CN102530913A - Method for preparing graphene-carbon nano tube composite material - Google Patents
Method for preparing graphene-carbon nano tube composite material Download PDFInfo
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- CN102530913A CN102530913A CN2010106164967A CN201010616496A CN102530913A CN 102530913 A CN102530913 A CN 102530913A CN 2010106164967 A CN2010106164967 A CN 2010106164967A CN 201010616496 A CN201010616496 A CN 201010616496A CN 102530913 A CN102530913 A CN 102530913A
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Abstract
The invention discloses a method for preparing a graphene-carbon nano tube composite material. The method comprises the following steps of: 1, adding graphite oxide and carbon nano tubes treated by using acid into water, performing ultrasonic oscillation, and stirring to obtain a uniformly dispersed mixed solution; and 2, filtering the mixed solution, drying the solid, heating the dried solid to the temperature of between 1,000 and 1,200 DEG C at the velocity of 10 DEG C per minute under an inert gas environment, preserving the heat for 10 to 30 minutes, cooling to room temperature, and thus obtaining the graphene-carbon nano tube composite material. The method has the advantages of simple process and low cost.
Description
[technical field]
The present invention relates to a kind of nano carbon composite material, particularly relate to a kind of preparation method of graphene-carbon nano tube matrix material.
[background technology]
The strong K sea nurses of the peace moral of Univ Manchester UK (Andre K.Geim) etc. were prepared grapheme material in 2004, pay attention to widely because its particular structure and photoelectric property have received people.Mono-layer graphite is because its big specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.As: 1, HS, the Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm
2/ V*s); 4, high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of the big specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.
Carbon nanotube is (S.Iijima, Nature354,56 of from the thomel that arc process is produced, finding in 1991 (1991).It is a kind of tubular carbon molecule, and each carbon atom is taked sp on the pipe
2Hydridization combines with C-C each other, forms the polynuclear plane be made up of the hexagon skeleton as carbon nanotube; The length-to-diameter ratio of carbon nanotube is generally more than 1000: 1, and strength ratio is high 100 times with the intensity of volume steel, and weight but has only the latter's 1/6 to 1/7; Hardness and diamond are suitable, but have good snappiness, are the ideal high tensile strength fibrous materials, thereby are claimed " super fiber ".
Aspect the Nano Carbon structure, mostly research concentrates on the aspect that combines of metallic particles, organic molecule and carbon nanotube or Graphene.Be equivalent to the doping research of one dimension, zero dimension carbon material.The complex body that forms between the carbon class material mainly concentrates in the carbon nano-tube process, produced simultaneously other carbon allotropes.Research has zero dimension and unidimensional complex structure body---the nanometer beanpod of finding (Smith, g.W.et al.Nature 396,323 (1998)) in 1998 more widely.Up in March, 2008, Fujitsu Research Institute has delivered it in the success that obtains aspect the novel nano carbon complex structure body of self-organization formation joint carbon nanotube and Graphene in the 34th the comprehensive symposial of fullerene nanotube.Fujitsu Research Institute utilizes the chemical vapour deposition flop-in method, under 510 ℃ temperature, on the multi-walled carbon nano-tubes that neatly generates in vertical direction with respect to base plate, has formed the complex structure body that is formed to the graphite self-organization of tens layers by which floor.This is the bonded structure of non-atomic structure of Graphene vertical engagement of realizing carbon nanotube and the two-dirnentional structure of one-dimentional structure first.
Yet the higher and reduction Graphene of method complex process, the cost of traditional preparation process graphene-carbon nano tube matrix material uses toxic reagent such as Hydrazine Hydrate 80.
[summary of the invention]
Based on this, be necessary to provide a kind of technology simple, the preparation method of lower-cost graphene-carbon nano tube matrix material.
A kind of preparation method of graphene-carbon nano tube matrix material comprises the steps:
Step 1, add in the entry with graphite oxide with through the carbon nanotube of s.t., ultrasonic concussion is stirred, and obtains homodisperse mixing solutions;
Step 2, said mixing solutions is filtered, solids is dry, under the environment of rare gas element, be warming up to 1000～1200 ℃ then with 10 ℃/minute speed, be incubated 10～30 minutes, be cooled to room temperature, obtain the graphene-carbon nano tube matrix material.
