CN101696491B - In-situ method for preparing graphene/carbon nanotube composite film - Google Patents
In-situ method for preparing graphene/carbon nanotube composite film Download PDFInfo
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- CN101696491B CN101696491B CN2009102184827A CN200910218482A CN101696491B CN 101696491 B CN101696491 B CN 101696491B CN 2009102184827 A CN2009102184827 A CN 2009102184827A CN 200910218482 A CN200910218482 A CN 200910218482A CN 101696491 B CN101696491 B CN 101696491B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 63
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title abstract description 13
- 238000000034 method Methods 0.000 title abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 130
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000007789 gas Substances 0.000 claims abstract description 88
- 229910052786 argon Inorganic materials 0.000 claims abstract description 65
- 239000001257 hydrogen Substances 0.000 claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 45
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims description 42
- 230000001105 regulatory effect Effects 0.000 claims description 27
- 238000010792 warming Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 abstract 3
- 239000011593 sulfur Substances 0.000 abstract 3
- 238000010923 batch production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 39
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 241000931526 Acer campestre Species 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 102000029749 Microtubule Human genes 0.000 description 1
- 108091022875 Microtubule Proteins 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004688 microtubule Anatomy 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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Abstract
The invention relates to an in-situ method for preparing a graphene/carbon nanotube composite film, which comprises the following steps of: 1. weighing ferrocene and sulfur, uniformly mixing and placing the mixture at the front end of a reaction vessel; placing a polycrystal nickel piece in the center of the reaction vessel and sealing the reaction vessel; 2. introducing a hydrogen/argon mixed gas into the reaction vessel, heating the center of the reaction vessel to 1100-1150 DEG C and adjusting the flow of the hydrogen/argon; 3. heating the ferrocene and the sulfur at the front end of the reaction vessel so as to enable the ferrocene and the sulfur to be volatilized and carrying a volatilized gas into the reaction vessel to react by the adjusted hydrogen/argon mixed gas in the step 2; 4. stopping heating the center of the reaction vessel, shutting off the hydrogen, adjusting the flow of the argon, drawing the nickel piece out of the center of the reaction vessel and cooling to room temperature; and obtaining the graphene/carbon nanotube composite film on the nickel piece. The invention realizes the batch production of the graphene/carbon nanotube composite film and has the characteristics of large area, controllable thickness, high electrical conductivity and continuation.
Description
Technical field
The present invention relates to nano-carbon material synthetic and Application Areas, particularly a kind of in-situ preparation method of Graphene/carbon nano-tube coextruded film.
Background technology
Carbon nanotube [reference 1:S.Iijima.Helical microtubules of graphitic carbon.Nature, 1991,354 (6348): 56-58.] and Graphene [reference 2:K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov.Electric field effect in atomically thin carbon films.Science, 2004,306 (5696): 666-669.] be two kinds of typical carbon nanomaterials.Graphene (Graphene) is " mono-layer graphite sheet ", is the basic structural unit that constitutes graphite; And carbon nanotube is the cylindrical structure that is curled and formed by Graphene.The two all can be as thin-film material.Yet all there are shortcoming in carbon nanotube and Graphene as thin-film material separately.Carbon nano-tube film is network structure, the space that interbank existence is bigger.Though these spaces help printing opacity, weakened the electroconductibility of film.Though and Graphene has high conductivity, number of plies difficulty is given accurate control in preparation process, and the size and dimension of synusia differs, and easily piles up in film process or breaks away from: synusia piles up the light transmission of understanding the reduction film; Synusia breaks away from then each other can increase face resistance.Carbon nanotube and Graphene have complementarity on structure and performance.Following researchdevelopment trend is exactly that research with carbon nanotube and Graphene combines, and makes full use of the complementarity of the two, and expection can obtain a kind of carbon back composite structure with new function.
