the technical field of carbon nanotubes, in particular to a carbon nanotube composite material with a hierarchical structure and a preparation method thereof.
Background
With the ever-developing requirements of implantable electronic products and flexible electronic products on energy technology, supercapacitors are receiving wide attention due to their unique properties. Especially in the field of flexible electronic products, the super capacitor has outstanding advantages compared with other energy storage devices, and can meet special requirements of flexible electronic devices. The development of electrode materials with graded and diversified nanostructures to improve the performance of supercapacitors is a hot point of research in recent years. Among them, carbon nanomaterials are widely used in electrode materials to prepare supercapacitors based on their high conductivity and high specific surface area. In porous carbon, the structure with extremely small pore size is reported to not only have little effect on improving the performance of the supercapacitor, but also reduce the rate performance of the device. On the other hand, when the carbon nano material with the hierarchical structure is used as the electrode material of the super capacitor, the energy density and the power density can be greatly improved. However, the preparation of carbon nanomaterials with hierarchical structures for application in supercapacitors still faces no small challenges. The spongy three-dimensional porous material prepared by taking the graphene as the base material has the advantages of good pore structure, excellent conductivity, light weight and the like, and is an excellent candidate material for constructing the electrode material of the supercapacitor with the hierarchical structure. However, the three-dimensional material using graphene as a matrix has a major disadvantage that strong pi-pi interaction exists between graphene layers, so that graphene can be stacked again to obtain graphite. In addition, the synthesis process of the electrode material with the graphene-based hierarchical structure is high in cost and difficult to scale up.
Carbon nanotubes have excellent electrical conductivity and electron transport properties, and are considered to be a promising electrode material for supercapacitors. However, the energy density level of carbon nanotube based supercapacitors still needs to be increased to meet the application requirements. Therefore, making up for the shortages of single structure electrode materials by designing composite electrodes constructed by multiple structures is an important way to improve the performance of supercapacitors.
Disclosure of Invention
The invention aims to provide a carbon nanotube composite material with a hierarchical structure. The composite material composed of two carbon nanotubes with different tube diameters obviously improves the electrochemical performance of the material.
The invention also aims to provide a preparation method of the carbon nano tube composite material.
The purpose of the invention is realized by the following technical scheme:
a carbon nanotube composite having a hierarchical structure, characterized in that: the carbon nano tube with the hierarchical structure is composed of a thin carbon nano tube with the tube diameter of 5-10 nm and a thick carbon nano tube with the tube diameter of about 200nm, the thick carbon nano tube has a branch structure, and the thin carbon nano tube is spirally wound on the surface of the thick carbon nano tube.
The invention discloses a three-dimensional carbon nano composite material with a hierarchical structure, namely, a carbon nano tube with a smaller tube diameter is spirally wound on the surface of a branched carbon nano tube with a larger tube diameter to form the composite material. The spirally wound thin carbon nano tube has a higher specific surface area, the adsorbed electric charge amount is improved, the carbon nano tube with a larger tube diameter has a branched structure, a charge transmission channel is increased, and the two have synergistic effect, so that the ion transfer speed can be obviously accelerated, the ion transfer distance is shortened, and the electrochemical performance is improved.
Furthermore, the carbon nanotube composite material with the hierarchical structure is prepared by using ethylene as a carbon source and Ni/MgO as a catalyst through two heating treatments.
The two-step heating treatment is to place the catalyst at the upstream end of the ethylene airflow, keep the temperature for 15-25 min at 740-760 ℃, then transfer the catalyst to the downstream end of the ethylene airflow, and keep the temperature for 15-25 min at 945-955 ℃.
The preparation method of the carbon nano tube composite material with the hierarchical structure is characterized by comprising the following steps: firstly preparing a Ni/MgO catalyst, placing the Ni/MgO catalyst in an upstream region of airflow of a tubular furnace, introducing ethylene, carrying out first heating treatment, then moving the Ni/MgO catalyst to the downstream region of the airflow of the tubular furnace, continuously introducing the ethylene, carrying out second heating treatment, then cooling to room temperature under the protection of argon, collecting a product, and purifying.
