CN103058172A - 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 the 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 be in conjunction with the characteristic of these two kinds of carbon nanomaterials, designing more preferably, carbon nano-composite material has extremely important value and significance.
At present, the method for 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 that the precursor-graphite oxide with carbon nanotube and Graphene carries out simple mechanically mixing in solution, and then reduction-oxidation graphite, become the hybrid composite of carbon nanotube and reduced graphene, but in such matrix material, only rely on the physical connection effect between carbon nanotube and the Graphene, 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 with 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 defectives in the growth of carbon nanotube on oxidized graphite flake, growth restriction, the preparation of related load catalyzer also are difficult to regulation and control, and this is also so that the performance of prepared carbon nanotube-graphene composite material and practical application limited space.In addition, the mixed catalyst that directly prepares 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 defective of Graphene is more, and 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 the carbon nano tube network, chemical gaseous phase depositing process by original position grows high-quality Graphene, remove after the 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 kind of preparation method of carbon nanotube-graphene composite material is characterized in that this preparation method carries out as follows:
1) the homodisperse carbon nano tube suspension of preparation in deionized water or organic solvent, wherein the quality percentage composition of carbon nanotube is 0.01～2%;
2) add the magnesia catalyst of 1～10 times of carbon nanotube quality in the above-mentioned carbon nano tube suspension, evenly mix, form uniform and stable mixture suspension;
3) said mixture suspension is separated with the method for filtering, drying, 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) with the mix powder of above-mentioned carbon nanotube and magnesia catalyst, the film of the independent support that perhaps obtains is placed in the rare gas element, in 500～600 ° of C calcinings;
5) sample after will calcining continues to be warming up to 800～1000 ° of C, passes into carbon source, carries out high temperature chemical vapor deposition, and the time is 5 minutes to 2 hours;
The product that 6) will carry out after the chemical vapour deposition is dissolved in the acid, removes magnesia catalyst; After super-dry, obtain carbon nanotube-graphene composite material or Composite Paper.
Magnesia catalyst of the present invention prepares the catalyst prod that is of a size of 5～10000nm by the compound that contains magnesium elements, and the compound that contains magnesium elements comprises magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, sal epsom, magnesium acetate and magnesiumcarbonate.
Carbon nanotube of the present invention is one or more in the Single Walled Carbon Nanotube of the vermiculite array multi-walled carbon nano-tubes of agglomerate multi-walled carbon nano-tubes, purification of primary agglomerate multi-walled carbon nano-tubes, primary overlength array multi-walled carbon nano-tubes, purification and purification.
Used organic solvent is one or several the mixing in ethanol, n-formyl sarcolysine base pyrrolidone, nitrogen nitrogen N,N-DIMETHYLACETAMIDE, nitrogen dimethylformamide and the ionic liquid in the step 1) of the present invention.
The carbon source that passes in the 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 the adsorption and desorption material of electrochemical energy storage materials, catalyzer preparation.
The present invention has following advantage and high-lighting effect: 1. whole technological process is very easy, and is with low cost, easily mass-produced.2. the Graphene growth in situ forms multistage carbon nano-composite material in carbon nano tube network.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 of electrochemical energy storage materials, catalyzer preparation.
