CN101830455B - Method for synthesizing continuous carbon nanometer tube film - Google Patents
Method for synthesizing continuous carbon nanometer tube film Download PDFInfo
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- CN101830455B CN101830455B CN2010101673119A CN201010167311A CN101830455B CN 101830455 B CN101830455 B CN 101830455B CN 2010101673119 A CN2010101673119 A CN 2010101673119A CN 201010167311 A CN201010167311 A CN 201010167311A CN 101830455 B CN101830455 B CN 101830455B
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Abstract
The invention relates to a technical method for synthesizing continuous carbon nanometer tube film, which comprises the following step of: with glycol, ethanol, acetone, hexane, benzene, toluene or xylene as a carbon source, ferrocene as catalyst, sulphur and thiophene as accelerators and with hydrogen, argon gas, nitrogen, helium or the mixed gas of hydrogen and inert gas as carrier gas, preparing a continuous carbon nanometer tube film at flow rate of carrier gas from 50 to 6000 ml/mi at temperature of 1000 to 1300 DEG C by use of a horizontal reaction furnace device, wherein the carbon nanometer tube mainly consists of a single-wall carbon nanometer tube and a double-wall carbon nanometer tube. The invention has the advantages that carbon nanometer tubes can be continuously synthesized, and scale production of carbon nanometer tubes is facilitated.
Description
Technical field
The present invention relates to a kind of production technique of synthesizing continuous carbon nanometer tube film, belong to the synthetic field of carbon nanomaterial.
Background technology
(Carbon Nanotube is the seamless monodimension nanometer material that is curled and form according to certain helix angle by the single or multiple lift graphite flake CNT) to carbon nanotube, and the geometry of this uniqueness and electronic band structure make its mechanics with superelevation, performances such as conduction and heat conduction.The tensile strength that experiment records multi-walled carbon nano-tubes surpasses 100GPa, and Young's modulus reaches 1.0TPa, maximum unit elongation 10～12%.In addition, the specific conductivity of carbon nanotube is up to 10
5Scm
-1, be 1000 times of thomel.The thermal conductivity of carbon nanotube is up to 3000Wm
-1K
-1, make it become good thermally conductive material.The aerial thermostability of carbon nanotube (not oxidized basically below 500 ℃ in air) makes it become excellent fire retardant (Flame Retardant) material.
In recent years, a lot of new technologies of synthetic appearance of carbon nanotube.Keep kind research group like the model of Tsing-Hua University and from directional carbon nanotube array, spun the multi-walled carbon nano-tubes silk thread.The R.H.Baughman research group of the U.S. and Yuntian Zhu research group adopt similar method respectively subsequently, list from carbon nano-pipe array and have spun carbon nano-tube fibre.The Wu De of Tsing-Hua University sea research group adopts vertical floating catalytic cracking process successfully directly to synthesize the SWCN long filament that length reaches 40cm, but this method can not synthesizing continuous carbon nanometer tube silk thread and large-scale production.In addition, and the A.H.Windle research group of univ cambridge uk (Science, Vol 304; 276-278,2004) and Li Yali research group of University Of Tianjin (Advanced Materials, Vol22; 692-696,2010) adopt chemical Vapor deposition process from the vertical response stove, to spin successive carbon nanotube silk thread, but owing to adopt the vertical response stove; Adopt pure hydrogen as carrier gas simultaneously, have certain potential safety hazard, be unfavorable for the large-scale production carbon nano-tube fibre.
The technology of existing preparation continuous carbon nano-tube silk thread all is to adopt catalystic pyrolysis and vertical response stove, and main drawback and deficiency are: (1) carrier gas is a pure hydrogen, has potential safety hazard like suitability for industrialized production; (2) the vertical response stove is unfavorable for the large scale collection carbon nanotube.The present invention directly spins the successive carbon nano-tube film from the angle of large-scale production continuous carbon nanometer tube film from the horizontal reacting stove; And obtain the carbon nano-tube film of orientation degree through the flow velocity of control carrier gas.
Summary of the invention
The objective of the invention is to: overcome the deficiency of prior art, a kind of process method of continuously synthetic big area carbon nano-tube film is provided, it is big that this method synthetic carbon nano-tube film has output, characteristics such as favorable orientation.
