CN103058172B - Preparation method of carbon nanometer tube-graphene composite material - Google Patents
Preparation method of carbon nanometer tube-graphene composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon nanometer tube-graphene composite material, and the method comprises the following steps of: directly mixing uniformly dispersed carbon nanometer tubes and a catalyst for graphene uniformly, causing the graphene to grow in situ in a carbon nanometer tube network by means of chemical vapor deposition, and removing the catalyst for the graphene after purification treatment to obtain the carbon nanometer tube-graphene composite material. The carbon nanometer tube-graphene composite material gives consideration to the characteristics of both the carbon nanometer tube and the graphene, and has significant application values in the aspects such as electrochemical energy storage, catalyst preparation, a transparent electroconductive film, enhancement, electric conduction, and an adsorption material as well as a desorption material, and in addition the preparation method is simple in operation, low in cost and easy for industrial production and is an important preparation method of a nanometer carbon material.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube-graphene composite material, belong to the field of Nano-composite materials and application.
Background technology
Carbon nano-composite material is with a wide range of applications, especially in fields such as electrochemical energy storage, catalyzer preparation, transparent conductive film, electro-conductive material, strongthener, adsorption and desorption materials.Wherein, the carbon nanotube in carbon nanomaterial and Graphene have extremely excellent characteristic especially.Carbon nanotube has high length-to-diameter ratio, good conductive characteristic and physical strength, and Graphene has large specific surface area, and excellent conduction and mechanical property, can, in conjunction with the characteristic of these two kinds of carbon nanomaterials, design more preferably carbon nano-composite material and there is extremely important value and significance.
At present, the method of preparing the matrix material of taking into account carbon nanotube and Graphene characteristic adopts method (the Nano Lett.9 of physical mixed substantially, 1949-55, 2009), its primary process is the precursor-graphite oxide of carbon nanotube and Graphene to be carried out in solution to simple mechanically mixing, and then reduction-oxidation graphite, become the hybrid composite of carbon nanotube and reduced graphene, but in such matrix material, between carbon nanotube and Graphene, only rely on physical connection effect, be difficult to form good interface contact, therefore, the synergisticing performance of carbon nanotube and Graphene is greatly diminished.Utilize the method for growth in situ, can be by the catalyst cupport of carbon nanotube to oxidized graphite flake, carry out growth in situ, and after further reducing, also can prepare the matrix material (Adv.Mater.22 of carbon nanotube-Graphene, 3723-3728,2010), but, there are a lot of defects in the growth of carbon nanotube on oxidized graphite flake, growth restriction, the preparation of related load catalyzer is also difficult to regulation and control, and this also makes performance and the practical application limited space of prepared carbon nanotube-graphene composite material.In addition, the mixed catalyst of directly preparing carbon nanotube and Graphene, the way of recycling growth in situ, also can grow the matrix material (application number: CN201210141649.6) of carbon nanotube-Graphene, but the carbon nano tube growth that this method is prepared or limited, and the defect of Graphene is more, for realizing real application, the homogeneity of material and the control of process cost also need to strengthen.
Summary of the invention
The object of the invention be to provide a kind of cheapness can easy operation the preparation method of the carbon nanotube-graphene composite material with wide application prospect.The method is dispersed in the catalyzer of Graphene in carbon nano tube network, chemical gaseous phase depositing process by original position grows high-quality Graphene, after removing graphen catalyst, obtaining the matrix material of carbon nanotube-Graphene, is the carbon nano-composite material that a class has significant application value.
Technical scheme of the present invention is as follows:
A preparation method for carbon nanotube-graphene composite material, is characterized in that this preparation method carries out as follows:
1) in deionized water or organic solvent, prepare homodisperse carbon nano tube suspension, wherein the quality percentage composition of carbon nanotube is 0.01～2%;
2) to the magnesia catalyst that adds 1～10 times of carbon nanotube quality in above-mentioned carbon nano tube suspension, evenly mix, form uniform and stable mixture suspension;
3) said mixture suspension is separated by the method for filtering, dry, the carbon nanotube that obtains mixing and the mixed powder of magnesia catalyst, or obtain the film of carbon nanotube and magnesia catalyst independent support;
4) by the mix powder of above-mentioned carbon nanotube and magnesia catalyst, or the film of the independent support obtaining is placed in rare gas element, in 500～600 ° of C calcinings;
5) sample after calcining is continued to be warming up to 800～1000 ° of C, pass into carbon source, carry out high temperature chemical vapor deposition, the time is 5 minutes to 2 hours;
6) product having carried out after chemical vapour deposition is dissolved in acid, removes magnesia catalyst; After super-dry, obtain carbon nanotube-graphene composite material or Composite Paper.