Further, the temperature of the first heating treatment is 740-760 ℃, the temperature is kept for 15-25 min, the temperature of the second heating treatment is 945-955 ℃, and the temperature is kept for 15-25 min.
Preferably, the temperature of the first heating treatment is 750 ℃, and the temperature is kept for 20min, and the temperature of the second heating treatment is 950 ℃, and the temperature is kept for 20 min.
The flow rate of the ethylene is 100-120 mL/min.
The method comprises the steps of firstly placing a catalyst at the upstream of a carbon source airflow, allowing an ethylene airflow to contact and react with a prepared large-particle Ni/MgO catalyst at a lower temperature to change the growth direction of the generated carbon nano tube so as to form a branched structure and generate a thick-diameter branched carbon nano tube, reducing the particle size of the Ni/MgO catalyst after the Ni/MgO catalyst is subjected to high temperature and reaction with the carbon source, dispersing the Ni/MgO catalyst into a structure with a larger size and attaching the structure to the surface of the thick-diameter carbon nano tube, secondly moving the generated thick-diameter branched carbon nano tube and catalyst components downwards to the downstream of the airflow, catalyzing ethylene reaction again at a higher temperature to generate the carbon nano tube with a small tube diameter, and finally spirally winding the carbon nano tube with the small tube diameter on the surface of the thick-diameter carbon nano tube.
Further, the Ni/MgO catalyst is Ni (NO)3)2And Mg (NO)3)2Dissolving in deionized water to obtain solution A, adding sodium hydroxide solution to obtain solution B, refluxing, filtering, washing, drying, calcining in air, and calcining in H2And keeping the temperature for 30-40 min under the mixed atmosphere of Ar and the mixture.
Further, Ni is contained in the solution A2+And Mg2+The total concentration of the sodium hydroxide solution is 0.2mol/L, the concentration of the sodium hydroxide solution is 2.5mol/L, and the volume ratio of the sodium hydroxide solution to the deionized water is 1: 4.
Further, the reflux temperature was 95 ℃ and the reflux time was 12 hours.
Further, the calcination temperature in the air is 600-620 ℃, the calcination time is 2 hours, and the calcination time is H2The gas flow of Ar and the gas flow of Ar are respectively 100-120 mL/min and 300-360 mL/min, H2And Ar in a gas flow ratio of 1: 3.
The invention firstly carries out reflux treatment, then calcines in air environment, and then carries out H with a certain gas flow proportion2In a system for preparing the carbon nano tube with the thick tube diameter by taking ethylene as a carbon source, the Ni/MgO catalyst prepared in the mixed atmosphere of Ar and the Ni/MgO effectively changes the growth direction of the nano tube in the reaction process of the carbon source and the catalyst, thereby forming a branched structure.
Further, the purification is that the collected product is washed by hydrochloric acid solution, sodium hydroxide solution and deionized water in sequence and then dried in vacuum at 80 ℃.
Furthermore, the concentration of the hydrochloric acid solution is 4-5 mol/L, and the concentration of the sodium hydroxide solution is 12-13 mol/L.