Research about carbon nanotube/Graphene composite structure at present still has the following disadvantages: 1) only can directly synthesize vertical composite structure, can't the horizontal composite structure of growth in situ [reference 3:D.Kondo, S.Sato, Y.Awano.Self-organization of novel carbon composite structure:Graphene multi-layers combinedperpendicularly with aligned carbon nanotubes.Appl.Phys.Express, 2008,1 (7): 074003.]; 2) liquid phase methods that adopt more, with the two simple mixing, and it is auxiliary with the reduction aftertreatment, can not bring into play characteristic [the reference 4:D.Y.Cai of the two fully effectively, M.Song, C.X.Xu.Highly conductive carbon-nanotube/graphite-oxidehybrid films.Adv.Mater., 2008,20 (9): 1706-1709. reference 5:H.Q.Zhu, Y.M.Zhang, L.Yue, W.S.Li, G.L.Li, D.Shu, H.Y.Chen.Graphite-carbon nanotube composite electrodes for allvanadium redox flow battery.J.Power Sources 2008,184 (2): 637-640. reference 6:V.C.Tung, L.M.Chen, M.J.Allen, J.K.Wassei, K.Nelson, R.B.Kaner, Y.Yang.Low-temperaturesolution processingof graphene-carbon nanotube hybrid materials for high-performancetransparent conductors.Nano Lett.2009,9 (5): 1949-1955.].
Summary of the invention
In order to overcome the defective of above-mentioned prior art, the object of the present invention is to provide a kind of in-situ preparation method of Graphene/carbon nano-tube coextruded film, realize the batch of Graphene/carbon nano-tube coextruded film, direct, easy manufacture.
In order to achieve the above object, technical scheme of the present invention is achieved in that
The in-situ preparation method of Graphene/carbon nano-tube coextruded film may further comprise the steps:
1, taking by weighing mass ratio is 58～116: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 1 * 1cm
2～10 * 10cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 100～200mL/min and the argon gas mixed gas that flow is 200～400mL/min, reactor center is warming up to 1100～1150 ℃ simultaneously, regulate flow to the 100～400mL/min of hydrogen, the flow to 800 of argon gas～2000mL/min;
3, the ferrocene of reactor heating front end and sulphur to 80～110 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 5～15 minutes;
4, reactor center stops heating, close hydrogen, regulate argon flow amount to 100～200mL/min, the nickel sheet is pulled out from the reactor center position, speed of cooling with 5～20 ℃/s is cooled to room temperature, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Described reactor is silica tube or a vitrified pipe reactor commonly used in the meteorological experiment of chemistry.
Graphene/carbon nano-tube coextruded film that the present invention makes is taken the two-dimentional homogeneous continuous structure of tying and constituting mutually by Graphene synusia and carbon nanotube, and this laminated film is determined that by reactor size area can reach 10～100cm
2The thickness of laminated film is in 30nm～500 mu m ranges; This laminated film has high conductivity, and the Graphene in the background technology and the vertical composite structure of carbon nanotube, the laminated film among the present invention are to be overlapped mutually and the horizontal composite structure that constitutes by Graphene and carbon nanotube on microcosmic.The laminated film that mixes through aftertreatment in the background technology, has synthesized Graphene/carbon nano-tube coextruded film at original position of the present invention with settling at one go, is convenient to directly use and batch preparations.This Graphene/carbon nano-tube coextruded film has big area, controllable thickness, high conductivity, continuous unremitting characteristics.
Description of drawings
Fig. 1 is to be 1150 ℃ in temperature of reaction, and hydrogen and argon flow amount are 200/1000mL/min, when the reaction raw materials volatilization temperature is 100 ℃, and the structural characterization of Graphene/carbon nano-tube coextruded film that reaction 10min prepares; Wherein, Fig. 1 (a) is the photomacrograph of Graphene/carbon nano-tube coextruded film; Fig. 1 (b) is the electron scanning micrograph of Graphene/carbon nano-tube coextruded film.
Fig. 2 is to be 1150 ℃ in temperature of reaction, and hydrogen and argon flow amount are 200/1000mL/min, when the reaction raw materials volatilization temperature is 100 ℃, and the Raman spectrum (optical maser wavelength 633nm) of Graphene/carbon nano-tube coextruded film that reaction 10min prepares.