Magnesia catalyst of the present invention is prepared the catalyst prod that is of a size of 5～10000nm by the compound that contains magnesium elements, the compound that contains magnesium elements comprises magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate and magnesiumcarbonate.
Carbon nanotube of the present invention is primary agglomerate multi-walled carbon nano-tubes, primary overlength array multi-walled carbon nano-tubes, the agglomerate multi-walled carbon nano-tubes of purification, one or more in the Single Walled Carbon Nanotube of the vermiculite array multi-walled carbon nano-tubes of purification and purification.
In step 1) of the present invention, organic solvent used is one or several the mixing in ethanol, nitrogen methyl-2-pyrrolidone, nitrogen nitrogen N,N-DIMETHYLACETAMIDE, nitrogen dimethylformamide and ionic liquid.
The carbon source passing in step 5) of the present invention comprises hydro carbons carbon source and the oxygen containing organic compound of carbon containing.Described hydro carbons carbon source adopts arene or non-aromatic hydro carbons.Described arene adopts benzene,toluene,xylene, vinylbenzene, naphthalene, anthracene or their mixture; Described non-aromatic hydro carbons adopts methane, ethane, propane, ethene, propylene, acetylene or their mixture.The oxygen containing organic compound of described carbon containing is methyl alcohol, ethanol, phenylcarbinol, acetone, formaldehyde, acetaldehyde or their mixture.
Carbon nanotube-graphene composite material of the present invention can be used as the application of solid support material, transparent conductive film material, strongthener, electro-conductive material and adsorption and desorption material prepared by electrochemical energy storage materials, catalyzer.
Tool of the present invention has the following advantages and high-lighting effect: 1. whole technological process is very easy, with low cost, easily mass-produced.2. Graphene growth in situ, in carbon nano tube network, forms multistage carbon nano-composite material.3. prepared carbon nanotube-graphene composite material has firm interface contact.4. prepared carbon nanotube-graphene composite material is taken into account the excellent properties of carbon nanotube and Graphene.5. prepared carbon nanotube-graphene composite material can be applied to the aspects such as solid support material, transparent conductive film material, strongthener, electro-conductive material and adsorption and desorption material prepared by electrochemical energy storage materials, catalyzer.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of carbon nanotube-graphene composite material.
Fig. 2 is the low power transmission electron microscope photo of the vermiculite array multi-walled carbon nano-tubes-graphene composite material of purification.
Fig. 3 is the high power transmission electron microscope photo of the vermiculite array multi-walled carbon nano-tubes-graphene composite material of purification.
Fig. 4 is the optical camera photo of Single Walled Carbon Nanotube-Graphene Composite Paper.
Fig. 5 is the electron scanning micrograph of overlength array multi-walled carbon nano-tubes-graphene composite material.
Fig. 6 is the electron scanning micrograph of the vermiculite array multi-walled carbon nano-tubes-graphene composite material of overlength array multi-walled carbon nano-tubes/purification.
