CN105731415B - A kind of overlength carbon nano pipe preparation facilities and preparation method thereof - Google Patents
A kind of overlength carbon nano pipe preparation facilities and preparation method thereof Download PDFInfo
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- CN105731415B CN105731415B CN201410744662.XA CN201410744662A CN105731415B CN 105731415 B CN105731415 B CN 105731415B CN 201410744662 A CN201410744662 A CN 201410744662A CN 105731415 B CN105731415 B CN 105731415B
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Abstract
The present invention proposes a kind of overlength carbon nano pipe preparation method and device; based on floating catalyst system chemical vapour deposition technique; designed using improved fixed bed device and special substrate; realize the prepare with scale of overlength High-conductivity carbon nanotube dust; the present invention is from liquid carbon source safe under pure inert atmosphere; the Quartz Microsphere good using chemical stability is used as substrate; intermittent water etching and improved sampler is taken to realize that CNT is quickly moved out into reaction system collects; preparation method operating procedure of the present invention is simple, and cost saves significantly on.
Description
Technical field
The present invention relates to carbon nanomaterial preparation technology field, more particularly to a kind of floating catalyst system chemical vapor deposition skill
Device of art prepare with scale overlength High-conductivity carbon nanotube and preparation method thereof.
Technical background
In recent years, the technology for CNT being manufactured with magnanimity is increasingly improved, and the scale application of CNT is gradual to be obtained
To development, the particularly nanometer reinforcing phase for composite.However, presently commercially available CNT is generally to roll into a ball cotton-shaped presence,
And the features such as generally existing length is short, caliber is thin, defect is more, cause its electrical conductivity relatively low, it is difficult when for preparing composite
Effectively scattered to obtain, conductivity threshold is low, and significant advantage is had no compared with as the conductive black of conventional conductive filler.Therefore,
Realize prepared by the magnanimity for being more easy to scattered highly conductive overlength carbon nano pipe, help further to promote the scale application of CNT
With.
Floating catalyst system chemical vapour deposition technique is that fixed bed chemical vapor deposition prepares vertical carbon nanotube array
One of basic skills, its carbon nano pipe array obtained have that crystallinity is high, the features such as length is big, and can pass through air-flow, temperature
Change control its caliber change.However, the extremely limited substrate of fixed bed makes it can not obtain volume production ability.Tsing-Hua University's profit
Carbon nano tube growth is carried out by the use of grade Ceramic Balls as growth substrate（Chinese invention patent, ZL 2005100120667.8）,
So as to effectively expand substrate specific surface area, however this method under fixed bed system because the air-flow containing carbon source is difficult to expand
The container lower floor for filling ceramic microsphere is dissipated to, so as to substantially only have one layer of surface Ceramic Balls to turn into carbon nano tube growth
Effective substrate, substrate utilization rate is greatly reduced, therefore be usually forced anti-using some complicated porous member insertion fixed beds
Answer device or use cost is higher, the more complicated moving bed and fluidized bed reaction of operation.Inserted in fixed bed reactors more
Pole is unfavorable for passing through for air-flow, and CNT and deposition carbon be possible to depend on porous member growth so as to by its
Obstruction, cause to react gas circuit by resistance initiation danger.What is more important, such a reaction system need to introduce more than 10% ratio
Hydrogen, so as to cause danger coefficient further to increase.In fact, hydrogen is not essential in floating catalyst system growing system
Factor.Therefore, the life of CNT in safe atmosphere is developed under the fixed bed system of floating catalyst system chemical vapor deposition
Long technique contributes to its scale application.
The content of the invention
To solve prior art in the defects of highly conductive overlength carbon nano pipe technique of prepare with scale, the invention provides
A kind of method that can high-volume prepare highly conductive overlength carbon nano pipe under safe atmosphere.