Fig. 3 is to be 1100 ℃ in temperature of reaction, and hydrogen and argon flow amount are 100/800mL/min, and when the reaction raw materials volatilization temperature was 90 ℃, the reaction times was the thickness and the face resistance of Graphene/carbon nano-tube coextruded film of preparing of 5min, 10min and 15min.
Fig. 4 is to be 1125 ℃ in temperature of reaction, and hydrogen and argon flow amount are 400/2000mL/min, when the reaction raw materials volatilization temperature is 110 ℃, and the electron scanning micrograph of Graphene/carbon nano-tube coextruded film that reaction 8min prepares.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
Embodiment one
Present embodiment may further comprise the steps:
1, taking by weighing mass ratio is 58: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 4 * 4cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 100mL/min and the argon gas mixed gas that flow is 200mL/min, reactor center is warming up to 1150 ℃ simultaneously, and the flow of regulating hydrogen is to 200mL/min, and the flow of argon gas is to 1000mL/min;
3, the ferrocene of reactor heating front end and sulphur to 100 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 10 minutes;
4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 100mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 20 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Fig. 1 (a) is the photomacrograph of present embodiment Graphene/carbon nano-tube coextruded film.Fig. 1 (b) is the electron scanning micrograph of present embodiment Graphene/carbon nano-tube coextruded film, and Graphene and carbon nanotube overlap mutually and constitute the successive composite structure.Fig. 2 is the Raman spectrum (optical maser wavelength 633nm) of present embodiment Graphene/carbon nano-tube coextruded film, and two character zones show that after amplifying (wherein CNT represents carbon nanotube for the characteristic peak of Graphene and carbon nanotube; G represents Graphene), prove and contain carbon nanotube and Graphene in the sample simultaneously.
Embodiment two
Present embodiment may further comprise the steps:
1, taking by weighing mass ratio is 78: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 150mL/min and the argon gas mixed gas that flow is 300mL/min, reactor center is warming up to 1100 ℃ simultaneously, and the flow of regulating hydrogen is to 100mL/min, and the flow of argon gas is to 800mL/min;
3, the ferrocene of reactor heating front end and sulphur to 90 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, stops to heat ferrocene/sulphur behind the reaction 5min;
4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 150mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 15 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Embodiment three
Present embodiment may further comprise the steps:
1, taking by weighing mass ratio is 78: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 150mL/min and the argon gas mixed gas that flow is 300mL/min, reactor center is warming up to 1100 ℃ simultaneously, and the flow of regulating hydrogen is to 100mL/min, and the flow of argon gas is to 800mL/min;
3, the ferrocene of reactor heating front end and sulphur to 90 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, stops to heat ferrocene/sulphur behind the reaction 10min;
4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 150mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 15 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Embodiment four
Present embodiment may further comprise the steps:
1, taking by weighing mass ratio is 78: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 150mL/min and the argon gas mixed gas that flow is 300mL/min, reactor center is warming up to 1100 ℃ simultaneously, and the flow of regulating hydrogen is to 100mL/min, and the flow of argon gas is to 800mL/min;
3, the ferrocene of reactor heating front end and sulphur to 90 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, stops to heat ferrocene/sulphur behind the reaction 15min;
4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 150mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 15 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Two, three, four of embodiment have changed the reaction times in the third step, and as can be seen from Figure 3, the thickness of the Graphene/carbon nano-tube coextruded film that obtains and face resistance increase along with the lengthening in reaction times respectively and reduces.Fig. 3 is the thickness and the face resistance of Graphene/carbon nano-tube coextruded film of preparing of 5min, 10min and 15min for two, three, four reaction times of embodiment.Along with the growth in reaction times, the thickness of laminated film increases, and face resistance reduces.
Embodiment five
Present embodiment may further comprise the steps:
1, taking by weighing mass ratio is 98: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 8 * 8cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 200mL/min and the argon gas mixed gas that flow is 400mL/min, reactor center is warming up to 1120 ℃ simultaneously, and the flow of regulating hydrogen is to 300mL/min, and the flow of argon gas is to 1500mL/min;
3, the ferrocene of reactor heating front end and sulphur to 80 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 12 minutes;
4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 200mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 10 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Present embodiment can obtain being similar to Fig. 1 (a) and (b) shown in Graphene/carbon nano-tube coextruded film.