The objective of the invention is to realize through following technical proposals: a kind of method of synthesizing continuous carbon nanometer tube film, utilize the horizontal reacting stove to realize that concrete steps are following:
(1) with catalyst dissolution in carbon source; Add promotor then and form even mixed solution; The mass percent of described carbon source, catalyzer and promotor is 90～99%, 0.2～6%, 0.1～4%, with said mixing solutions ultra-sonic dispersion, obtains reaction soln then;
(2) the temperature speed with the horizontal reacting stove rises to 1000～1300 ℃ of high temperature; Reaction solution is injected in the air-flow of carrier gas, in the horizontal reacting stove, when reaction soln reaches 1000～1300 ℃ of temperature; Carbon nano-tube film flows out with air-flow; Rotate the terminal rotation axis of silica tube in the horizontal reacting stove, obtain carbon nano-tube film, realize the continuous preparation of carbon nano-tube film.
Described carbon source is with terepthaloyl moietie, ethanol, acetone, hexane, benzene, toluene or YLENE.
Said catalyzer is ferrocene or catalyzer such as Cobaltous diacetate or nickel acetate.Ferrocene or title cyclopentadienyl moiety iron comprise two cyclopentadiene rings and iron atom Cheng Jian, to air-stable, when being heated to 100 ℃, distil rapidly, are fit to the body series synthesizing carbon nanotubes.Cobaltous diacetate, nickel acetate also can be used as the catalyzer of body series synthesizing carbon nanotubes in addition.
Said promotor is sulfocompounds such as thiophene or sulphur, and its reason is that sulphur has katalysis in the carbon nano tube growth process.
Said carrier gas is rare gas elementes such as nitrogen, argon gas, helium, or the mixed gas of hydrogen and rare gas element.
Described flow rate of carrier gas is 50～6000ml/min, if carrier gas is the mixed gas of rare gas element and hydrogen, the volume ratio of rare gas element and hydrogen is 1: 1～1: 20.
Described ultra-sonic dispersion time range is 5-30min.
The temperature of horizontal reacting stove rises to 1000～1300 ℃ with the speed of 5-20 ℃/min in the said step (2).
Reaction soln 1-200ml/hour is injected in the air-flow of carrier gas in the said step (2).
Principle of the present invention: utilize the horizontal reacting furnace apparatus; Carbon source, catalyzer and promotor uniform mixing are made into clear solution; When waiting to reach synthesis temperature, reaction solution together introduced with carrier gas with the form of steam carry out catalytic pyrolysis in the horizontal reacting stove, the carbon nano-tube film that reaction zone generates flows out and adheres on the stir shaft of Reaktionsofen tail end along with carrier gas; Realize the continuous preparation of carbon nano-tube film, it is characterized in that this method is the continuous production carbon nano-tube film.
The present invention's advantage compared with prior art is:
(1) adopts horizontal reacting stove and carbon nano-tube film to spin device, help the large-scale production carbon nanotube;
(2) there is not potential safety hazard in the mixed gas of employing hydrogen and rare gas element;
(3) through the inflow velocity of control carrier gas, effectively aligned carbon nanotube obtains the good carbon nano-tube film of orientation.
Description of drawings
The horizontal reacting furnace apparatus that Fig. 1 uses for the present invention;
The carbon nano-tube film that Fig. 2 obtains for the embodiment of the invention 1;
The scanning electron microscope figure of the carbon nanotube that Fig. 3 obtains for the embodiment of the invention 1;
The scanning electron microscope figure of the carbon nanotube that Fig. 4 obtains for the embodiment of the invention 3;
The laser Raman spectrum figure of the carbon nanotube that Fig. 5 obtains for the embodiment of the invention 3;
The transmission electron microscope(TEM) figure of the carbon nanotube that Fig. 6 obtains for the embodiment of the invention 3;
The transmission electron microscope(TEM) figure of the carbon nanotube that Fig. 7 obtains for the embodiment of the invention 3.
Embodiment
As shown in Figure 1, be the horizontal reacting furnace apparatus that uses in the inventive method, it is made up of micro-injection pump 1, carrier gas 2, kapillary 3, flange 4, gas tube 5, silica tube 6, horizontal electric furnace 7, motor 8 and rotation axis 9.When temperature reaches temperature of reaction, bring into use micro-injection pump that reaction solution is injected silica tube, reaction solution runs into high temperature reaction stove moment and becomes gas, then along with carrier gas gets in the Reaktionsofen.The catalyzer ferrocene decomposites nano iron particles, and carbon source just deposits the production carbon nanotube and taken out of by carrier gas stream around the iron particle, opens motor 8 and collects with the effusive carbon nanotube of carrier gas with rotation axis 9.
(1) takes by weighing the 0.026g ferrocene, be dissolved in the 12.87g toluene solution, drip the 0.1g thiophene, with mixing solutions ultra-sonic dispersion 5min, obtain the yellow transparent reaction soln then.
(2) temperature of horizontal reacting stove is risen to 1000 ℃ with the speed of 10 ℃/min; The speed of reaction solution with 15ml/h is injected in the air-flow that the 50ml/min argon gas is carrier gas 2; In high temperature reaction stove; Carbon nano-tube film flows out with air-flow, rotates the rotation axis 9 of silica tube 6 ends, obtains carbon nano-tube film.
Fig. 2 is continuous spun carbon nano-tube film, the about 15cm of length, and the about 100 μ m of thickness, the reaction times is 20min.
(1) takes by weighing the 0.78g ferrocene, be dissolved in 11.7 ethanolic solns, drip the 0.52g thiophene.With mixing solutions ultra-sonic dispersion 5min, obtain the yellow transparent reaction soln then.
(2) temperature of horizontal reacting stove is risen to 1100 ℃ with the speed of 10 ℃/min, reaction solution is injected into the (H that mixes of 550ml/min hydrogen and argon gas with the speed of 15ml/h
2: Ar=5: 1) in the carrier gas stream 2, in high temperature reaction stove, carbon nano-tube film flows out with air-flow, rotates the rotation axis 9 of silica tube 6 ends, obtains carbon nano-tube film.
(1) takes by weighing the 0.4g ferrocene, be dissolved in the 12.5g xylene solution, drip the 0.26g thiophene.With mixing solutions ultra-sonic dispersion 5min, obtain the yellow transparent reaction soln then.
2) temperature of horizontal reacting stove is risen to 1150 ℃ with the speed of 10 ℃/min, reaction solution is injected into the (H that mixes of 1000ml/min hydrogen and argon gas with the speed of 15ml/h
2: Ar=10: 1) in the carrier gas stream 2, in high temperature reaction stove, carbon nano-tube film flows out with air-flow, rotates the rotation axis 9 of silica tube 6 ends, obtains carbon nano-tube film.
(1) takes by weighing the 0.4g ferrocene, be dissolved in the 12.5g benzole soln, drip the 0.1g thiophene.With mixing solutions ultra-sonic dispersion 5min, obtain the yellow transparent reaction soln then.
(2) temperature of horizontal reacting stove is risen to 1150 ℃ with the speed of 10 ℃/min, reaction solution is injected into the (H that mixes of 2500ml/min hydrogen and argon gas with the speed of 15ml/h
2: Ar=20: 1) in the carrier gas stream 2, in high temperature reaction stove, carbon nano-tube film flows out with air-flow, rotates the rotation axis 9 of silica tube 6 ends, obtains carbon nano-tube film.
(1) takes by weighing the 0.4g ferrocene, be dissolved in the 12.5g hexane solution, drip the 0.1g thiophene.With mixing solutions ultra-sonic dispersion 5min, obtain the yellow transparent reaction soln then.
(2) temperature of horizontal reacting stove is risen to 1200 ℃ with the speed of 10 ℃/min, reaction solution is injected into the (H that mixes of 4500ml/min hydrogen and nitrogen with the speed of 15ml/h
2: N
2=1: 1) in the carrier gas stream 2, in high temperature reaction stove, carbon nano-tube film flows out with air-flow, rotates the terminal rotation axis 9 of quartzy 6 pipes, obtains carbon nano-tube film.
(1) takes by weighing the 0.4g ferrocene, be dissolved in the 12.5g ethylene glycol solution, drip the 0.1g thiophene.With mixing solutions ultra-sonic dispersion 5min, obtain the yellow transparent reaction soln then.
(2) temperature of horizontal reacting stove is risen to 1250 ℃ with the speed of 10 ℃/min, reaction solution is injected into the (H that mixes of 6000ml/min hydrogen and nitrogen with the speed of 15ml/h
2: N
2=20: 1) in the carrier gas stream 2, in 1250 ℃ of Reaktionsofens of high temperature, carbon nano-tube film flows out with air-flow, rotates the rotation axis 9 of silica tube 6 ends, obtains carbon nano-tube film.
Claims (4)
1. the method for a synthesizing continuous carbon nanometer tube film is characterized in that: utilize the horizontal reacting stove to realize that concrete steps are following:
(1) with catalyst dissolution in carbon source; Add promotor then and form even mixed solution; The mass percent of described carbon source, catalyzer and promotor is 90～99%, 0.2～6%, 0.1～4%; With said mixing solutions ultra-sonic dispersion 5-30min, obtain the yellow transparent reaction soln then; The temperature of said horizontal reacting stove rises to 1000～1300 ℃ with 5-20 ℃/min;
(2) the temperature speed with the horizontal reacting stove rises to 1000～1300 ℃ of high temperature; Reaction solution is injected in the air-flow of carrier gas, in the horizontal reacting stove, when reaction soln reaches 1000～1300 ℃ of temperature; Carbon nano-tube film flows out with air-flow; Rotate the terminal rotation axis of silica tube in the horizontal reacting stove, obtain carbon nano-tube film, realize the continuous preparation of carbon nano-tube film;
Described flow rate of carrier gas is 50～6000ml/min, and carrier gas is the mixed gas of rare gas element and hydrogen, and the volume ratio of rare gas element and hydrogen is 1: 1～1: 20;
Reaction soln is injected in the air-flow of carrier gas in the said step (2) with 1-200ml/hour;
The speed of the terminal rotation axis of silica tube increases with the injection speed of reaction liquid in the said step (2).
2. the method for a kind of synthesizing continuous carbon nanometer tube film according to claim 1, it is characterized in that: described carbon source is terepthaloyl moietie, ethanol, acetone, hexane, benzene, toluene or YLENE.
3. the method for a kind of synthesizing continuous carbon nanometer tube film according to claim 1, it is characterized in that: said catalyzer is ferrocene or Cobaltous diacetate or nickel acetate.
4. the method for a kind of synthesizing continuous carbon nanometer tube film according to claim 1, it is characterized in that: said promotor is thiophene or sulphur.
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| CN102199872B (en) * | 2011-03-29 | 2013-04-03 | 北京航空航天大学 | Method for in-situ growing carbon nanotubes on fiber surfaces |
| CN103031531B (en) * | 2012-12-28 | 2015-07-22 | 苏州汉纳材料科技有限公司 | Preparation method and system for transparent conductive film of flexible carbon nanotube |
| CN103204492A (en) * | 2013-05-03 | 2013-07-17 | 苏州汉纳材料科技有限公司 | New method for improving yield of single-walled carbon nanotube |
| CN103910352A (en) * | 2014-04-08 | 2014-07-09 | 上海电机学院 | Method for preparing multi-walled carbon nano tube |
| CN103922311A (en) * | 2014-04-14 | 2014-07-16 | 北京航空航天大学 | High-orientation and high-densification carbon nano tube membrane and preparation method thereof |
| CN104985719B (en) * | 2015-06-08 | 2017-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of Nano Materials Modified Polymers base fibrous composite |
| US10266411B2 (en) | 2015-07-16 | 2019-04-23 | Toray Industries, Inc. | Method of producing carbon nanotube-containing composition |
| CN106517146A (en) * | 2016-11-11 | 2017-03-22 | 苏州赛福德备贸易有限公司 | Method for preparing composite nanocarbon material |
| CN106517159A (en) * | 2016-11-11 | 2017-03-22 | 苏州赛福德备贸易有限公司 | A preparing method of a composite nanometer carbon material |
| CN107057278B (en) * | 2016-11-25 | 2023-07-14 | 深圳前海量子翼纳米碳科技有限公司 | Preparation device and preparation method for preparing carbon nano tube film composite material in one step |
| CN108584917B (en) * | 2018-06-05 | 2019-11-15 | 中南民族大学 | A kind of preparation method of hydrophilic carbon nano tube film |
| CN110878433B (en) * | 2018-09-05 | 2022-09-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for continuously preparing metal type single-walled carbon nanotube fiber |
| CN109437157B (en) * | 2018-11-29 | 2022-02-18 | 中国科学院金属研究所 | Floating catalyst chemical vapor deposition method for single-walled carbon nanotube |
| CN109704310A (en) * | 2019-03-04 | 2019-05-03 | 无锡远稳烯科技有限公司 | A kind of manufacture craft of graphene carbon nano-tube film |
| CN109967078B (en) * | 2019-03-26 | 2022-02-22 | 南京工业大学 | Preparation method of morphology-controllable carbon nanotube-based gas catalytic membrane |
| CN114477141B (en) * | 2020-10-24 | 2023-11-24 | 江苏天奈科技股份有限公司 | Oligowall carbon nanotube fiber bundle and preparation process thereof |
| CN112279238B (en) * | 2020-10-29 | 2023-03-24 | 南京源昌新材料有限公司 | Preparation method of high-conductivity double-wall carbon nanotube film |
| CN112174114B (en) * | 2020-10-29 | 2022-05-24 | 南京源昌新材料有限公司 | Mixed carbon nanotube film and preparation method thereof |
| CN113401906B (en) * | 2021-06-17 | 2022-11-08 | 北京佰耐特能源科技有限公司 | Non-bonding integrated titanium carbide material and preparation method thereof |
| CN114132918B (en) * | 2021-12-31 | 2023-10-20 | 西安交通大学 | Preparation method of mass-produced high-conductivity multi-wall carbon nano tube film material |
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