The overlength carbon nano pipe preparation facilities of the present invention includes a quartz ampoule reaction chamber, and the quartz ampoule reaction chamber front end is to add
Hot-zone gasifying mouth, including carbon source, water and inert body gas entrance, one end are gas outlet, and a stone is placed at quartz ampoule reaction chamber center
Ying Zhou, quartz boat have a large amount of micropores close to air inlet side, and quartz boat is growth substrate built with quartz glass pearl；Quartz boat leans on
Nearly gas outlet side penetrates a high temperature alloy agitating paddle, agitating paddle through quartz ampoule reaction chamber outlet port flange with it is electronic
Machine is connected, and a high temperature alloy scraping ring consistent with quartz ampoule reaction chamber inner wall size is terminated before quartz boat, and reaction chamber afterbody is set
There is collector.
A diameter of 2-500 centimetres of quartz ampoule reaction chamber in the present invention, quartz boat micropore size are 0.1-5 millimeters, quartzy glass
The a diameter of 0.01-5 millimeters of glass pearl.
Technical scheme additionally provides the preparation method that overlength carbon nano pipe is prepared using the device, this method step
Suddenly it is：
1）, by inert gas, liquid carbon source, catalyst through front end heating zone gasify after be directly injected into described in claim 1
Device in carry out floating catalyst system chemical vapor deposition, reaction temperature is 600-1200 DEG C, and the reaction time is 0.5-10 small
When；
2）, step 1）Stop being passed through carbon source after end, start to cool, a small amount of water is passed through in temperature-fall period so that the carbon of generation
Nanotube separates with quartz glass pearl substrate；
3）, treat that temperature is down to less than 400 DEG C, pull out quartz boat and received tube wall and the carbon in sample cell by high temperature alloy ring
Mitron together blows into collector.
Step 1）In inert gas be helium, argon gas or its arbitrary proportion gaseous mixture, flow 20-2000 mL/min；
Liquid carbon source includes but is not limited to one kind of ethanol, methanol, toluene, dimethylbenzene, benzene, n-hexane, hexamethylene, acetone, acetonitrile etc.
Or its mixing, catalyst are any one of iron chloride, ferric nitrate, ferric acetyl acetonade, ferrocene etc..Catalyst is dissolved in liquid carbon
In source, mass percent 1%-5%.Injection rate dissolved with the liquid carbon source of catalyst is 0.1-50ml/h.Step 2）Middle note
Water is 0.5-500ml, and the time is no longer than from the duration for stopping being heated to be cooled to 400 degree.
Growth atmosphere is pure inert atmosphere, predominantly nitrogen or argon gas or the two with a certain proportion of gaseous mixture；Carbon source is
Hydro carbons, alcohols or the ketone of liquid, catalyst is any one of iron chloride, ferric nitrate, ferric acetyl acetonade, ferrocene etc., molten
In liquid carbon source, growth course reaction chamber is directly injected into after front end heating zone is gasified.When starting cooling after growth terminates
Stop liquid carbon source of the injection dissolved with catalyst, and start to inject water, by being converted into vapor during the heating zone of front end, inject
Reaction chamber etches the contact portion of CNT and substrate, so as to reach the effect that CNT separates with substrate.
Carbon nano tube growth substrate selects the optimum growth substrate Quartz Microsphere life of CNT under inert atmosphere
Long CNT, being placed on one, stove center inlet end one side has in the quartz boat of a large amount of micropores.In order to ensure carbonaceous sources gas
Stream can fully contact all Quartz Microsphere surfaces as far as possible, install a deeply reaction additional in quartz ampoule outlet end flanges
The high temperature alloy puddler in area, can be sufficiently stirred Quartz Microsphere, so as to ensure the Gao Bibiao of Quartz Microsphere
Area can be fully used, and grow a large amount of CNTs.
A high temperature alloy scraping ring consistent with quartz ampoule inner wall size is terminated before quartz boat, for striking off on tube wall
CNT, growth terminates and completes to be down to room temperature after water etching can be during quartz boat be taken out disposably by tube wall
CNT all wipes collection off, is placed in the collection vessel below pipe tail.