Description of drawings
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 among the present invention, and concrete preparation process is as described below:
1) the homodisperse carbon nano tube suspension of preparation in deionized water or organic solvent, wherein the quality percentage composition of carbon nanotube is 0.01～2%; Used organic solvent is one or several in ethanol, n-formyl sarcolysine base pyrrolidone, nitrogen nitrogen N,N-DIMETHYLACETAMIDE, nitrogen dimethylformamide and the ionic liquid; The carbon nanotube that adds 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) add the magnesia catalyst of 1～10 times of carbon nanotube quality in the above-mentioned carbon nano tube suspension, evenly mix, form uniform and stable mixture suspension; Described magnesia catalyst is by easy ultra-sonic 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, sal epsom, magnesium acetate and magnesiumcarbonate;
3) said mixture suspension is separated with the method for filtering, drying, 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) with the mix powder of above-mentioned carbon nanotube and magnesia catalyst, the film of the independent support that perhaps obtains is placed in the rare gas element, in 500～600 ° of C calcinings;
5) sample after will calcining continues to be warming up to 800～1000 ° of C, passes into carbon source, carries out high temperature chemical vapor deposition, and 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.The hydro carbons carbon source can be arene, such as benzene,toluene,xylene, vinylbenzene, naphthalene, anthracene and their mixture etc.; The hydro carbons carbon source also can be non-arene, such as methane, ethane, propane, ethene, propylene, acetylene and their mixture etc.; The oxygen containing organic compound of carbon containing is as carbon source, such as mixture of methyl alcohol, ethanol, phenylcarbinol, acetone, formaldehyde, acetaldehyde and above-mentioned substance etc.
The product that 6) will carry out after the chemical vapour deposition is dissolved in the acid, removes magnesia catalyst; After super-dry, obtain carbon nanotube-graphene composite material or Composite Paper.
In the carbon nanotube-graphene composite material or Composite Paper of aforesaid method preparation, 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, amplifies easily.The below will the present invention is further illustrated by several each and every one specific embodiments:
Embodiment 1:
5.0g magnesium hydroxide and 5.0g segmented copolymer P123 ultra-sonic dispersion in the 1L deionized water, are obtained the magnesium oxide powder product of particle diameter before and after～1000nm after the spraying drying.The vermiculite array multi-walled carbon nano-tubes later of purifying is dispersed in the ionic liquid, and the quality percentage composition of configuration carbon nanotube accounts for 0.6% carbon nano tube suspension 50g in solution.Add 1.0g magnesium oxide powder catalyzer in above-mentioned suspension, stirring forms both mixture suspension.The said mixture suspension filtered is separated, form the multi-walled carbon nano-tubes of purification and the powder-product that the graphen catalyst uniform particles is mixed.This mixed powder was put in the nitrogen of 550 ° of C calcining 1 hour, and then was warming up to 900 ° of C, pass into methane and carried out chemical vapor deposition 20 minutes as carbon source.It is in 14% the hydrochloric acid soln that the product that obtains is immersed in the quality percentage composition, removes the magnesia catalyst particle, as shown in Figure 2, thus the multi-walled carbon nano-tubes-graphene composite material that obtains purifying.Among Fig. 3, further the high power transmission electron microscope shows, the Graphene growth in situ is in carbon nanotube, and forming firmly, carbon nanotube contacts with the Graphene interface.
Embodiment 2:
In the 2L deionized water, filtration drying obtains size distribution at the magnesium oxide powder of 50～200nm size with the direct ultra-sonic dispersion of 2.0g magnesium oxide particle.Primary agglomerate multi-wall carbon nano-tube tube particle is dispersed in the ethanol, and the quality percentage composition of configuration carbon nanotube accounts for 2.0% agglomerate carbon nanotube particulate suspension 50g in solution.Add the 1.0g magnesium oxide powder to mentioned solution, stirring forms mixture suspension.The said mixture suspension filtered is separated, obtain the mixed uniformly powder-product of agglomerate carbon nanotube and magnesia catalyst.This powder-product was put in the nitrogen of 500 ° of C calcining 1 hour, and then continued to be warming up to 900 ° of C, pass into ethene and carried out chemical vapor deposition 2 hours as carbon source.The powder-product that obtains is immersed in the hydrochloric acid soln of quality percentage composition 14%, removes the magnesia catalyst particle, thereby obtain agglomerate carbon nanotube-graphene composite material.