Embodiment
Fig. 1 is preparation technology's schema of carbon nanotube-graphene composite material in the present invention, and concrete preparation process is as described below:
1) in deionized water or organic solvent, prepare homodisperse carbon nano tube suspension, wherein the quality percentage composition of carbon nanotube is 0.01～2%; Organic solvent used is one or several in ethanol, nitrogen methyl-2-pyrrolidone, nitrogen nitrogen N,N-DIMETHYLACETAMIDE, nitrogen dimethylformamide and ionic liquid; The carbon nanotube adding is primary agglomerate multi-walled carbon nano-tubes, primary overlength array multi-walled carbon nano-tubes, the agglomerate multi-walled carbon nano-tubes of purification, the vermiculite array multi-walled carbon nano-tubes of purification, one or several in the Single Walled Carbon Nanotube of purification;
2) to the magnesia catalyst that adds 1～10 times of carbon nanotube quality in above-mentioned carbon nano tube suspension, evenly mix, form uniform and stable mixture suspension; Described magnesia catalyst is by easy ultrasonic dispersion, hydro-thermal or mist projection granulating method prepare from the various compounds that contain magnesium elements, it is of a size of the size of 5～10000nm, and these compounds that contain magnesium elements comprise magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate and magnesiumcarbonate;
3) said mixture suspension is separated by the method for filtering, dry, the carbon nanotube that obtains mixing and the mixed powder of magnesia catalyst, or obtain the carbon nanotube of independent support and the film of magnesia catalyst;
4) by the mix powder of above-mentioned carbon nanotube and magnesia catalyst, or the film of the independent support obtaining is placed in rare gas element, in 500～600 ° of C calcinings;
5) sample after calcining is continued to be warming up to 800～1000 ° of C, pass into carbon source, carry out high temperature chemical vapor deposition, the time is 5 minutes to 2 hours; The carbon source of high temperature chemical vapor deposition comprises hydro carbons and the oxygen containing organic compound of other carbon containing.Hydro carbons carbon source can be arene, as benzene,toluene,xylene, vinylbenzene, naphthalene, anthracene and their mixture etc.; Hydro carbons carbon source can be also non-arene, as methane, ethane, propane, ethene, propylene, acetylene and their mixture etc.; The oxygen containing organic compound of carbon containing is as carbon source, as mixture of methyl alcohol, ethanol, phenylcarbinol, acetone, formaldehyde, acetaldehyde and above-mentioned substance etc.
6) product having carried out after chemical vapour deposition is dissolved in acid, removes magnesia catalyst; After super-dry, obtain carbon nanotube-graphene composite material or Composite Paper.
In carbon nanotube-graphene composite material or Composite Paper prepared by aforesaid method, carbon nanotube has firm interface with Graphene and contacts, and has taken into account both excellent properties, has good conductive characteristic and high specific surface area.The method is simple and easy to operate, easily amplifies.To come by several each and every one specific embodiments that the present invention is further illustrated below:
Embodiment 1:
By 5.0g magnesium hydroxide with 5.0g segmented copolymer P123 is ultrasonic is dispersed in 1L deionized water, after spraying is dry, obtain the magnesium oxide powder product of particle diameter before and after～1000nm.The vermiculite array multi-walled carbon nano-tubes later of purifying is dispersed in ionic liquid, and the quality percentage composition of configuration carbon nanotube accounts for 0.6% carbon nano tube suspension 50g in solution.In above-mentioned suspension, add 1.0g magnesium oxide powder catalyzer, stir and form both mixture suspension.Said mixture suspension filtered is separated, form the multi-walled carbon nano-tubes of purification and the powder-product that graphen catalyst uniform particles is mixed.This mixed powder is put in the nitrogen of 550 ° of C and calcines 1 hour, be then warming up to 900 ° of C, pass into methane and carry out chemical vapor deposition 20 minutes as carbon source.It is in 14% hydrochloric acid soln that the product obtaining is immersed in to quality percentage composition, removes magnesia catalyst particle, as shown in Figure 2, thereby obtains the multi-walled carbon nano-tubes-graphene composite material of purifying.In Fig. 3, further high power transmission electron microscope shows, Graphene growth in situ, in carbon nanotube, forms firmly carbon nanotube and contacts with Graphene interface.
Embodiment 2:
By direct ultrasonic being dispersed in 2L deionized water of 2.0g magnesium oxide particle, filtration drying, obtains size distribution at the magnesium oxide powder of 50～200nm size.Primary agglomerate multi-wall carbon nano-tube tube particle is dispersed in ethanol, and the quality percentage composition of configuration carbon nanotube accounts for 2.0% agglomerate carbon nanotube particulate suspension 50g in solution.To above-mentioned solution, add 1.0g magnesium oxide powder, stir and form mixture suspension.Said mixture suspension filtered is separated, obtain the mixed uniformly powder-product of agglomerate carbon nanotube and magnesia catalyst.This powder-product is put in the nitrogen of 500 ° of C and calcines 1 hour, then continue to be warming up to 900 ° of C, pass into ethene and carry out chemical vapor deposition 2 hours as carbon source.The powder-product obtaining is immersed in the hydrochloric acid soln of quality percentage composition 14%, removes magnesia catalyst particle, thereby obtain agglomerate carbon nanotube-graphene composite material.