Implement technical scheme, compared to prior art itself obvious advantage is that：
The present invention grows overlength High-conductivity carbon nanotube using inert atmosphere, on the one hand improves the safety of growing environment
Property, on the other hand also reduce cost.Grow obtained CNT in the form of orthogonal array to exist, there is high crystallinity
Longer length, CNT is more conducive in conductive plastics reinforcement, cell conductive paste, electric heating film etc. because obtained from
The application in field.In addition, aid in external agitating paddle and quartz boat preposition by designing Quartz Microsphere high-specific surface area substrate
Air inlet micropore, the specific surface area of carbon nano tube growth substrate can be effectively improved, so as to lift the yield of CNT.During cooling
The step of injecting water vapour can realize the decrease of CNT and substrate adhesion under conditions of the time is effectively utilized, front end
High temperature alloy scraping ring, which then disposably can all scrape a large amount of CNTs on tube wall the collection for helping to be collected into pipe tail, to be held
In device, the length of carbon nanotube of acquisition is at 100 to 5000 microns, diameter 50-150nm.This series of steps and improvement can be significantly
The preparation efficiency of CNT is improved, so as to contribute to its scale application.
Brief description of the drawings
Fig. 1-prepare overlength carbon nano pipe installation drawing；
Fig. 2-quartz boat structure schematic diagram；
Fig. 3-High-conductivity carbon nanotube microstructure photograph
In figure：1- carbon source entrances；
2- water inlets；
3- inert gas entrances；
4- gas outlets；
5- CNT collectors；
6- motor；
7- high temperature alloy scraping rings；
8- inlet ends have micropore quartz boat；
9- high temperature alloy agitating paddles；
10- quartz glass pearls；
11- quartz boats top is open；
The micropore that 12- quartz boats are surveyed on boat wall towards inlet end one.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
The overlength carbon nano pipe preparation facilities of the present invention includes a quartz ampoule reaction chamber, and the quartz ampoule reaction chamber front end is to add
Hot-zone gasifying mouth, including carbon source, water and inert gas entrance, the other end are gas outlet, and one is placed at quartz ampoule reaction chamber center
Quartz boat, quartz boat have a large amount of micropores close to air inlet side, and quartz boat is growth substrate built with quartz glass pearl；Quartz boat
A high temperature alloy agitating paddle is penetrated close to gas outlet side, agitating paddle passes through quartz ampoule reaction chamber outlet port flange and electricity
Motivation is connected, and a high temperature alloy scraping ring consistent with quartz ampoule reaction chamber inner wall size, reaction chamber afterbody are terminated before quartz boat
Provided with collector.
A diameter of 2-500 centimetres of quartz ampoule reaction chamber in invention, quartz boat micropore size are 0.1-5 millimeters, quartz glass
The a diameter of 0.01-5 millimeters of pearl.
Overlength nanometer tube preparation method bag following steps in technical solution of the present invention：Front end there is into breathable microporous and connected
The quartz boat of high temperature alloy scraping ring is positioned over the stove heart, built-in Quartz Microsphere, and has the high temperature alloy stirring for penetrating quartz boat
Oar is connected by gas outlet flange with external motor.CNT is grown under the inert atmospheres such as nitrogen, argon gas, is injected dissolved with urging
The liquid carbon source of agent, growth terminate water flowing etching separating carbon nano-tube and growth substrate in rear temperature-fall period, are down to nearly room temperature
The CNT on tube wall can disposably be scraped during quartz boat is pulled out afterwards and be collected into the receipts of pipe tail positioned beneath
Collect in container, a diameter of 2-500 centimetres of quartz ampoule reaction chamber, quartz boat micropore size is 0.1-5 millimeters, quartz glass pearl diameter
For 0.01-5 millimeters.
Embodiment 1：
As shown in figure 1, structure used in being main implementation of the invention, comprises the following steps：
Quartz Microsphere is fitted into push-in quartz ampoule reaction zone in quartz boat, using benzene as carbon source, dissolves in 1% two cyclopentadienyls
For iron as catalyst, growth temperature is 720 DEG C, and carrier gas is nitrogen, and carrier gas flux 20ml/min, growth time is 0.5 hour.
Benzene and ferrocene mixed liquor injection rate 0.1ml/h.Growth stops injection mixed liquor after terminating, start water filling, and injection l amounts are
0.5 milliliter, it is down to temperature after 400 degree and stops water flowing, is opened outlet end flanges and disposably scrape the CNT on tube wall
And it is collected into the collection vessel of pipe tail positioned beneath.
Embodiment 2：
Quartz Microsphere is fitted into push-in quartz ampoule reaction zone in quartz boat, using acetone as carbon source, dissolves in 4% chlorine
Change iron as catalyst, growth temperature is 600 DEG C, and carrier gas is argon gas, and carrier gas flux 800ml/min, growth time is 2 small
When.When acetone is with iron chloride mixed liquor injection rate 10ml/h.Growth stops injection toluene solution of ferrocene after terminating, start to note
Water, injection volume 100ml, it is down to temperature after 400 degree and stops water flowing, air inlet end flanges to be opened takes out CNT, and carbon is received
Mitron microscopic appearance is as shown in Figure 3.
Embodiment 3：
Quartz Microsphere is fitted into push-in quartz ampoule reaction zone in quartz boat, using n-hexane as carbon source, dissolves in 2%
Ferric nitrate is catalyst, and growth temperature is 1000 DEG C, and carrier gas is argon gas and nitrogen mixture, carrier gas flux 1600ml/min,
Growth time is 8 hours.N-hexane and ferric nitrate mixed liquor injection rate 25ml/h.Growth stops injection mixed liquor after terminating,
Start water filling, injection volume 300ml, stop water flowing after being down to 400 degree to temperature, carbon nanometer is taken out after temperature is down to room temperature
Pipe.
Embodiment 4：
Quartz Microsphere is fitted into push-in quartz ampoule reaction zone in quartz boat, using ethanol as carbon source, dissolves in 5% second
For acyl acetone iron as catalyst, growth temperature is 1200 DEG C, and carrier gas is argon gas, carrier gas flux 2000, ml/min, growth time
For 10 hours.Ethanol closes liquid injection rate 50ml/h with ferric acetyl acetonade.Growth stops injection mixed liquor after terminating, start to note
Water, injection volume 500ml, stop water flowing after being down to 400 degree to temperature, CNT is taken out after temperature is down to room temperature.
The length of carbon nanotube obtained by above example is at 100 to 5000 microns, diameter 50-150nm.This is a series of
Step and improvement can greatly improve the preparation efficiency of CNT, so as to contribute to its scale application.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, the change or replacement that can readily occur in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be with protection model that claim is defined
Enclose and be defined.
Claims (7)
1. a kind of overlength carbon nano pipe preparation facilities, the device includes a quartz ampoule reaction chamber, and the quartz ampoule reaction chamber front end is
Heating zone gasifying mouth, including carbon source, water and inert gas entrance, the other end are gas outlet, are placed at quartz ampoule reaction chamber center
One quartz boat, quartz boat have a large amount of micropores close to front end heating zone gasifying mouth side, and quartz boat is made a living built with quartz glass pearl
Long substrate；Quartz boat penetrates a high temperature alloy agitating paddle close to gas outlet side, and agitating paddle goes out through quartz ampoule reaction chamber
Gas port end flanges are connected with motor, and a high temperature alloy consistent with quartz ampoule reaction chamber inner wall size is terminated before quartz boat and is scraped
Ring, reaction chamber afterbody are provided with collector.
A kind of 2. overlength carbon nano pipe preparation facilities according to claim 1, it is characterised in that described quartzy tube reaction
Chamber diameter of section is 2-500 centimetres.