Most particularly, the carbon nanotube composite material with the hierarchical structure and the preparation method thereof are characterized by comprising the following steps:
the method comprises the following steps: preparation of the catalyst
Mixing Ni (NO)3)2And Mg (NO)3)2Dissolving in deionized water to obtain Ni2+And Mg2+The concentration sum of the sodium hydroxide solution and deionized water is 0.2mol/L, 2.5mol/L sodium hydroxide solution is added to obtain mixed solution, the volume ratio of the sodium hydroxide solution to the deionized water is 1:4, the mixed solution is refluxed for 12 hours at 95 ℃, then filtered, a filtered product is washed by the deionized water, is frozen and dried, then the product is divided into medium parts by air, is calcined for 2 hours at 600-620 ℃, and then H is added2Continuously calcining for 30-40 min at the same temperature in the mixed atmosphere of Ar to obtain a Ni nanoparticle product supported by MgO as a substrate, namely the Ni/MgO catalyst, wherein H is2The gas flow of Ar and the gas flow of Ar are respectively 100-120 mL/min and 300-360 mL/min, H2And Ar in a gas flow ratio of 1: 3;
step two: preparation of hierarchical carbon nanotube composite material
Placing a Ni/MgO catalyst in an upstream area of a tubular furnace gas flow, introducing ethylene according to the gas flow of 100-120 mL/min, heating the tubular furnace to 740-760 ℃, keeping for 15-25 min, then moving the Ni/MgO catalyst to the downstream area of the tubular furnace gas flow, heating the tubular furnace to 940-960 ℃, keeping for 15-25 min, then cooling to room temperature under the protection of Ar, and collecting a product;
step three: purification of
And washing the product with 4-5 mol/L hydrochloric acid solution, 12-13 mol/L sodium hydroxide solution and deionized water in sequence, and then drying in vacuum at 80 ℃.
The invention has the following technical effects:
the carbon nano tube with the superfine tube diameter is spirally wound, the specific surface area of the carbon nano tube with a branch structure with a larger tube diameter is increased, the adsorbed electric charge amount is increased, the circulation path of charge transfer is increased by the branch structure with the larger tube diameter, and the large tube diameter and the branch structure have synergistic effect, so that the charge transfer rate is increased, the charge transfer distance is shortened, the electrochemical performance of the material is improved, and the power density reaches 73.2 Wh-kg-1When the current density is 1A/g, the specific capacitance is 252.6F/g, which is 1.4 times of that of a single branch carbon nano tube with a large tube diameter, the high-capacitance carbon nano tube has excellent circulation stability, and after circulation for 10000 times, the high-capacitance carbon nano tube still keeps extremely high capacitanceAnd (4) rate.
In the carbon nanotube composite material with the superfine pipe diameter and the branched structure, which is prepared by the method, of the carbon nanotube spirally wound, the pipe diameter of the carbon nanotube with the superfine pipe diameter is 5-10 nm, the pipe diameter of the carbon nanotube with the branched structure with the thick pipe diameter is about 200nm, the pipe diameter distribution uniformity is good, and the excellent electrochemical performance and the performance stability of the material are ensured.
Drawings
FIG. 1: the structure of the carbon nanotube composite material with the hierarchical structure prepared by the invention is shown schematically.
FIG. 2: the scanning electron microscope image of the carbon nano tube composite material with the hierarchical structure prepared by the invention is shown.
FIG. 3: the transmission electron microscope image of the carbon nano tube composite material with the hierarchical structure prepared by the invention is shown.
FIG. 4: the X-ray diffraction pattern of the carbon nano tube composite material with the hierarchical structure is prepared by the invention.
FIG. 5: the energy density-power density curve chart of the carbon nano tube composite material with the hierarchical structure prepared by the invention.
FIG. 6: the carbon nano tube composite material with the hierarchical structure prepared by the invention has the capacitance retention rate of more than 10000 times of circulation.