Embodiment 3:
Use high-power ultrasonic rod ultra-sonic dispersion in the 1L deionized water 1.0g magnesium oxide particle and 5.0g segmented copolymer F127, filtration drying obtains size distribution at the bitter earth nano particle of 10～100nm.The Single Walled Carbon Nanotube of purifying is dispersed in the n-formyl sarcolysine base pyrrolidone, and the quality percentage composition that disposes homodisperse carbon nanotube accounts for 0.05% carbon nano tube suspension 50g in solution.Add the 0.2g magnesium oxide particle to above-mentioned suspension, mix and form mixture suspension.With the said mixture suspension filtered, form the film of independent support.This film was put in the argon gas of 600 ° of C calcining 1 hour, and then was warming up to 800 ° of C, pass into propine and carried out chemical vapor deposition 5 minutes.The film product that obtains is immersed in the hydrochloric acid soln of quality percentage composition 14%, removes the magnesia catalyst particle, as shown in Figure 3, thereby obtain the matrix material of the flexible Single Walled Carbon Nanotube of having of independent film forming-Graphene paper.
Embodiment 4:
The 4.6g magnesium nitrate is dispersed in the 0.5L deionized water, then add 3.0g segmented copolymer P123, stirred 2 hours, form the solution of thermal spray, then mist projection granulating under 450 ° of C, the particle that spraying obtains was processed 1 hour under 500 ° of C, obtained the magnesium oxide particle of 300～2000nm size.Primary overlength array multi-walled carbon nano-tubes is dispersed in the nitrogen dimethylformamide, and the quality percentage composition that disposes homodisperse carbon nanotube is 0.01% carbon nano tube suspension 20g.Add the 0.02g magnesium oxide particle in above-mentioned suspension, stirring forms mixture suspension.With the said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 500 ° of C calcining 1 hour, and then continued 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, carried out chemical vapor deposition 30 minutes.The film product that obtains is immersed in the salpeter solution of quality percentage composition 5%, removes the magnesia catalyst particle, thereby obtain the matrix material of overlength array carbon nano tube-Graphene paper.
Embodiment 5:
Prepare the magnesium oxide particle of 1000～3000nm size take magnesium basic carbonate as raw material with the method for hydro-thermal reaction.The agglomerate multi-walled carbon nano-tubes of purifying is dispersed in the n-formyl sarcolysine base pyrrolidone, and the quality percentage composition that disposes homodisperse carbon nanotube is 1% carbon nano tube suspension 20g in solution.Add 0.2g magnesia catalyst particle in above-mentioned carbon nano tube suspension, stirring forms mixture suspension.With the 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 calcining 1 hour, and then was warming up to 1000 ° of C, pass into the gas mixture of methane, ethane and propane (volume ratio 1:1:1) as carbon source, carried out chemical vapor deposition 10 minutes.The powder-product that obtains is immersed in the hydrochloric acid soln of quality percentage composition 14%, removes the magnesia catalyst particle, thereby obtain carbon nanotube-graphene composite material.
Embodiment 6:
In the 1L deionized water, filtration drying obtains size distribution at the bitter earth nano particle of 10～100nm with 1.0g magnesium oxide particle and 5.0g segmented copolymer F127 ultra-sonic dispersion.To be dispersed in the n-formyl sarcolysine base pyrrolidone with the overlength array multi-walled carbon nano-tubes that rare nitric acid was washed, the quality percentage composition that disposes homodisperse carbon nanotube is 0.05% carbon nano tube suspension 50g in solution.Add the 0.1g magnesium oxide particle in above-mentioned suspension, stirring forms mixture suspension.With the said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 550 ° of C calcining 1 hour, and then continued to be warming up to 900 ° of C, pass into propylene as carbon source, carried out chemical vapor deposition 30 minutes.The film sample that obtains is steeped in the hydrochloric acid soln of quality percentage composition 14%, remove the magnesia catalyst particle, thereby obtain the matrix material of overlength carbon nano pipe-Graphene paper.As shown in Figure 5, the Graphene growth in situ is in the array carbon nano tube network of overlength.
Embodiment 7:
In the 1L deionized water, filtration drying obtains size distribution at the bitter earth nano particle of 10～100nm with 1.0g magnesium oxide particle and 3.0g segmented copolymer F127 ultra-sonic dispersion.The overlength array multi-walled carbon nano-tubes that to wash with rare nitric acid and the vermiculite array multi-walled carbon nano-tubes of purification are dispersed in the n-formyl sarcolysine base pyrrolidone, and the quality percentage composition that disposes homodisperse total carbon nanotube is 0.02% carbon nano tube suspension 100g.Add 0.12g magnesia catalyst particle in above-mentioned suspension, stirring forms mixture suspension.The said mixture suspension filtered is separated, form the film of independent support.This film was put in the argon gas of 550 ° of C calcining 1 hour, and then was warming up to 900 ° of C, pass into methane and carry out chemical vapor deposition as carbon source.The film product that obtains is steeped in the hydrochloric acid soln of quality percentage composition 14%, remove the magnesia catalyst particle, thereby obtain mixing the matrix material of carbon nanotube-Graphene paper.As shown in Figure 6, scanning electronic microscope shows that overlength carbon nano pipe and short vermiculite array carbon nano tube form multistage reticulated structure, and Graphene then is grown in these networks.
Embodiment 8:
The 50g magnesium chloride is dispersed in the 0.5L deionized water, then adds 10.0g segmented copolymer P123, stirred 2 hours, form the solution of thermal spray, and under 200 ° of C mist projection granulating, with the spraying particle under 500 ° of C, processed 1 hour, obtain the magnesium oxide particle of 5000～10000nm size.To be dispersed in the nitrogen dimethylformamide with the vermiculite array multi-walled carbon nano-tubes that rare nitric acid was washed, the quality percentage composition that disposes homodisperse carbon nanotube is 0.5% carbon nano tube suspension 40g.Add the 3g magnesium oxide particle in above-mentioned suspension, stirring forms mixture suspension.With the said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 500 ° of C calcining 1 hour, and then continued 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, carried out chemical vapor deposition 30 minutes.The film product that obtains is immersed in the salpeter solution of quality percentage composition 5%, removes the magnesia catalyst particle, thereby obtain the matrix material of array carbon nano tube-Graphene paper.
Embodiment 9:
10g magnesium acetate ultra-sonic dispersion in the 1L deionized water, is then added 5.0g segmented copolymer F127, stirred 2 hours, form the solution of thermal spray, and under 450 ° of C mist projection granulating, the particle of spraying was processed 1 hour under 500 ° of C, obtain～magnesium oxide particle of 1000nm size.To be dispersed in the n-formyl sarcolysine base pyrrolidone with the overlength array multi-walled carbon nano-tubes that rare nitric acid was washed, the quality percentage composition that disposes homodisperse carbon nanotube is 0.03% carbon nano tube suspension 50g.Add the 0.1g magnesium oxide particle in above-mentioned suspension, stirring forms mixture suspension.With the said mixture suspension filtered, obtain the film product of independent support.This film product is put in the nitrogen of 550 ° of C calcining 1 hour, and then continued 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, carried out chemical vapor deposition 1 hour.The film product that obtains is immersed in the hydrochloric acid soln of quality percentage composition 5%, removes the magnesia catalyst particle, thereby obtain overlength array carbon nano tube-Graphene paper.
Embodiment 10:
The 100g magnesium acetate is dispersed in the 1L deionized water, then adds 10.0g polyvinyl alcohol thickening material, stirred 2 hours, form the solution of thermal spray, and under 180 ° of C mist projection granulating, with the spraying particle under 500 ° of C, processed 1 hour, obtain the magnesium oxide particle of 8000～10000nm size.The agglomerate multi-walled carbon nano-tubes of purifying is dispersed in the nitrogen nitrogen N,N-DIMETHYLACETAMIDE, and the quality percentage composition that disposes homodisperse carbon nanotube is 0.1% carbon nano tube suspension 10g.In above-mentioned suspension, add the 0.5g magnesium oxide particle, stir, form mixture suspension.The said mixture suspension filtered is separated, 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 calcining 1 hour, and then continued to be warming up to 850 ° of C, pass into the acetone steam as carbon source, carried out chemical vapor deposition 1 hour.The powder-product that obtains is immersed in the salpeter solution of quality percentage composition 5%, removes the magnesia catalyst particle, thereby obtain the matrix material of carbon nanotube-Graphene.
Embodiment 11:
0.5g magnesium oxide particle and 3.0g segmented copolymer F127 ultra-sonic dispersion in the 0.5L deionized water, were processed 24 hours in the water-bath of 94 ° of C, and filtration drying obtains size distribution at the bitter earth nano particle of 10～50nm.To be dispersed in the n-formyl sarcolysine base pyrrolidone with the overlength array multi-walled carbon nano-tubes that rare nitric acid was washed, the quality percentage composition that disposes homodisperse carbon nanotube is 0.01% carbon nano tube suspension 100g in solution.Add the 0.1g magnesium oxide particle in above-mentioned suspension, stirring forms mixture suspension.With the said mixture suspension filtered, form the film of independent support.This film is put in the nitrogen of 550 ° of C calcining 1 hour, and then continued to be warming up to 900 ° of C, pass into the mixed vapour of formaldehyde and acetaldehyde (volume ratio 1:1) as carbon source, carried out chemical vapor deposition 30 minutes.The film sample that obtains is steeped in the hydrochloric acid soln of quality percentage composition 14%, remove the magnesia catalyst particle, thereby obtain the matrix material of overlength carbon nano pipe-Graphene paper.
Claims (9)
1. the preparation method of a carbon nanotube-graphene composite material is characterized in that this preparation method carries out as follows:
1) the homodisperse carbon nano tube suspension of preparation in deionized water or organic solvent, wherein the quality percentage composition of carbon nanotube is 0.01～2%;
2) add the magnesia catalyst of 1～10 times of carbon nanotube quality in the above-mentioned carbon nano tube suspension, evenly mix, form uniform and stable mixture suspension;
3) said mixture suspension is separated with the method for filtering, drying, 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) with the mix powder of above-mentioned carbon nanotube and magnesia catalyst, the film of the independent support that perhaps obtains is placed in the rare gas element, in 500～600 ° of C calcinings;
5) sample after will calcining continues to be warming up to 800～1000 ° of C, passes into carbon source, carries out high temperature chemical vapor deposition, and the time is 5 minutes to 2 hours;
The product that 6) will carry out after the chemical vapour deposition is dissolved in the acid, removes magnesia catalyst; After super-dry, obtain carbon nanotube-graphene composite material or Composite Paper.
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 prepares the catalyst prod that is of a size of 5～10000nm by the compound that contains magnesium elements, and the compound that contains magnesium elements comprises magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium nitrate, sal epsom, 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 that adopts is one or more in the Single Walled Carbon Nanotube of the vermiculite array multi-walled carbon nano-tubes of agglomerate multi-walled carbon nano-tubes, purification of primary agglomerate multi-walled carbon nano-tubes, primary overlength array multi-walled carbon nano-tubes, 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: used organic solvent is one or several the mixing in ethanol, n-formyl sarcolysine base pyrrolidone, nitrogen nitrogen N,N-DIMETHYLACETAMIDE, nitrogen dimethylformamide and the ionic liquid in the step 1).
5. 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 source that passes in the step 5) comprises 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 carbon nanotube-graphene composite material claimed in claim 1, it is characterized in that: this matrix material is as the application of solid support material, transparent conductive film material, strongthener, electro-conductive material and the adsorption and desorption material of electrochemical energy storage materials, catalyzer preparation.
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