Embodiment 3:
By 1.0g magnesium oxide particle and 5.0g segmented copolymer F127, with ultrasonic being dispersed in 1L deionized water of high-power ultrasonic rod, filtration drying, obtains size distribution at the bitter earth nano particle of 10～100nm.The Single Walled Carbon Nanotube of purifying is dispersed in nitrogen methyl-2-pyrrolidone, and the quality percentage composition that configures homodisperse carbon nanotube accounts for 0.05% carbon nano tube suspension 50g in solution.To above-mentioned suspension, add 0.2g magnesium oxide particle, mix and form mixture suspension.By said mixture suspension filtered, form the film of independent support.This film is put in the argon gas of 600 ° of C and calcines 1 hour, be then warming up to 800 ° of C, pass into propine and carry out chemical vapor deposition 5 minutes.The film product obtaining is immersed in the hydrochloric acid soln of quality percentage composition 14%, removes magnesia catalyst particle, as shown in Figure 3, thereby obtain the matrix material of the flexible Single Walled Carbon Nanotube-Graphene of having of independent film forming paper.
Embodiment 4:
4.6g magnesium nitrate is dispersed in 0.5L deionized water, then add 3.0g segmented copolymer P123, stir 2 hours, form the solution of thermal spray, then mist projection granulating under 450 ° of C, the particle that spraying is obtained is processed 1 hour under 500 ° of C, obtains the magnesium oxide particle of 300～2000nm size.Primary overlength array multi-walled carbon nano-tubes is dispersed in nitrogen dimethylformamide to the carbon nano tube suspension 20g that the quality percentage composition that configures homodisperse carbon nanotube is 0.01%.In above-mentioned suspension, add 0.02g magnesium oxide particle, stir and form mixture suspension.By said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 500 ° of C and calcines 1 hour, then continue to be warming up to 800 ° of C, pass into the mixture steam of benzene, toluene and p-Xylol (volume ratio 2:1:1) as carbon source, carry out chemical vapor deposition 30 minutes.The film product obtaining is immersed in the salpeter solution of quality percentage composition 5%, removes magnesia catalyst particle, thereby obtain the matrix material of overlength array carbon nano tube-Graphene paper.
Embodiment 5:
By the method for hydro-thermal reaction, take magnesium basic carbonate and prepare the magnesium oxide particle of 1000～3000nm size as raw material.The agglomerate multi-walled carbon nano-tubes of purification is dispersed in nitrogen methyl-2-pyrrolidone, and the quality percentage composition that configures homodisperse carbon nanotube is 1% carbon nano tube suspension 20g in solution.In above-mentioned carbon nano tube suspension, add 0.2g magnesia catalyst particle, stir and form mixture suspension.By said mixture suspension filtered, isolate the agglomerate multi-walled carbon nano-tubes carbon of purification and the mixed powder of magnesia catalyst.This mixed powder is put in the argon gas of 500 ° of C and calcines 1 hour, be then warming up to 1000 ° of C, pass into the gas mixture of methane, ethane and propane (volume ratio 1:1:1) as carbon source, carry out chemical vapor deposition 10 minutes.The powder-product obtaining is immersed in the hydrochloric acid soln of quality percentage composition 14%, removes magnesia catalyst particle, thereby obtain carbon nanotube-graphene composite material.
Embodiment 6:
By 1.0g magnesium oxide particle with 5.0g segmented copolymer F127 is ultrasonic is dispersed in 1L deionized water, filtration drying, obtains size distribution at the bitter earth nano particle of 10～100nm.The overlength array multi-walled carbon nano-tubes of washing with rare nitric acid is dispersed in nitrogen methyl-2-pyrrolidone, and the quality percentage composition that configures homodisperse carbon nanotube is 0.05% carbon nano tube suspension 50g in solution.In above-mentioned suspension, add 0.1g magnesium oxide particle, stir and form mixture suspension.By said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 550 ° of C and calcines 1 hour, then continue to be warming up to 900 ° of C, pass into propylene as carbon source, carry out chemical vapor deposition 30 minutes.The film sample bubble obtaining, in the hydrochloric acid soln of quality percentage composition 14%, is removed to magnesia catalyst particle, thereby obtained the matrix material of overlength carbon nano pipe-Graphene paper.As shown in Figure 5, Graphene growth in situ is in the array carbon nano tube network of overlength.