In a preferred embodiment, said graphite oxide and be 1: 1～2: 1 through the mass ratio of the carbon nanotube of s.t..
In a preferred embodiment, also comprise the step that said graphene-carbon nano tube matrix material is further purified after the step 2:
Under hydrogen atmosphere, said graphene-carbon nano tube matrix material is heated to 1000～1200 ℃, be incubated 30～60 minutes, be cooled to room temperature, obtain the graphene-carbon nano tube matrix material of purifying.
In a preferred embodiment, the time of ultrasonic concussion is 20～40 minutes in the step 1, and the time of stirring is 30～60 minutes.
In a preferred embodiment, the exsiccant temperature is 50～60 ℃ in the step 2, and be 5～10 hours time of drying.
In a preferred embodiment; Graphite oxide described in the step 1 prepares through following method: with graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in 80～120 ℃ the vitriol oil; The back naturally cooling stirs; Washing to neutral after drying obtains preoxidation graphite;
Said preoxidation graphite is slowly joined in the vitriol oil, keep the temperature of mixing solutions slowly adding potassium permanganate below 20 ℃; Then 25～35 ℃ of following oil baths 1～3 hour; Add deionized water, controlled temperature was kept 15 minutes below 98 ℃; Add deionized water and hydrogen peroxide solution then, suction filtration, collection solid; And
Said solid washs with Hydrogen chloride, and drying obtains said graphite oxide.
In a preferred embodiment, said carbon nanotube through s.t. prepares through following method:
Carbon nanotube is joined in the mix acid liquor of the vitriol oil and concentrated nitric acid composition, ultra-sonic dispersion 30 minutes～1 hour reacted 1～3 hour down at 70～90 ℃;
Use distilled water diluting solution, remove supernatant liquid, clean, suction filtration is got solid water and is washed till neutrality, and drying obtains said carbon nanotube through s.t..
What in a preferred embodiment, said suction filtration used is that the aperture is the polyethylene microporous membrane of 0.2 μ m～0.5 μ m.
In a preferred embodiment, in the said mix acid liquor, the volume ratio of the vitriol oil and concentrated nitric acid is 3～5: 1.
Above-mentioned preparing method's technology is simple, through ultrasonic agitation that graphite oxide and carbon nanotube are dissolved in the water, through the thermal reduction Graphene.Can better carbon nanotube be inserted between the Graphene lamella, bring into play the effect of performance complement better.In addition, adopt the method for thermal reduction to make graphite oxide generate Graphene, when improving purity, avoid the use of toxic reagent such as Hydrazine Hydrate 80, make that this method cost is lower, and environmental pollution is less.
[description of drawings]
Through the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, characteristic and advantage of the present invention will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part.Painstakingly do not draw accompanying drawing, focus on illustrating purport of the present invention by physical size equal proportion convergent-divergent.
Fig. 1 is preparing method's the schema of the graphene-carbon nano tube matrix material of an embodiment;
Fig. 2 is the electron scanning micrograph through the carbon nanotube of s.t. of an embodiment;
Fig. 3 is the electron scanning micrograph of the graphene-carbon nano tube matrix material of an embodiment.
[embodiment]
For make above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, does detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.A lot of details have been set forth in the following description so that make much of the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention does not receive the restriction of following disclosed practical implementation.
The two-dirnentional structure of the unimolecular layer of Graphene is easy to take place to reunite in drying loses the water process of interlayer and is range upon range of, curls or height fold, finally causes the utilization ratio of its specific surface area to reduce greatly.Because carbon nanotube and Graphene have a lot of similarities on structure and performance; Therefore can be inserted between graphene layer through carbon nanotube, perhaps functional group on the carbon nanotube and the functional group on the Graphene react each other, make carbon nanotube be grafted on the Graphene surface; Make and be separated from each other out between graphene layer and the layer; Improve the dried specific surface area of Graphene to reach, avoid Graphene to reunite and lamination, and then increase the purpose of the ratio electric capacity of ultracapacitor.