FIG. 7: the comparison graph of the performance of the carbon nanotube composite material with the hierarchical structure prepared by the invention and the carbon nanotube with single thick-diameter and branched structure prepared by the comparative example 1 is shown.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A carbon nanotube composite material with a hierarchical structure and a preparation method thereof are carried out according to the following steps:
the method comprises the following steps: preparation of the catalyst
Mixing Ni (NO)3)2And Mg (NO)3)2Dissolving in deionized water to obtain Ni2+And Mg2+The concentration sum of the sodium hydroxide solution and deionized water is 1:4, then the mixed solution is refluxed for 12H at 95 ℃, then filtered, the filtered product is washed by the deionized water, freeze-dried, then the product is divided into medium air, calcined for 2H at 600 ℃, and then the product is subjected to H2Calcining for 35min at the same temperature under the mixed atmosphere of Ar to obtain a Ni nanoparticle product supported by MgO as a substrate, namely the Ni/MgO catalyst, wherein H is2The gas flow of Ar and the gas flow of Ar are respectively 100mL/min and 300-330 mL/min, H2And Ar in a flow rate of 1: 3;
step two: preparation of hierarchical carbon nanotube composite material
Placing a Ni/MgO catalyst in an upstream area of a tubular furnace gas flow, introducing ethylene according to the gas flow of 100mL/min, heating the tubular furnace to 750 ℃, keeping for 20min, then moving the Ni/MgO catalyst to the downstream area of the tubular furnace gas flow, heating the tubular furnace to 950 ℃, keeping for 20min, then cooling to room temperature under the protection of Ar, and collecting a product;
step three: purification of
The product was washed successively with 5mol/L hydrochloric acid solution, 13mol/L sodium hydroxide solution and deionized water, and then dried under vacuum at 80 ℃.
Fig. 1 shows that the carbon nanotube with a hierarchical structure and a larger diameter has a branched structure, and the carbon nanotube with a smaller diameter spirally winds on the surface of the branched carbon nanotube with a larger diameter from an enlarged position in the figure.
Fig. 2 and 3 are a scanning electron microscope image and a transmission electron microscope image of the carbon nanotube composite material prepared by the present invention, respectively, and it can be seen from the images that the carbon nanotube with thicker tube diameter has an obvious branched structure, the tube diameter is about 200nm, the tube diameter of the carbon nanotube with thinner tube diameter is 5-10 nm, and the carbon nanotube is spirally wound on the surface of the carbon nanotube with thicker tube diameter and branched shape.
As shown in FIG. 5, the hierarchical structure carbon nano prepared by the present inventionThe power density of the rice-tube composite material reaches 73.2 Wh-kg-1It should be noted that, since the value span of the abscissa function density is relatively large, the abscissa is usually simplified in the art as shown in fig. 5 for convenience of drawing the graph.
The result of cyclic voltammetry test on the carbon nanotube composite material with the hierarchical structure prepared by the invention is shown in fig. 6, and after 10000 cycles of cyclic voltammetry test, the carbon nanotube composite material still maintains high capacitance retention rate and has excellent electrochemical cyclic stability.
Comparative example 1
A preparation method of carbon nanotubes comprises the following steps:
the method comprises the following steps: preparing a Ni/MgO catalyst by adopting the process of the first step in the example 1;
step two: putting the Ni/MgO catalyst in a tubular furnace, introducing ethylene according to the gas flow of 100mL/min, heating the tubular furnace to 750 ℃, keeping the temperature for 20min, then cooling to room temperature under the protection of Ar, and collecting a product;
step three: same as step three in example 1.
The product prepared in the comparative example 1 only has carbon nano tubes with a smaller tube diameter, and the carbon nano tubes with the tube diameter of 5-10 nm are not spirally wound on the surface with a larger tube diameter like the product prepared in the invention.
Through the performance comparison of the example 1 and the comparative example 1, the maximum energy density of the branched carbon nanotube composite material with the thin-tube diameter and the winding larger-tube diameter, which is prepared by the invention, is more than 1.4 times that of the comparative example 1.
The carbon nanotube composite material with the hierarchical structure prepared by the invention adopts 1mol/L sulfuric acid solution as electrolyte, the performance of the carbon nanotube composite material is detected, when the current density is 1A/g, the specific capacitance is 252.6F/g, and when the current density is increased to 10A/g, the specific capacitance is 176F/g which is far higher than that of the single thick-diameter branched carbon nanotube prepared in the comparative example 1, and the specific capacitance is shown in fig. 7.