Embodiment 7:
By 1.0g magnesium oxide particle with 3.0g segmented copolymer F127 is ultrasonic is dispersed in 1L deionized water, filtration drying, obtains size distribution at the bitter earth nano particle of 10～100nm.The vermiculite array multi-walled carbon nano-tubes of the overlength array multi-walled carbon nano-tubes of washing with rare nitric acid and purification is dispersed in nitrogen methyl-2-pyrrolidone to the carbon nano tube suspension 100g that the quality percentage composition that configures homodisperse total carbon nanotube is 0.02%.In above-mentioned suspension, add 0.12g magnesia catalyst particle, stir and form mixture suspension.Said mixture suspension filtered is separated, the film of formation independent support.This film is put in the argon gas of 550 ° of C and calcines 1 hour, be then warming up to 900 ° of C, pass into methane and carry out chemical vapor deposition as carbon source.The film product bubble obtaining, in the hydrochloric acid soln of quality percentage composition 14%, is removed to magnesia catalyst particle, thereby obtained mixing the matrix material of carbon nanotube-Graphene paper.As shown in Figure 6, scanning electronic microscope demonstration, overlength carbon nano pipe and shorter vermiculite array carbon nano tube form multistage reticulated structure, and Graphene is grown in these networks.
Embodiment 8:
50g magnesium chloride is dispersed in 0.5L deionized water, then adds 10.0g segmented copolymer P123, stir 2 hours, form the solution of thermal spray, and under 200 ° of C mist projection granulating, the particle of spraying is processed 1 hour under 500 ° of C, obtain the magnesium oxide particle of 5000～10000nm size.The vermiculite array multi-walled carbon nano-tubes of washing with rare nitric acid is dispersed in nitrogen dimethylformamide to the carbon nano tube suspension 40g that the quality percentage composition that configures homodisperse carbon nanotube is 0.5%.In above-mentioned suspension, add 3g magnesium oxide particle, stir and form mixture suspension.By said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 500 ° of C and calcines 1 hour, then continue to be warming up to 850 ° of C, pass into the mixture steam of vinylbenzene, naphthalene and anthracene (volume ratio 2:1:1) as carbon source, carry out chemical vapor deposition 30 minutes.The film product obtaining is immersed in the salpeter solution of quality percentage composition 5%, removes magnesia catalyst particle, thereby obtain the matrix material of array carbon nano tube-Graphene paper.
Embodiment 9:
Be dispersed in 1L deionized water 10g magnesium acetate is ultrasonic, then add 5.0g segmented copolymer F127, stir 2 hours, form the solution of thermal spray, and under 450 ° of C mist projection granulating, the particle of spraying is processed 1 hour under 500 ° of C to the magnesium oxide particle of obtain～1000nm size.The overlength array multi-walled carbon nano-tubes of washing with rare nitric acid is dispersed in nitrogen methyl-2-pyrrolidone to the carbon nano tube suspension 50g that the quality percentage composition that configures homodisperse carbon nanotube is 0.03%.In above-mentioned suspension, add 0.1g magnesium oxide particle, stir and form mixture suspension.By said mixture suspension filtered, obtain the film product of independent support.This film product is put in the nitrogen of 550 ° of C and calcines 1 hour, then continue to be warming up to 900 ° of C, pass into the mixture steam of methyl alcohol, ethanol and phenylcarbinol (volume ratio 5:2:1) as carbon source, carry out chemical vapor deposition 1 hour.The film product obtaining is immersed in the hydrochloric acid soln of quality percentage composition 5%, removes magnesia catalyst particle, thereby obtain overlength array carbon nano tube-Graphene paper.
Embodiment 10:
100g magnesium acetate is dispersed in 1L deionized water, then adds 10.0g polyvinyl alcohol thickening material, stir 2 hours, form the solution of thermal spray, and under 180 ° of C mist projection granulating, the particle of spraying is processed 1 hour under 500 ° of C, obtain the magnesium oxide particle of 8000～10000nm size.The agglomerate multi-walled carbon nano-tubes of purifying is dispersed in nitrogen nitrogen N,N-DIMETHYLACETAMIDE to the carbon nano tube suspension 10g that the quality percentage composition that configures homodisperse carbon nanotube is 0.1%.In above-mentioned suspension, add 0.5g magnesium oxide particle, stir, form mixture suspension.By the separation of said mixture suspension filtered, obtain the mixed powder of agglomerate multi-walled carbon nano-tubes and magnesia catalyst.This powder-product is put in the nitrogen of 500 ° of C and calcines 1 hour, then continue to be warming up to 850 ° of C, pass into acetone steam as carbon source, carry out chemical vapor deposition 1 hour.The powder-product obtaining is immersed in the salpeter solution of quality percentage composition 5%, removes magnesia catalyst particle, thereby obtain the matrix material of carbon nanotube-Graphene.
