CN1724343A - Method for large-batch preparing overlength carbon nano pipe array and its apparatus - Google Patents
Method for large-batch preparing overlength carbon nano pipe array and its apparatus Download PDFInfo
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- CN1724343A CN1724343A CN 200510012067 CN200510012067A CN1724343A CN 1724343 A CN1724343 A CN 1724343A CN 200510012067 CN200510012067 CN 200510012067 CN 200510012067 A CN200510012067 A CN 200510012067A CN 1724343 A CN1724343 A CN 1724343A
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Abstract
A process and equipment for preparing ultra-long carbon nano-tube array in batch is disclosed. Said process includes such steps as providing monolithic reactor with artery structure, adding ZrO2, SiO2 or Al2O3 particles or their mixture, inserting structural member in fixed bed and chemical vapor deposition. Its advantages are high purity and output.
Description
Technical field:
A kind of method of large-batch preparing overlength carbon nano pipe array and device thereof belong to the nano material preparation technical field.
Background technology:
Carbon nanotube can be regarded the one dimension tubular nanometer structure of being curled and being formed by graphite linings as, and 1991 by Japanese Electronic Speculum scholar's Iijima discovery.According to the graphite number of plies difference of curling, carbon nanotube is divided into many walls and Single Walled Carbon Nanotube.The mechanics of carbon nanotube excellence, electromagnetic property make it have immeasurable application prospect in a lot of fields, especially aspect functional composite materials such as conduction, suction ripple, enhancing, have obtained great progress both at home and abroad.Yet the prerequisite of these application marketizations is to prepare carbon nanotube in enormous quantities, at low cost.
Preparation method of carbon nano-tube has arc process, laser method and chemical Vapor deposition process at present.Wherein chemical Vapor deposition process mainly is divided into loaded catalyst method, substrate method and the method for swimming again.(Chemical Physics Letters 2002:364,5-6 568-572) utilize loaded catalyst to realize the preparation in enormous quantities of many walls and Single Walled Carbon Nanotube respectively in fluidized-bed to people such as Wei Fei.Yet the carbon nanotube of being produced by loaded catalyst is single all to be random orientation, forms the poly-group of the micron order that is difficult to open easily, and this has a greatly reduced quality its a lot of excellent properties as one-dimensional material.
On the other hand, (Science 1998 for Ren ZF; 282:1105-7) and Fan, (Science 1999 for SS; 283,512-4) on glass and porous silicon substrate, grown the array of multi-walled carbon nanotubes on vertical substrate surface respectively.But be not difficult to find out, substrate method catalyst preparation process complexity, strict for substrate surface, reaction atmosphere, main, used substrate is tabular, be difficult to find the reactor types capable of being industrialized that adapts to it, make these class methods only can in the laboratory, obtain very a spot of directional carbon nanotube array.
1999, people such as Andrews (Chem Phys Lett 1999:303 (5-6): 467-74) utilize the method for swimming on silicon-dioxide substrate and tube wall, also to prepare directed array of multi-walled carbon nanotubes, because this method is compared with the conventional substrate method, need not other react supplementary meanss, the substrate pre-treatment is simple, easy handling, with low cost, quilt be it is believed that the incident of the milestone that is the carbon nano pipe array production in enormous quantities.The people such as Windle of Cambridge University in 2003 (Chem Phys Lett 2003:372 (5-6): 860-5) based on this, reduced the thickness of silicon-dioxide, obtained the array of more carbon nanotube in the unit volume, but their used collection substrate still only limits to the flaky silicon dioxide of atomically flating, make this method still can not with existing various reactors coupling, generally with truly prepare carbon nano pipe array in enormous quantities certain distance still arranged.
(Science 2004 for people such as nearest Ijima; 306:1362-4) proposed the method that preparation length reaches several millimeters single-wall carbon nanotube array again, but similar when used substrate and treatment process and aforementioned preparation array of multi-walled carbon nanotubes in this method, engineering method also has suitable distance in enormous quantities.