Example 2
A carbon nanotube composite material with a hierarchical structure and a preparation method thereof are carried out according to the following steps:
the method comprises the following steps: preparation of the catalyst
Mixing Ni (NO)3)2And Mg (NO)3)2Dissolving in deionized water to obtain Ni2+And Mg2+The concentration sum of the sodium hydroxide solution and deionized water is 1:4, then the mixed solution is refluxed for 12H at 95 ℃, then filtered, the filtered product is washed by the deionized water, freeze-dried, then the product is divided into medium parts by air, calcined for 2H at 620 ℃, and then the product is subjected to H2Calcining for 40min at the same temperature under the mixed atmosphere of Ar to obtain a Ni nanoparticle product supported by MgO as a substrate, namely the Ni/MgO catalyst, wherein H is2And the gas flow rates of Ar are 110mL/min and 330mL/min respectively;
step two: preparation of hierarchical carbon nanotube composite material
Placing a Ni/MgO catalyst in an upstream area of a tubular furnace gas flow, introducing ethylene according to the gas flow of 110mL/min, heating the tubular furnace to 740 ℃, keeping for 25min, then moving the Ni/MgO catalyst to the downstream area of the tubular furnace gas flow, heating the tubular furnace to 940 ℃, keeping for 25min, then cooling to room temperature under the protection of Ar, and collecting a product;
step three: purification of
The product was washed successively with 4mol/L hydrochloric acid solution, 12mol/L sodium hydroxide solution and deionized water, and then dried under vacuum at 80 ℃.
Example 3
A carbon nanotube composite material with a hierarchical structure and a preparation method thereof are carried out according to the following steps:
the method comprises the following steps: preparation of the catalyst
Mixing Ni (NO)3)2And Mg (NO)3)2Dissolving in deionized water to obtain Ni2+And Mg2+The concentration sum of the sodium hydroxide solution and deionized water is 1:4, then the mixed solution is refluxed for 12h at 95 ℃, then filtered, the filtered product is washed by the deionized water, and after freeze drying, the product is separated in air at 600 ℃ to obtain a mixtureCalcining at deg.C for 2 hr, and calcining at H2Calcining for 30min at the same temperature under the mixed atmosphere of Ar to obtain a Ni nanoparticle product supported by MgO as a substrate, namely the Ni/MgO catalyst, wherein H is2And the gas flow of Ar is 120mL/min and 360mL/min respectively;
step two: preparation of hierarchical carbon nanotube composite material
Placing a Ni/MgO catalyst in an upstream area of a tubular furnace gas flow, introducing ethylene according to the gas flow of 120mL/min, heating the tubular furnace to 760 ℃, keeping for 15min, then moving the Ni/MgO catalyst to the downstream area of the tubular furnace gas flow, heating the tubular furnace to 960 ℃, keeping for 15min, then cooling to room temperature under the protection of Ar, and collecting a product;
step three: purification of
The product was washed successively with 4.5mol/L hydrochloric acid solution, 12.5mol/L sodium hydroxide solution and deionized water, and then dried under vacuum at 80 ℃.
Claims (7)
1. A preparation method of a carbon nano tube composite material with a hierarchical structure is characterized by comprising the following steps: firstly preparing a Ni/MgO catalyst, placing the Ni/MgO catalyst in an upstream area of airflow of a tubular furnace, introducing ethylene, carrying out first heating treatment, moving the Ni/MgO catalyst to the downstream area of the airflow of the tubular furnace, continuously introducing the ethylene, carrying out second heating treatment, cooling to room temperature under the protection of argon, collecting a product, and purifying, wherein the first heating treatment temperature is 740-760 ℃, the temperature is kept for 15-25 min, the second heating treatment temperature is 945-955 ℃, the temperature is kept for 15-25 min, the carbon nano tube with the hierarchical structure is composed of a fine carbon nano tube with the tube diameter of 5-10 nm and a coarse carbon nano tube with the tube diameter of about 200nm, the coarse carbon nano tube has a branched structure, and the fine carbon nano tube is spirally wound on the surface of the coarse carbon nano tube.