Embodiment 11:
By 0.5g magnesium oxide particle with 3.0g segmented copolymer F127 is ultrasonic is dispersed in 0.5L deionized water, in the water-bath of 94 ° of C, to process 24 hours, filtration drying, obtains size distribution at the bitter earth nano particle of 10～50nm.The overlength array multi-walled carbon nano-tubes of washing with rare nitric acid is dispersed in nitrogen methyl-2-pyrrolidone, and the quality percentage composition that configures homodisperse carbon nanotube is 0.01% carbon nano tube suspension 100g in solution.In above-mentioned suspension, add 0.1g magnesium oxide particle, stir and form mixture suspension.By said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 550 ° of C and calcines 1 hour, then continue to be warming up to 900 ° of C, pass into the mixed vapour of formaldehyde and acetaldehyde (volume ratio 1:1) as carbon source, carry out chemical vapor deposition 30 minutes.The film sample bubble obtaining, in the hydrochloric acid soln of quality percentage composition 14%, is removed to magnesia catalyst particle, thereby obtained the matrix material of overlength carbon nano pipe-Graphene paper.
Claims (9)
1. a preparation method for carbon nanotube-graphene composite material, is characterized in that this preparation method carries out as follows:
1) in deionized water or organic solvent, prepare homodisperse carbon nano tube suspension, wherein the quality percentage composition of carbon nanotube is 0.01～2%;
2) to the magnesia catalyst that adds 1～10 times of carbon nanotube quality in above-mentioned carbon nano tube suspension, evenly mix, form uniform and stable mixture suspension;
3) said mixture suspension is separated by the method for filtering, dry, the carbon nanotube that obtains mixing and the mixed powder of magnesia catalyst, or obtain the film of carbon nanotube and magnesia catalyst independent support;
4) by the mix powder of above-mentioned carbon nanotube and magnesia catalyst, or the film of the independent support obtaining is placed in rare gas element, in 500～600 ℃ of calcinings;
5) sample after calcining is continued to be warming up to 800～1000 ℃, pass into carbon source, carry out high temperature chemical vapor deposition, the time is 5 minutes to 2 hours;
6) product having carried out after chemical vapour deposition is dissolved in acid, removes magnesia catalyst; After super-dry, obtain carbon nanotube-graphene composite material.
2. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 1, it is characterized in that: described magnesia catalyst is prepared the catalyst prod that is of a size of 5～10000nm by the compound that contains magnesium elements, the compound that contains magnesium elements comprises magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate and magnesiumcarbonate.
3. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 1, it is characterized in that: the carbon nanotube adopting is primary agglomerate multi-walled carbon nano-tubes, primary overlength array multi-walled carbon nano-tubes, the agglomerate multi-walled carbon nano-tubes of purification, one or more in the Single Walled Carbon Nanotube of the vermiculite array multi-walled carbon nano-tubes of purification and purification.
4. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 1, it is characterized in that: step 1) in organic solvent used be one or several the mixing in ethanol, nitrogen methyl-2-pyrrolidone, nitrogen nitrogen N,N-DIMETHYLACETAMIDE, nitrogen dimethylformamide and ionic liquid.
5. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 1, it is characterized in that: step 5) in the carbon source that passes into comprise hydro carbons carbon source and the oxygen containing organic compound of carbon containing.
6. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 5, it is characterized in that: described hydro carbons carbon source adopts arene or non-aromatic hydro carbons.
7. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 6, it is characterized in that described arene adopts benzene,toluene,xylene, vinylbenzene, naphthalene, anthracene or their mixture; Described non-aromatic hydro carbons adopts methane, ethane, propane, ethene, propylene, acetylene or their mixture.
8. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 5, it is characterized in that: the oxygen containing organic compound of described carbon containing is methyl alcohol, ethanol, phenylcarbinol, acetone, formaldehyde, acetaldehyde or their mixture.
9. according to the preparation method of a kind of carbon nanotube-graphene composite material claimed in claim 1, it is characterized in that: the application of the solid support material that this matrix material is prepared as electrochemical energy storage materials, catalyzer, transparent conductive film material, strongthener, electro-conductive material and adsorption and desorption material.
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| CN114836645B (en) * | 2022-04-06 | 2022-11-01 | 西北工业大学 | Preparation method of carbon nanotube-graphene hybrid porous preform with designable configuration |
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