Summary of the invention:
Discover through us, except the smooth plane of atomic level, carbon nano pipe array also can be on various coarse planes in addition sphere form, the chemical ingredients of body phase also is not limited to silicon-dioxide simultaneously, the oxide compound of stable in properties under a lot of other high temperature, as zirconium dioxide, can both well collect carrier as array, this big quantum jump various carbon nano pipe array preparation methods' technical limitation, make us can in limited space, provide bigger surface energy low-cost, easily as the array collection body.Be equipped with in the legal system of swimming such as us that to insert diameter in the carbon nano pipe array reactor be 100 microns spheroidal particle, collect surface-area 10000 times when only using reactor wall.In conjunction with suitable reactor types, we have proposed to solve loaded catalyst and existing volume production of conventional substrate method and one-dimension oriented contradiction, realize new approaches of the production in enormous quantities of directed overlength carbon nano pipe.
The purpose of this invention is to provide a kind of method for preparing carbon nano pipe array in enormous quantities, and realize the device that this method adopted.
The feature of present method is that the surface in the suitable carbon nano pipe array growth of inside reactor increase generates carbon nano pipe array in enormous quantities with chemical Vapor deposition process; The surface of described increase is plane or curved surface, and the absolute value of the radius-of-curvature of described curved surface is greater than 1 micron; Described surface is atomically flating or non-atomically flating; It is zirconium dioxide, silicon-dioxide or aluminium sesquioxide that the body phase chemistry on described surface is formed, or is the mixture of major ingredient with described zirconium dioxide, silicon-dioxide or aluminium sesquioxide.
Described on the surface of the suitable carbon nano tube growth of inside reactor increase, realize by in reactor, filling solid particulate.Described solid particulate is that the surface is the planar polyhedron, or the surface is the solid of curved surface, or the surface is that the planar polyhedron is the combination of the solid of curved surface with the surface.The reactor that is adopted is fixed bed, moving-bed or fluidized-bed, or the reactor of the array configuration of described fixed bed, moving-bed, fluidized-bed.
Described carrier surface at the suitable carbon nano tube growth of inside reactor increase also can be realized by insert member in reactor.The member of described insertion is tabular, column or spirrillum member.The reactor that is adopted is fixed-bed reactor.
Describedly increase to be fit to the carrier surface of carbon nano tube growth, also can to realize by the reactor that utilization have a pore passage structure at inside reactor.The reactor that is adopted is only stone reactor.
Experimental results show that: utilize the present invention can be on various planes or curved surface prepare super long multi-wall and single-wall carbon nanotube array in enormous quantities with chemical Vapor deposition process, reached its intended purposes.
The present invention has following tangible advantage:
1. the bigger plane or the curved surface that utilize particle or reactor itself to provide, the carbon nano-tube oriented property of gained is good, output is big.
2. reaction atmosphere is loose with the requirement of collection carrier, and device is simple, and processing ease is with low cost.
3. very easily control the carbon length of tube, and can regulate other parameters such as external diameter in the carbon pipe, the interior iron-holder of tube chamber and array density.
4. the carbon nanotube that obtains of this method is higher than the product purity that obtains with loaded catalyst.
Description of drawings:
Fig. 1 is the picture of the spherome surface product of digital camera shooting.
Fig. 2 is the scanning electron microscope picture of spherome surface product, and for the ease of observing, partial array is manually destroyed, and upper left corner illustration is not ruined complete array.
Fig. 3 is the transmission electron microscope picture of reaction product, and the product carbon nanotube has good graphite linings structure as can be seen.
Fig. 4 is for can be used for reactor synoptic diagram of the present invention.