Embodiment six
Present embodiment may further comprise the steps:
1, taking by weighing mass ratio is 116: 1 ferrocene and sulphur, and uniform mixing places the reactor front end, is 99.5% with purity, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor;
2, feeding flow to reactor is the hydrogen of 120mL/min and the argon gas mixed gas that flow is 240mL/min, reactor center is warming up to 1125 ℃ simultaneously, and the flow of regulating hydrogen is to 400mL/min, and the flow of argon gas is to 2000mL/min;
3, the ferrocene of reactor heating front end and sulphur to 110 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 8 minutes;
4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 120mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 5 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
Fig. 4 is the electron scanning micrograph of present embodiment Graphene/carbon nano-tube coextruded film.
Claims (7)
1. the in-situ preparation method of Graphene/carbon nano-tube coextruded film is characterized in that, may further comprise the steps: 1, take by weighing mass ratio and be 58～116: 1 ferrocene and sulphur, uniform mixing places the reactor front end, is 99.5% with purity, thickness is 0.1mm, and area is 1 * 1cm
2～10 * 10cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 100～200mL/min and the argon gas mixed gas that flow is 200～400mL/min, reactor center is warming up to 1100～1150 ℃ simultaneously, regulate flow to the 100～400mL/min of hydrogen, the flow to 800 of argon gas～2000mL/min; 3, the ferrocene of reactor heating front end and sulphur to 80～110 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 5～15 minutes; 4, reactor center stops heating, close hydrogen, regulate argon flow amount to 100～200mL/min, the nickel sheet is pulled out from the reactor center position, speed of cooling with 5～20 ℃/s is cooled to room temperature, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
2. the in-situ preparation method of Graphene/carbon nano-tube coextruded film according to claim 1, it is characterized in that, may further comprise the steps: the ferrocene and the sulphur that 1, take by weighing mass ratio and be 58: 1, uniform mixing, place the reactor front end, with purity is 99.5%, and thickness is 0.1mm, and area is 4 * 4cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 100mL/min and the argon gas mixed gas that flow is 200mL/min, reactor center is warming up to 1150 ℃ simultaneously, and the flow of regulating hydrogen is to 200mL/min, and the flow of argon gas is to 1000mL/min; The flow of regulating hydrogen/argon gas is to 200/1000mL/min; 3, the ferrocene of reactor heating front end and sulphur to 100 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 10 minutes; 4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 100mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 20 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
3. the in-situ preparation method of Graphene/carbon nano-tube coextruded film according to claim 1, it is characterized in that, may further comprise the steps: the ferrocene and the sulphur that 1, take by weighing mass ratio and be 78: 1, uniform mixing, place the reactor front end, with purity is 99.5%, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 150mL/min and the argon gas mixed gas that flow is 300mL/min, reactor center is warming up to 1100 ℃ simultaneously, and the flow of regulating hydrogen is to 100mL/min, and the flow of argon gas is to 800mL/min; 3, the ferrocene of reactor heating front end and sulphur to 90 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, stops to heat ferrocene/sulphur behind the reaction 5min; 4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 150mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 15 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
4. the in-situ preparation method of Graphene/carbon nano-tube coextruded film according to claim 1, it is characterized in that, may further comprise the steps: the ferrocene and the sulphur that 1, take by weighing mass ratio and be 78: 1, uniform mixing, place the reactor front end, with purity is 99.5%, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 150mL/min and the argon gas mixed gas that flow is 300mL/min, reactor center is warming up to 1100 ℃ simultaneously, and the flow of regulating hydrogen is to 100mL/min, and the flow of argon gas is to 800mL/min; 3, the ferrocene of reactor heating front end and sulphur to 90 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, stops to heat ferrocene/sulphur behind the reaction 10min; 4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 150mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 15 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