See also Fig. 1, the preparation method of the graphene-carbon nano tube matrix material of an embodiment comprises the steps:
Step S110 provides or prepares graphite oxide and through the carbon nanotube of s.t..
Graphite oxide can use conventional methods and prepare.Preferably, can adopt improved Hummers method preparation:
(a), with graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in 80～120 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains the preoxidation Graphene.This graphite is preferably flaky graphite.
(b), said preoxidation graphite is slowly joined in the vitriol oil, keep the temperature of mixing solutions slowly adding potassium permanganate below 20 ℃; Then 25～35 ℃ of following oil baths 1～3 hour; Add deionized water, controlled temperature was kept 15 minutes below 98 ℃; Add deionized water and hydrogen peroxide solution then, suction filtration, collection solid; And
(c), solid washs with Hydrogen chloride, drying obtains graphite oxide.
Can use conventional methods through the carbon nanotube of s.t. and to prepare.Preferably, can adopt following method preparation:
(A), carbon nanotube is joined in the mix acid liquor that the vitriol oil and concentrated nitric acid form, ultra-sonic dispersion 30 minutes～1 hour is 70～90 ℃ of reactions 1～3 hour down.Preferably, in the said mix acid liquor, the volume ratio of the vitriol oil and concentrated nitric acid is 3～5: 1.
(B), use distilled water diluting solution, remove supernatant liquid, clean, suction filtration is got solid water and is washed till neutrality, drying obtains said carbon nanotube through s.t..What preferably, suction filtration used is that the aperture is the polyethylene microporous membrane of 0.2 μ m～0.5 μ m.
Step S120, the graphite oxide that step S110 is obtained and add in the entry through the carbon nanotube of s.t., ultrasonic concussion is stirred, and obtains homodisperse mixing solutions.
Preferably, add in the entry with graphite oxide with through the carbon nanotube of the s.t. ratio with 1: 1～2: 1, ultrasonic concussion 20～40min at room temperature stirs 30～60min then, obtains homodisperse mixing solutions.
Step S130 filters above-mentioned mixing solutions, and solids is dry, under the environment of rare gas element, is warming up to 1000～1200 ℃ with 10 ℃/minute speed then, is incubated 10～30 minutes, is cooled to room temperature, obtains the graphene-carbon nano tube matrix material.
Preferably; Solids is placed in the vacuum drying oven with 50～60 ℃ of dryings 2 hours, then this solids is put into the tube furnace that is connected with the rare gas element that nitrogen or argon gas form, slowly heat up with 10 ℃/minute speed; 1000～1200 ℃ of insulations 10～30 minutes; Make the graphite oxide thermal reduction peel off the formation Graphene, be cooled to room temperature, form the graphene-carbon nano tube matrix material at last.
In order further to obtain the higher graphene-carbon nano tube matrix material of purity, also can comprise:
Step S140 under hydrogen atmosphere, is heated to 1000～1200 ℃ with said graphene-carbon nano tube matrix material, is incubated 30～60 minutes, is cooled to room temperature, obtains the graphene-carbon nano tube matrix material of purifying.
Preferably, the flow with 60mL/min in above-mentioned tube furnace feeds hydrogen 5～10min, and original rare gas element is discharged.Temperature with tube furnace is increased to 1000～1200 ℃ then, and under this temperature, is incubated 30～60min, carries out reduction reaction, makes among the S130 and partly is not reduced into Graphene by complete reductive graphite oxide, eliminates material internal defect simultaneously.After reaction finishes, matrix material is cooled to room temperature under hydrogen atmosphere, the graphene-carbon nano tube matrix material that obtains being further purified.Be appreciated that step S140 also can omit.
Above-mentioned preparation method has following advantage:
(1) through ultrasonic agitation that graphite oxide and carbon nanotube are dissolved in the water, through the thermal reduction Graphene.Can better carbon nanotube be inserted between the Graphene lamella, bring into play the effect of performance complement better.