2. The method of claim 1, wherein the carbon nanotube composite material has a hierarchical structure, and the method comprises: the Ni/MgO catalyst is Ni (NO)3)2And Mg (NO)3)2Dissolving in deionized water to obtain solution A, and addingAdding sodium hydroxide solution to obtain solution B, refluxing, filtering, washing, drying, calcining in air, and adding H2And keeping the temperature for 30-40 min under the mixed atmosphere of Ar and the mixture.
3. The method of claim 2, wherein the carbon nanotube composite material has a hierarchical structure, and the method comprises: ni in the solution A2+And Mg2+ The total concentration of the sodium hydroxide solution is 0.2mol/L, the concentration of the sodium hydroxide solution is 2.5mol/L, and the volume ratio of the sodium hydroxide solution to the deionized water is 1: 4.
4. The method for preparing a carbon nanotube composite material having a hierarchical structure according to claim 2 or 3, wherein: the calcining temperature in the air is 600-620 ℃, the calcining time is 2H, and the calcining time is H2The gas flow of Ar and the gas flow of Ar are respectively 100-120 mL/min and 300-360 mL/min, H2And Ar in a gas flow ratio of 1: 3.
5. A method for preparing a carbon nanotube composite material having a hierarchical structure according to any one of claims 1 to 3, wherein: the purification is to wash the collected product with hydrochloric acid solution, sodium hydroxide solution and deionized water in turn, and then to dry the product in vacuum at 80 ℃.
6. The method of claim 4, wherein the carbon nanotube composite material has a hierarchical structure, and the method comprises: the purification is to wash the collected product with hydrochloric acid solution, sodium hydroxide solution and deionized water in turn, and then to dry the product in vacuum at 80 ℃.
7. A preparation method of a carbon nano tube composite material with a hierarchical structure is characterized by comprising the following steps:
the method comprises the following steps: preparation of the catalyst
Mixing Ni (NO3)2And Mg (NO3)2Dissolving in deionized water to obtain Ni2+And Mg2+The concentration sum of the sodium hydroxide solution and deionized water is 0.2mol/L, 2.5mol/L sodium hydroxide solution is added to obtain mixed solution, the volume ratio of the sodium hydroxide solution to the deionized water is 1:4, then the mixed solution is refluxed and filtered, a filtered product is washed by the deionized water and is frozen and dried, the product is calcined for 2 hours at the temperature of 600-620 ℃ in the air atmosphere, and then H is added2Continuously calcining for 30-40 min at the same temperature in the mixed atmosphere of Ar to obtain a Ni nanoparticle product supported by MgO as a substrate, namely the Ni/MgO catalyst, wherein H is2The gas flow of Ar and the gas flow of Ar are respectively 100-120 mL/min and 300-360 mL/min, H2And Ar in a gas flow ratio of 1: 3;
step two: preparation of hierarchical carbon nanotube composite material
Placing a Ni/MgO catalyst in an upstream area of a tubular furnace gas flow, introducing ethylene according to the gas flow of 100-120 mL/min, heating the tubular furnace to 740-760 ℃, keeping for 15-25 min, then moving the Ni/MgO catalyst to the downstream area of the tubular furnace gas flow, heating the tubular furnace to 940-960 ℃, keeping for 15-25 min, then cooling to room temperature under the protection of Ar, and collecting a product;
step three: purification of
Washing the product with hydrochloric acid solution, sodium hydroxide solution and deionized water in sequence, and then drying in vacuum at 80 ℃;
the carbon nano tube with the hierarchical structure is composed of a thin carbon nano tube with the tube diameter of 5-10 nm and a thick carbon nano tube with the tube diameter of about 200nm, the thick carbon nano tube has a branch structure, and the thin carbon nano tube is spirally wound on the surface of the thick carbon nano tube.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210552164.XA CN114883117B (en) | 2021-05-17 | 2021-05-17 | Preparation method of composite carbon nano tube |