Embodiment:
It is consistent with the operational condition of the conventional substrate method and the method for swimming to prepare the used chemical Vapor deposition process of carbon nano pipe array among the present invention, and be specially: catalyzer is that diameter is iron, cobalt, the nickel metallic particles of 0.5～100nm; The deposition method of granules of catalyst is pre-soaked, sputter, molecular beam epitaxy, perhaps in-situ deposition in the reaction; Carbon source is various liquid state or gasiform hydro carbons, alcohol compound, as benzene,toluene,xylene, hexanaphthene, ethanol, methane, ethene, acetylene etc.; Temperature of reaction is 500～900 ℃; Shielding gas is the mixture of hydrogen and argon gas or nitrogen, wherein the ratio 1～10: 1 of argon gas or nitrogen and hydrogen; It is 0.01～10 hour that raw material injects volume space velocity
-1
Among the present invention used its working method of various forms of reactors of preparation carbon nano pipe array with prior art in the use-pattern of reactor consistent, its synoptic diagram such as Fig. 4.
Describe below in conjunction with specific embodiment.
Example 1
The spherical ceramic particle of aluminum oxide that diameter is about 1mm is filled in the fixed-bed reactor, and reactor feeds argon gas and hydrogen (air-flow also can be from top to bottom or about capable) from top to bottom, throughput ratio 5: 1, and 850 ℃ of temperature of reaction were with 0.1 hour
-1Air speed from the ferrocene benzole soln of reactor head spray 5mg/ml to reactor, react 30 minutes, stop heating and be cooled to room temperature taking-up ceramic particle.The particle surface product turns out to be the array of multi-walled carbon nanotubes of the about 500 microns marshalling of length through scanning and projection electron microscopic observation.Fig. 1 is the product pictorial diagram, and Fig. 2,3 is respectively its scanning and projection Electronic Speculum figure.Thermogravimetric analysis shows that product does not contain any agraphitic carbon, and multi-walled pipes content is greater than 95%.
Example 2
Median size is about the spherical ceramic particle of 50 microns zirconium dioxides and adds the reactor from the moving-bed top, and the autoreactor bottom feeds nitrogen and hydrogen, flow 20: 1, and 700 ℃ of temperature of reaction were with 1 hour
-1Air speed add 100mg/ml dicarbapentaborane iron hoop hexane solution from reactor bottom, react and open valve after 30 minutes, particle moves into segregation section, and this section is planted the surperficial also collection of product array lift-off particles, is transported to reactor head by riser tube after particle is calcined down through 600 ℃ of RS Regenerator Section and recycles.Product turns out to be the array of multi-walled carbon nanotubes of the about 200 microns marshalling of length through scanning and projection electron microscopic observation.
Example 3
Median size is about 100 microns glass microballons and is filled in the fluidized-bed reactor, feeds 10: 1 nitrogen of throughput ratio and hydrogen shield gas and feeds reactor from bottom to top, and the adjustments of gas flow makes particle near fluidisation, and 550 ℃ of temperature of reaction were with 0.05 hour
-1Air speed inject the ferrocene ethanolic soln of 20mg/ml; react and stop raw material supplying after 2 hours; increase shield gas flow rate and make the complete fluidisation of glass microballon; reactor head is collected product with whirlwind; after treating that product is deviate from fully, switching air valve bubbling air calcining residue carbon distribution returns to reaction conditions and carries out second circulation after 10 minutes.Product turns out to be the array of multi-walled carbon nanotubes of the about 100 microns marshalling of length through scanning and projection electron microscopic observation.
Example 4
To be that 2 millimeters, length are that the member that 500 millimeters cylindrical silicon oxide is formed inserts in the fixed-bed reactor by 100 diameters, (air-flow also can be from bottom to top or about row) feeds argon gas and hydrogen from top to bottom, throughput ratio 1: 1,800 ℃ of temperature of reaction were with 10 hours
-1Air speed inject the dicarbapentaborane iron xylene solution of 1mg/ml from the top, react 4 hours postcooling taking-up members.The periphery product turns out to be the array of multi-walled carbon nanotubes that length reaches 2 millimeters marshalling through scanning and projection electron microscopic observation.
Example 5
The duct is a square, and the aperture length of side is the only stone reactor of 4000 microns aluminum oxide, and its surface is the iron of 0.5nm by the molecular beam epitaxy deposit thickness, (air-flow also can be from bottom to top or about row) feeds argon gas and hydrogen from top to bottom, throughput ratio 1: 1,900 ℃ of temperature of reaction were with 10 hours
-1Air speed inject methane gas from reactor head, reacted 20 minutes.Solely the stone duct is shown
The face product turns out to be the single-wall carbon nanotube array of the marshalling of 2 millimeters of length through scanning and projection electron microscopic observation.
Claims (9)
1, the method for large-batch preparing overlength carbon nano pipe array is characterized in that, increases the surface that is fit to the carbon nano pipe array growth at inside reactor, generates carbon nano pipe array in enormous quantities with chemical Vapor deposition process; The surface of described increase is plane or curved surface, and the absolute value of the radius-of-curvature of described curved surface is greater than 1 micron; Described surface is atomically flating or non-atomically flating; It is zirconium dioxide, silicon-dioxide or aluminium sesquioxide that the body phase chemistry on described surface is formed, or is the mixture of major ingredient with described zirconium dioxide, silicon-dioxide or aluminium sesquioxide.
2, the method for large-batch preparing overlength carbon nano pipe array as claimed in claim 1 is characterized in that, and is described on the surface of the suitable carbon nano tube growth of inside reactor increase, realizes by fill solid particulate in reactor.
3, the method for large-batch preparing overlength carbon nano pipe array as claimed in claim 2, it is characterized in that, described solid particulate is that the surface is the planar polyhedron, or the surface is the solid of curved surface, or the surface is that the planar polyhedron is the combination of the solid of curved surface with the surface.
4, realizing the reactor that method adopted of large-batch preparing overlength carbon nano pipe array as claimed in claim 2, it is characterized in that, is fixed bed, moving-bed or fluidized-bed, or the reactor of the array configuration of described fixed bed, moving-bed, fluidized-bed.
5, the method for large-batch preparing overlength carbon nano pipe array as claimed in claim 1 is characterized in that, described carrier surface at the suitable carbon nano tube growth of inside reactor increase is realized by insert member in reactor.
6, as the method for large-batch preparing overlength carbon nano pipe array as described in the claim 5, it is characterized in that the member of described insertion is tabular, column or spirrillum member.
7, realizing the reactor that method adopted of large-batch preparing overlength carbon nano pipe array as claimed in claim 5, it is characterized in that, is fixed-bed reactor.
8, the method for large-batch preparing overlength carbon nano pipe array as claimed in claim 1 is characterized in that, describedly increase to be fit to the carrier surface of carbon nano tube growth at inside reactor, is to realize by the reactor that utilization has a pore passage structure.
9, realizing the reactor that method adopted of large-batch preparing overlength carbon nano pipe array as claimed in claim 8, it is characterized in that, is only stone reactor.
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| WO2008055421A1 (en) * | 2006-11-10 | 2008-05-15 | Tsinghua University | Carbon-nanotube arrays, yarns, films and composites, and the methods for preparing the same |
| CN101092234B (en) * | 2006-06-21 | 2011-03-23 | 鸿富锦精密工业（深圳）有限公司 | Apparatus and method for developing film of Nano carbon tube |
| CN102482098A (en) * | 2009-09-10 | 2012-05-30 | 国立大学法人东京大学 | Method For Simultaneously Producing Carbon Nanotubes And Hydrogen, And Device For Simultaneously Producing Carbon Nanotubes And Hydrogen |
| CN102515140A (en) * | 2011-11-29 | 2012-06-27 | 清华大学 | Method for large-scale preparation for nitrogen-doped carbon nanotube aligned array |
| CN103827025A (en) * | 2011-09-14 | 2014-05-28 | 株式会社藤仓 | Structure for forming carbon nanofiber, carbon nanofiber structure and method for producing same, and carbon nanofiber electrode |
| US8900367B2 (en) | 2006-06-16 | 2014-12-02 | Tsinghua University | Apparatus and method for manufacturing large-area carbon nanotube films |
| US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
| CN107565115A (en) * | 2017-08-30 | 2018-01-09 | 北方奥钛纳米技术有限公司 | Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material |
| CN108232144A (en) * | 2017-12-25 | 2018-06-29 | 北方奥钛纳米技术有限公司 | A kind of modified silicon-carbon composite electrode material and preparation method thereof |
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| CN1207185C (en) * | 2000-09-26 | 2005-06-22 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| US7182924B2 (en) * | 2001-03-13 | 2007-02-27 | Corning Incorporated | Substrate packing for monolith reactors |
| CN1224573C (en) * | 2001-08-22 | 2005-10-26 | 中国科学院成都有机化学研究所 | Continuous carbon nano-tube preparation by rotary moving-bed reactor |
| CN1207187C (en) * | 2003-07-18 | 2005-06-22 | 清华大学 | Purification method of carbon nano pipe and its device |
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| US8900367B2 (en) | 2006-06-16 | 2014-12-02 | Tsinghua University | Apparatus and method for manufacturing large-area carbon nanotube films |
| CN101092234B (en) * | 2006-06-21 | 2011-03-23 | 鸿富锦精密工业（深圳）有限公司 | Apparatus and method for developing film of Nano carbon tube |
| WO2008055421A1 (en) * | 2006-11-10 | 2008-05-15 | Tsinghua University | Carbon-nanotube arrays, yarns, films and composites, and the methods for preparing the same |
| US10633249B2 (en) * | 2009-09-10 | 2020-04-28 | The University Of Tokyo | Device for simultaneously producing carbon nanotubes and hydrogen |
| CN102482098A (en) * | 2009-09-10 | 2012-05-30 | 国立大学法人东京大学 | Method For Simultaneously Producing Carbon Nanotubes And Hydrogen, And Device For Simultaneously Producing Carbon Nanotubes And Hydrogen |
| US9061909B2 (en) | 2009-09-10 | 2015-06-23 | The University Of Tokyo | Method for simultaneously producing carbon nanotubes and hydrogen, and device for simultaneously producing carbon nanotubes and hydrogen |
| CN103827025A (en) * | 2011-09-14 | 2014-05-28 | 株式会社藤仓 | Structure for forming carbon nanofiber, carbon nanofiber structure and method for producing same, and carbon nanofiber electrode |
| CN103827025B (en) * | 2011-09-14 | 2016-08-24 | 株式会社藤仓 | Carbon nano-fiber is formed with tectosome, carbon nano-fiber tectosome and manufacture method thereof and carbon nano-fiber electrode |
| CN102515140A (en) * | 2011-11-29 | 2012-06-27 | 清华大学 | Method for large-scale preparation for nitrogen-doped carbon nanotube aligned array |
| US9506194B2 (en) | 2012-09-04 | 2016-11-29 | Ocv Intellectual Capital, Llc | Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media |
| CN107565115A (en) * | 2017-08-30 | 2018-01-09 | 北方奥钛纳米技术有限公司 | Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material |
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| CN117646198A (en) * | 2024-01-30 | 2024-03-05 | 浙江大学 | Automatic control method and system for pressure of atomic-level-precision CVD equipment |
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Assignee: Tsinghua University Assignor: XINNA TECHNOLOGY CO., LTD. Contract record no.: 2010990000860 Denomination of invention: Method for large-batch preparing overlength carbon nano pipe array and its apparatus Granted publication date: 20070425 License type: Exclusive License Open date: 20060125 Record date: 20101027 |
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Application publication date: 20060125 Assignee: Jiangsu Nanai Polytron Technologies Inc Assignor: Tsinghua University Contract record no.: X2019990000138 Denomination of invention: Method for large-batch preparing overlength carbon nano pipe array and its apparatus Granted publication date: 20070425 License type: Exclusive License Record date: 20191024 |