(2) after thermal reduction, feed the hydrogen heating again and carry out secondary reduction, can further make the Graphene purifying, reduce the content of Sauerstoffatom in the Graphene, improve the withstand voltage degree of Graphene electrodes material.
(3) in the process of reduction Graphene, adopt the method for thermal reduction and hydrogen reducing, in raising purity, avoid the use of toxic reagent such as Hydrazine Hydrate 80, make the economic environmental protection of this method.
Below explain with specific embodiment.Below all reagent be analytical pure.
Embodiment 1
(1) purity being provided is 99.5% natural flake graphite.
(2) be equipped with graphite oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 80 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃; After in 35 ℃ oil bath, keeping 2h then; Slowly add the 920mL deionized water, controlled temperature is below 98 ℃, keep 15min after; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphite oxide at 60 ℃ of vacuum-drying 48h.
(3) carbon nanotube of graphite oxide in (2) and the s.t. ratio with 1: 1 is added in the entry, ultrasonic 20min, stirring at room 60min obtains homodisperse graphene oxide, carbon nano-tube solution.Wherein the concrete steps of acid-treated carbon nanotube are: take by weighing the 2g carbon nanotube in there-necked flask, add vitriol oil 60ml, concentrated nitric acid 20ml; Ultra-sonic dispersion 30min, the 1h that in 70 ℃ oil bath, refluxes uses distilled water diluting with solution; Remove supernatant liquid, wash repeatedly for several times, with the polyethylene microporous membrane suction filtration in 0.2 μ m aperture; Washing is to neutral, and vacuum drying oven is dry, obtains acid-treated MWNTs (multi-walled carbon nano-tubes).
(4) solution with (3) gained filters; In vacuum drying oven with 50 ℃ of dry 5h; Final powder is put into the tube furnace that is connected with rare gas element be warming up to 1000 ℃ of heating 30min, the graphene-carbon nano tube matrix material after obtaining reducing with the slow speed of 10 ℃/min.
(5) cool to the powder in (4) with the furnace room temperature, in tube furnace, feed hydrogen 5min earlier, the flow of control hydrogen is at 60ml/min; Rare gas element in the tube furnace is discharged; Then temperature is warming up to 1000 ℃, under this temperature, keeps heating 60min, after reduction finishes; Under hydrogen atmosphere, be cooled to room temperature, the graphene-carbon nano tube matrix material that obtains being further purified.
Embodiment 2
(1) purity being provided is 99.5% natural flake graphite.
(2) be equipped with graphite oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 80 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃; After in 35 ℃ oil bath, keeping 2h then; Slowly add the 920mL deionized water, controlled temperature is below 98 ℃, keep 15min after; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) carbon nanotube of graphite oxide in (2) and the s.t. ratio with 1: 1 is added in the entry, ultrasonic 30min, stirring at room 30min obtains homodisperse graphene oxide, carbon nano-tube solution.Wherein the concrete steps of acid-treated carbon nanotube are: take by weighing the 2g carbon nanotube in there-necked flask, add vitriol oil 80ml, concentrated nitric acid 20ml; Ultra-sonic dispersion 40min, the 2h that in 80 ℃ oil bath, refluxes uses distilled water diluting with solution; Remove supernatant liquid, wash repeatedly for several times, with the polyethylene microporous membrane suction filtration in 0.3 μ m aperture; Washing is to neutral, and vacuum drying oven is dry, obtains acid-treated MWNTs.
(4) solution with (3) gained filters; In vacuum drying oven with 50 ℃ of dry 7h; Final powder is put into the tube furnace that is connected with rare gas element be warming up to 1200 ℃ of heating 10min, the Graphene composite carbon nanometer tube after obtaining reducing with the slow speed of 10 ℃/min.
(5) high purity graphite alkene composite carbon nanometer tube material: cool to the powder in (4) with the furnace room temperature, in tube furnace, feed hydrogen 5min earlier, the flow of control hydrogen is at 60ml/min; Rare gas element in the tube furnace is discharged; Then temperature is warming up to 1000 ℃, under this temperature, keeps heating 60min, after reduction finishes; Under hydrogen atmosphere, be cooled to room temperature, the Graphene composite carbon nanometer tube that obtains being further purified.
Embodiment 3
(1) purity being provided is 99.5% natural flake graphite.
(2) be equipped with graphite oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 80 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 35 ℃ oil bath, behind the maintenance 2h, slowly adds the 920mL deionized water then, and controlled temperature is kept below 98 ℃.Behind the 15min; Add 2.8L deionized water (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) carbon nanotube of graphite oxide in (2) and the s.t. ratio with 2: 1 is added in the entry, ultrasonic 30min, stirring at room 30min obtains homodisperse graphene oxide, carbon nano-tube solution.Wherein the concrete steps of acid-treated carbon nanotube are: take by weighing the 2g carbon nanotube in there-necked flask, add vitriol oil 90ml, concentrated nitric acid 20ml; Ultra-sonic dispersion 50min, the 3h that in 80 ℃ oil bath, refluxes uses distilled water diluting with solution; Remove supernatant liquid, wash repeatedly for several times, with the polyethylene microporous membrane suction filtration in 0.4 μ m aperture; Washing is to neutral, and vacuum drying oven is dry, obtains acid-treated MWNTs.
(4) solution with (3) gained filters; In vacuum drying oven with 50 ℃ of dry 9h; Final powder is put into the tube furnace that is connected with rare gas element be warming up to 1000 ℃ of heating 30min, the graphene-carbon nano tube matrix material after obtaining reducing with the slow speed of 10 ℃/min.
(5) high purity graphite alkene composite carbon nanometer tube material: cool to the powder in (4) with the furnace room temperature, in tube furnace, feed hydrogen 5min earlier, the flow of control hydrogen is at 60ml/min; Rare gas element in the tube furnace is discharged; Then temperature is warming up to 1200 ℃, under this temperature, keeps heating 30min, after reduction finishes; Under hydrogen atmosphere, be cooled to room temperature, the graphene-carbon nano tube matrix material that obtains being further purified.
Embodiment 4
(1) purity being provided is 99.5% natural flake graphite.
(2) be equipped with graphite oxide through improved Hummers legal system.Its concrete steps are that 20g 50 order Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in 80 ℃ the vitriol oil, stir, and more than the cooling 6h, washing is to neutral, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 35 ℃ oil bath, behind the maintenance 2h, slowly adds the 920ml deionized water then.Behind the 15min; Add 2.8L deionized water (wherein contain 50ml concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) carbon nanotube of graphite oxide in (2) and the s.t. ratio with 2: 1 is added in the entry, ultrasonic 40min, stirring at room 30min obtains homodisperse graphene oxide, carbon nano-tube solution.Wherein the concrete steps of acid-treated carbon nanotube are: take by weighing the 2g carbon nanotube in there-necked flask, add vitriol oil 100ml, concentrated nitric acid 20ml; Ultra-sonic dispersion 1h, the 1h that in 90 ℃ oil bath, refluxes uses distilled water diluting with solution; Remove supernatant liquid, wash repeatedly for several times, with the polyethylene microporous membrane suction filtration in 0.5 μ m aperture; Washing is to neutral, and vacuum drying oven is dry, obtains acid-treated MWNTs.
(4) solution with (3) gained filters; In vacuum drying oven with 60 ℃ of dry 10h; Final powder is put into the tube furnace that is connected with rare gas element be warming up to 1200 ℃ of heating 20min, the graphene-carbon nano tube matrix material after obtaining reducing with the slow speed of 10 ℃/min.
(5) cool to the powder in (4) with the furnace room temperature, in tube furnace, feed hydrogen 5min earlier, the flow of control hydrogen is at 60ml/min; Rare gas element in the tube furnace is discharged; Then temperature is warming up to 1200 ℃, under this temperature, keeps heating 30min, after reduction finishes; Under hydrogen atmosphere, be cooled to room temperature, the graphene-carbon nano tube matrix material that obtains being further purified.
See also Fig. 2, be depicted as among the embodiment 1 sem (SEM) photo through the carbon nanotube of s.t..Can know that by Fig. 2 there is agglomeration clearly in carbon nanotube itself.
See also Fig. 3, be depicted as the SEM photo of graphene-carbon nano tube matrix material among the embodiment 1.Can know that by Fig. 3 the Graphene in the graphene-carbon nano tube matrix material is kept apart by carbon nanotube is well-proportioned, and lamination or aggregation phenomenon do not take place.
See also table 1, be depicted as before each embodiment process hydrogen reducing and the oxygen atom content after the reduction.
Test condition: test is carried out on PHI15300X X-ray photoelectron spectroscopy X appearance, is excitaton source with Mg K α (hv=1253.6eV), and power is 240W.
Oxygen atom content in the table 1 graphene-carbon nano tube matrix material
Can be known that by table 1 through behind the hydrogen reducing, the oxygen atom content of graphene-carbon nano tube matrix material declines to a great extent, and has not been reduced into Graphene by complete reductive graphite oxide before explaining, purity improves a lot.
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
Claims (9)
1. the preparation method of a graphene-carbon nano tube matrix material is characterized in that, comprises the steps:
Step 1, add in the entry with graphite oxide with through the carbon nanotube of s.t., ultrasonic concussion is stirred, and obtains homodisperse mixing solutions;
Step 2, said mixing solutions is filtered, solids is dry, under the environment of rare gas element, be warming up to 1000～1200 ℃ then with 10 ℃/minute speed, be incubated 10～30 minutes, be cooled to room temperature, obtain the graphene-carbon nano tube matrix material.
2. the preparation method of graphene-carbon nano tube matrix material according to claim 1 is characterized in that: said graphite oxide and be 1: 1～2: 1 through the mass ratio of the carbon nanotube of s.t..
3. the preparation method of graphene-carbon nano tube matrix material according to claim 1 is characterized in that, also comprises the step that said graphene-carbon nano tube matrix material is further purified after the step 2:
Under hydrogen atmosphere, said graphene-carbon nano tube matrix material is heated to 1000～1200 ℃, be incubated 30～60 minutes, be cooled to room temperature, obtain the graphene-carbon nano tube matrix material of purifying.
4. the preparation method of graphene-carbon nano tube matrix material according to claim 1 is characterized in that: the time of ultrasonic concussion is 20～40 minutes in the step 1, and the time of stirring is 30～60 minutes.
5. the preparation method of graphene-carbon nano tube matrix material according to claim 1 is characterized in that: the exsiccant temperature is 50～60 ℃ in the step 2, and be 5～10 hours time of drying.
6. the preparation method of graphene-carbon nano tube matrix material according to claim 1 is characterized in that: graphite oxide described in the step 1 prepares through following method,
With graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in 80～120 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains preoxidation graphite;
Slowly join said preoxidation graphite in the vitriol oil; The temperature that keeps mixing solutions then 25～35 ℃ of following oil baths 1～3 hour, adds deionized water slowly adding potassium permanganate below 20 ℃; Controlled temperature is below 98 ℃; Kept 15 minutes, and added deionized water and hydrogen peroxide solution then, suction filtration, collection solid; And
Said solid washs with Hydrogen chloride, and drying obtains said graphite oxide.
7. the preparation method of graphene-carbon nano tube matrix material according to claim 1 is characterized in that, said carbon nanotube through s.t. prepares through following method:
Carbon nanotube is joined in the mix acid liquor of the vitriol oil and concentrated nitric acid composition, ultra-sonic dispersion 30 minutes～1 hour reacted 1～3 hour down at 70 ℃～90 ℃; Use distilled water diluting solution, remove supernatant liquid, clean, suction filtration is got solid water and is washed till neutrality, and drying obtains said carbon nanotube through s.t..
8. the preparation method of graphene-carbon nano tube matrix material according to claim 7 is characterized in that: what said suction filtration used is that the aperture is the polyethylene microporous membrane of 0.2 μ m～0.5 μ m.
9. the preparation method of graphene-carbon nano tube matrix material according to claim 7 is characterized in that: in the said mix acid liquor, the volume ratio of the vitriol oil and concentrated nitric acid is 3～5: 1.
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