| CN202110534272.XA CN113192762B (en) | 2021-05-17 | 2021-05-17 | Carbon nanotube composite material with hierarchical structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110534272.XA CN113192762B (en) | 2021-05-17 | 2021-05-17 | Carbon nanotube composite material with hierarchical structure and preparation method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210552164.XA Division CN114883117B (en) | 2021-05-17 | 2021-05-17 | Preparation method of composite carbon nano tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113192762A CN113192762A (en) | 2021-07-30 |
| CN113192762B true CN113192762B (en) | 2022-04-05 |
Family
ID=76981995
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110534272.XA Active CN113192762B (en) | 2021-05-17 | 2021-05-17 | Carbon nanotube composite material with hierarchical structure and preparation method thereof |
| CN202210552164.XA Active CN114883117B (en) | 2021-05-17 | 2021-05-17 | Preparation method of composite carbon nano tube |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210552164.XA Active CN114883117B (en) | 2021-05-17 | 2021-05-17 | Preparation method of composite carbon nano tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113192762B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922316A (en) * | 2014-01-03 | 2014-07-16 | 电子科技大学 | Foamed carbon nano tube material, preparation method, heat dissipation structure and determination method |
| CN106971859A (en) * | 2017-04-14 | 2017-07-21 | 同济大学 | A kind of carbon fiber/carbon nanotube flexible super capacitor electrode material and its preparation |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3755662B2 (en) * | 2002-12-04 | 2006-03-15 | 独立行政法人産業技術総合研究所 | Method for producing carbon nanotube |
| JP4378350B2 (en) * | 2003-03-20 | 2009-12-02 | チェオル−ジン リー | Large-scale synthesis of double-walled carbon nanotubes by vapor deposition |
| CN1207187C (en) * | 2003-07-18 | 2005-06-22 | 清华大学 | Purification method of carbon nano pipe and its device |
| KR100962171B1 (en) * | 2007-12-26 | 2010-06-10 | 제일모직주식회사 | Metal Nano Catalyst for Synthesizing Carbon Nanotube and Method for Preparing Carbon Nanotubes Using thereof |
| WO2010141130A1 (en) * | 2009-02-27 | 2010-12-09 | Lockheed Martin Corporation | Low temperature cnt growth using gas-preheat method |
| CN102267693B (en) * | 2011-07-06 | 2013-03-06 | 天津理工大学 | Low-temperature preparation method of carbon nanotube |
| CN102330069B (en) * | 2011-10-18 | 2013-03-06 | 天津理工大学 | Preparation method of carbon nano tube |
| CN102502580B (en) * | 2011-10-27 | 2014-08-27 | 清华大学 | Carbon nano tube array and preparation method thereof as well as application of carbon nano tube array in preparation of super capacitor |
| EP2841379A4 (en) * | 2012-04-23 | 2015-12-16 | Seerstone Llc | Carbon nanotubes having a bimodal size distribution |
| JP2016503751A (en) * | 2013-01-17 | 2016-02-08 | サウディ ベーシック インダストリーズ コーポレイション | Production of carbon nanotubes from carbon dioxide |
| US9926200B1 (en) * | 2014-03-26 | 2018-03-27 | Yazaki Corporation | Highly purified carbon nanotubes and method of their preparation |
| CN107597118B (en) * | 2017-09-01 | 2020-07-17 | 哈尔滨万鑫石墨谷科技有限公司 | Catalyst for preparing clustered carbon nanotubes, preparation method thereof and clustered carbon nanotubes |
| WO2021071453A2 (en) * | 2019-10-10 | 2021-04-15 | Gaziantep Universitesi Rektorlugu | Aluminum matrix hybrid composite with mgo and cnt exhibiting enhanced mechanical properties |
| AU2020102823A4 (en) * | 2020-10-16 | 2020-12-10 | Yancheng Institute Of Technology | Method for preparing carbon nanotube-porous carbon composite materials |
| KR102220563B1 (en) * | 2020-11-09 | 2021-02-25 | (주)케이에이치 케미컬 | Preparation method of branched carbon nanotubes with improved hydrophilicity |
-
2021