A kind of 3. overlength carbon nano pipe preparation facilities according to claim 1, it is characterised in that described quartz boat micropore
Aperture is 0.1-5 millimeters.
A kind of 4. overlength carbon nano pipe preparation facilities according to claim 1, it is characterised in that described quartz glass pearl
A diameter of 0.01-5 millimeters.
5. a kind of preparation method of overlength carbon nano pipe, comprises the following steps：
1）, by inert gas and dissolved with the liquid carbon source of catalyst hold before menstruation heating zone gasify after be directly injected into claim 1 institute
Floating catalyst system chemical vapor deposition is carried out in the device stated, reaction temperature is 600-1200 DEG C, and the reaction time is 0.5-10 small
When；
2）, step 1）Stop being passed through carbon source after end, start to cool, a small amount of water is passed through in temperature-fall period so that the carbon nanometer of generation
Pipe separates with quartz glass pearl substrate, until temperature is down to less than 400 degree；
3）, treat that temperature is down to less than 400 DEG C, pull quartz boat by alloy hoop by the CNT in tube wall and quartz boat together
Blow into collecting tank；
Step 1）In liquid carbon source be hydro carbons, alcohols or ketone, described catalyst is iron chloride, ferric nitrate, acetylacetone,2,4-pentanedione
Any one of iron, ferrocene；
Step 1）In catalyst be dissolved in liquid carbon source, mass percent 0.1%-5%；
Step 1）In carbon source and catalyst mixed solution injection rate be 0.1-50ml/h；
Step 2）Middle water injection rate is 0.5-500ml.
A kind of 6. preparation method of overlength carbon nano pipe according to claim 5, it is characterised in that described inert gas
For the gaseous mixture of helium, argon gas or its arbitrary proportion, flow 20-2000ml/min.
7. the preparation method of a kind of overlength carbon nano pipe according to claim 5, it is characterised in that described hydro carbons, alcohol
Class or the liquid carbon source of ketone are one kind in ethanol, methanol, toluene, dimethylbenzene, benzene, n-hexane, hexamethylene, acetone, acetonitrile
Or its mixing.
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| CN110451486B (en) * | 2019-08-08 | 2022-11-22 | 江西铜业技术研究院有限公司 | Device and method for preparing carbon nanotubes in batches |
| CN112678805A (en) * | 2021-01-26 | 2021-04-20 | 中国科学院金属研究所 | Method and device for preparing multi-wall carbon nanotube film by floating catalyst chemical vapor deposition method |
| CN114267492B (en) * | 2021-12-31 | 2023-07-25 | 大连工业大学 | Uniform transparent conductive film with long tube bundle carbon nano tubes and preparation method thereof |
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| KR20010027422A (en) * | 1999-09-13 | 2001-04-06 | 이영희 | High yield purification of multiwalled carbon nanotubes by thermal annealing method |
| CN1837034A (en) * | 2005-03-25 | 2006-09-27 | 清华大学 | Carbon nanotube array growing device |
| CN1935637A (en) * | 2005-09-23 | 2007-03-28 | 清华大学 | Method for preparing carbon nano tube |
| CN103466594A (en) * | 2013-08-27 | 2013-12-25 | 西北工业大学 | Temperature control CVD furnace and method for controllably preparing single-wall carbon nano tubes with temperature control CVD furnace |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010027422A (en) * | 1999-09-13 | 2001-04-06 | 이영희 | High yield purification of multiwalled carbon nanotubes by thermal annealing method |
| CN1837034A (en) * | 2005-03-25 | 2006-09-27 | 清华大学 | Carbon nanotube array growing device |
| CN1935637A (en) * | 2005-09-23 | 2007-03-28 | 清华大学 | Method for preparing carbon nano tube |
| CN103466594A (en) * | 2013-08-27 | 2013-12-25 | 西北工业大学 | Temperature control CVD furnace and method for controllably preparing single-wall carbon nano tubes with temperature control CVD furnace |
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