5. the in-situ preparation method of Graphene/carbon nano-tube coextruded film according to claim 1, it is characterized in that, may further comprise the steps: the ferrocene and the sulphur that 1, take by weighing mass ratio and be 78: 1, uniform mixing, place the reactor front end, with purity is 99.5%, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 150mL/min and the argon gas mixed gas that flow is 300mL/min, reactor center is warming up to 1100 ℃ simultaneously, and the flow of regulating hydrogen is to 100mL/min, and the flow of argon gas is to 800mL/min; 3, the ferrocene of reactor heating front end and sulphur to 90 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, stops to heat ferrocene/sulphur behind the reaction 15min; 4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 150mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 15 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
6. the in-situ preparation method of Graphene/carbon nano-tube coextruded film according to claim 1, it is characterized in that, may further comprise the steps: the ferrocene and the sulphur that 1, take by weighing mass ratio and be 98: 1, uniform mixing, place the reactor front end, with purity is 99.5%, and thickness is 0.1mm, and area is 8 * 8cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 200mL/min and the argon gas mixed gas that flow is 400mL/min, reactor center is warming up to 1120 ℃ simultaneously, and the flow of regulating hydrogen is to 300mL/min, and the flow of argon gas is to 1500mL/min; 3, the ferrocene of reactor heating front end and sulphur to 80 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 12 minutes; 4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 200mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 10 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
7. the in-situ preparation method of Graphene/carbon nano-tube coextruded film according to claim 1, it is characterized in that, may further comprise the steps: the ferrocene and the sulphur that 1, take by weighing mass ratio and be 116: 1, uniform mixing, place the reactor front end, with purity is 99.5%, and thickness is 0.1mm, and area is 2 * 2cm
2Polycrystalline nickel sheet, place the reactor center position, sealed reactor; 2, feeding flow to reactor is the hydrogen of 120mL/min and the argon gas mixed gas that flow is 240mL/min, reactor center is warming up to 1125 ℃ simultaneously, and the flow of regulating hydrogen is to 400mL/min, and the flow of argon gas is to 2000mL/min; 3, the ferrocene of reactor heating front end and sulphur to 110 ℃ make its volatilization, and volatilization gas is written in the reactor by the hydrogen/argon gas mixed gas after regulating in the step 2, react to stop to heat ferrocene and sulphur after 8 minutes; 4, reactor center stops heating, closes hydrogen, regulates argon flow amount to 120mL/min, and the nickel sheet is pulled out from the reactor center position, is cooled to room temperature with the speed of cooling of 5 ℃/s, can obtain Graphene/carbon nano-tube coextruded film on the nickel sheet.
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| CN101941695B (en) * | 2010-09-09 | 2012-07-04 | 北京化工大学 | Method for synthesizing graphene |
| CN102208566A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate used in luminescent device and preparation method thereof |
| CN102208548B (en) * | 2011-04-18 | 2014-06-04 | 电子科技大学 | Flexible optoelectronic device substrate and preparation method thereof |
| CN102208546A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Flexible substrate used in optoelectronic device and preparation method thereof |
| CN102208537B (en) * | 2011-04-18 | 2013-09-25 | 电子科技大学 | Substrate for flexible photoelectronic device and preparation method thereof |
| CN102795613B (en) * | 2011-05-27 | 2014-09-10 | 清华大学 | Preparation method of graphene-carbon nano tube composite structure |
| CN102887498B (en) * | 2011-07-21 | 2014-10-15 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN102887501B (en) * | 2011-07-21 | 2016-02-03 | 海洋王照明科技股份有限公司 | A kind of preparation method of nitrating Graphene |
| CN102417176A (en) * | 2011-09-06 | 2012-04-18 | 天津大学 | Preparation method of graphene-carbon nanotube compound film based on three-dimensional network appearance |
| CN103456520B (en) * | 2012-05-31 | 2016-12-14 | 海洋王照明科技股份有限公司 | A kind of preparation method and applications of graphene/carbon nanotube composite film |
| CN106367717B (en) * | 2016-08-19 | 2018-07-13 | 中国科学院重庆绿色智能技术研究院 | One-dimensional carbon nanotube and the growing patterned method of three-dimensional graphene composite material |
| CN109440081B (en) * | 2018-12-21 | 2021-01-26 | 南京工程学院 | Method for preparing magnetic graphene film based on chemical vapor deposition method |
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