- 2021-05-17 CN CN202110534272.XA patent/CN113192762B/en active Active
- 2021-05-17 CN CN202210552164.XA patent/CN114883117B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922316A (en) * | 2014-01-03 | 2014-07-16 | 电子科技大学 | Foamed carbon nano tube material, preparation method, heat dissipation structure and determination method |
| CN106971859A (en) * | 2017-04-14 | 2017-07-21 | 同济大学 | A kind of carbon fiber/carbon nanotube flexible super capacitor electrode material and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113192762A (en) | 2021-07-30 |
| CN114883117A (en) | 2022-08-09 |
| CN114883117B (en) | 2023-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | A review of performance optimization of MOF‐derived metal oxide as electrode materials for supercapacitors | |
| Mustaqeem et al. | Rational design of metal oxide based electrode materials for high performance supercapacitors–A review | |
| Zhao et al. | Recent advances in metal-organic framework-based electrode materials for supercapacitors: A review | |
| Fan et al. | Carbon nanosheets: synthesis and application | |
| Wang et al. | Preparation of MnO2/carbon nanowires composites for supercapacitors | |
| Wang et al. | Dimensional optimization enables high-performance capacitive deionization | |
| Ju et al. | Prussian blue analogue derived low-crystalline Mn2O3/Co3O4 as high-performance supercapacitor electrode | |
| Zhang et al. | Metal organic frameworks-derived porous carbons/ruthenium oxide composite and its application in supercapacitor | |
| Gao et al. | Sulfur & nitrogen co-doped electrospun carbon nanofibers as freestanding electrodes for membrane capacitive deionization | |
| Chen et al. | Wood-derived scaffolds decorating with nickel cobalt phosphate nanosheets and carbon nanotubes used as monolithic electrodes for assembling high-performance asymmetric supercapacitor | |
| CN110517900A (en) | A kind of preparation method of supercapacitor N doping low temperature carbon nanofiber electrode material | |
| Zuo et al. | N-doped mesoporous thin carbon tubes obtained by exhaust directional deposition for supercapacitor | |
| CN110148524A (en) | A kind of nested type CeO2/ GO/AAO nano-array electrode material for super capacitor and preparation method thereof | |
| Zhang et al. | NiCo-MOF directed NiCoP and coconut shell derived porous carbon as high-performance supercapacitor electrodes | |
| Yang et al. | Co 3 O 4 nanocrystals derived from a zeolitic imidazolate framework on Ni foam as high-performance supercapacitor electrode material | |
| Jadhav et al. | Probing electrochemical charge storage of 3D porous hierarchical cobalt oxide decorated rGO in ultra-high-performance supercapacitor | |
| Zou et al. | Construction of polypyrrole nanotubes interconnected ZIFs-templated nickel-cobalt layered double hydroxide via varying the mass of ZIF-67 for supercapacitors with tunable performance | |
| Park et al. | Prospective synthesis approaches to emerging materials for supercapacitor | |
| Yan et al. | Hierarchical MnO2@ NiCo2O4@ Ti3SiC2/carbon cloth core-shell structure with superior electrochemical performance for all solid-state supercapacitors | |
| Wei et al. | Review of NiCo2S4 nanostructures and their composites used in supercapacitors | |
| Pathak et al. | Integrating V-doped CoP on Ti3C2Tx MXene-incorporated hollow carbon nanofibers as a freestanding positrode and MOF-derived carbon nanotube negatrode for flexible supercapacitors | |
| CN113192762B (en) | Carbon nanotube composite material with hierarchical structure and preparation method thereof | |
| Bi et al. | Stable copper tin sulfide nanoflower modified carbon quantum dots for improved supercapacitors | |
| Wang et al. | Co2SiO4/CoO heterostructure anchored on graphitized carbon derived from rice husks with hierarchical pore as electrode material for supercapacitor | |
| CN113643908B (en) | One kind (Ni, co) 3 S 4 CNT material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |