CN102557012B - Chemical vapor deposition method for continuously preparing carbon nanotubes with few walls under condition of no carrier gas - Google Patents

Chemical vapor deposition method for continuously preparing carbon nanotubes with few walls under condition of no carrier gas Download PDF

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CN102557012B
CN102557012B CN2012100639463A CN201210063946A CN102557012B CN 102557012 B CN102557012 B CN 102557012B CN 2012100639463 A CN2012100639463 A CN 2012100639463A CN 201210063946 A CN201210063946 A CN 201210063946A CN 102557012 B CN102557012 B CN 102557012B
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reactor
carrier gas
carbon nanotube
gas
precursor solution
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CN2012100639463A
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CN102557012A (en
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侯峰
常美艳
阮丁山
董留兵
赵莎
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天津大学
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Abstract

The invention discloses a method for continuously preparing carbon nanotubes with a few walls under the condition of no carrier gas. The method comprises the following steps of: uniformly mixing a carbon source, a catalyst and a promoter through ultrasonic waves to obtain a precursor solution; and heating a reactor to the temperature of between 600 and 1,200DEG C in the inert atmosphere, stoppingintroducing gas, respectively injecting the precursor solution and methanol into the reactor, and continuously synthesizing a carbon nanotube material with a few walls at high temperature without carrier gas. The method has the advantages of safe operation, simple process, uniform product appearance and the like, and the carbon nanotube material with a few walls (n is less than or equal to 10) can be continuously synthesized.

Description

The method of chemical gas-phase method continuous production few-wall carbon nanotube under the no carrier gas condition

Technical field

The invention relates to the preparation nano material, particularly a kind of under the no carrier gas condition method of chemical Vapor deposition process continuous production few-wall carbon nanotube.

Background technology

Carbon nanotube is a kind of typical monodimension nanometer material, owing to have the performances such as unique structure, high specific surface area, high electric conductivity and thermal conductivity and good machinery, Chu Qing, so that it all has wide practical use in matrix material and material preparation, the energy, Chu Qing field.For example: with carbon nanotube and metal oxide or compound (TiO 2, SnO 2, MnO 2, LiMn 2O 4, LiFePO 4Deng) compound electrode materials as lithium ion battery, solar cell, ultracapacitor, its conductivity be can greatly strengthen and then specific storage and cycle performance improved; As support of the catalyst, but loaded metal particle (such as Pt) preparation effective catalyst; With compound mechanical property and conductivities that strengthens polymkeric substance such as polymkeric substance; Carbon nanotube also can be made the toughener of metal, pottery simultaneously.In addition, carbon nanotube also has huge potential using value at aspects such as medical science and military affairs.

The method of synthesizing carbon nanotubes mainly contains arc discharge method, laser ablation method, chemical Vapor deposition process, solid-phase pyrolysis and polyreaction synthesis method etc. at present.Wherein chemical gas-phase method because of have product purity high and evenly, can produce, the advantage such as cheap, be more a kind of method of synthesizing carbon nanotubes of present application.There is at present patent (CN101153413, CN101187094, CN 200910069120.6, CN 101696519A) to disclose and adopts water-lute and water to help chemical gas phase reaction to prepare the method for carbon nano-tube fibre, but these methods all need adopt hydrogen or rare gas element (argon gas or nitrogen) as carrier gas, and this has brought the problem of secure context to industrial production in enormous quantities.

Summary of the invention

The present invention seeks to the shortcoming and defect for prior art, provide a kind of no carrier gas, product continuously, be applicable to the preparation method of the carbon nanotube of suitability for industrialized production.In the difference injecting reactor, under no carrier gas atmosphere, carry out pyroreaction Formed nanotube during specifically with precursor mixed solution and methyl alcohol high temperature.

In the mixing solutions and methyl alcohol difference while injecting reactor of the method with carbon source, catalyzer, promotor, under the no carrier gas condition, prepare carbon nanotube.Simultaneously, the factors such as the notes speed of mass percent, precursor solution and the methyl alcohol by regulating catalyzer and promotor and temperature of reactor are regulated the microscopic appearance of Formed nanotube.

The present invention relates to the method for chemical gas-phase method continuous production few-wall carbon nanotube under a kind of no carrier gas condition, concrete steps are as follows:

(1) configuration precursor solution

Ultrasonic the mixing of carbon source, catalyzer and promotor is made into precursor solution;

Described carbon source is carbonaceous organic material: any one or multiple mixture in ethanol, acetone, hexanaphthene, ether, benzene, the normal hexane account for the 95-99% of reactant total mass;

Described catalyzer is one or more the mixture in ferrocene, nickelous oxalate, ironic oxalate, Cobaltous diacetate, the ammonium molybdate, accounts for the 0.5-3% of reactant total mass;

Described promotor is the mixture of any one or two kinds of thiophene and water, accounts for the 0.1-2% of reactant total mass;

(2) high temperature building-up reactions

Under inert atmosphere protection, reactor is warmed up to 600-1200 ℃, stop to reactor ventilation body, with the precursor solution that obtains in the step (1) and methyl alcohol respectively in the speed injecting reactor with 2-20ml/h and 40-100ml/h, continuously synthetic few-wall carbon nanotube material under the no carrier gas hot conditions;

Described rare gas element is the gas mixture of any one or two kinds of argon gas and nitrogen.

Described step (2) preferred range that reactor heats up under inert atmosphere protection is 1000-1200 ℃.

The precursor solution of described step (2) and the preferred rate in the methyl alcohol injecting reactor are respectively 5-12ml/h and 40-70ml/h.

The invention has the beneficial effects as follows, introduce methyl alcohol, under the condition of no carrier gas, synthesize continuously the carbon nanotube of few wall.It has operational safety, technique simple, can synthesize continuously, the advantage such as the product pattern is even, provide new approaches for the chemical gas-phase method synthetic materials simultaneously.The present invention can generate the carbon nano-tube material of few wall (n≤10) continuously.

Description of drawings

Fig. 1 is the electron scanning micrograph of the carbon nanotube of example 1 preparation;

Fig. 2 is the low power transmission electron microscope photo of the carbon nanotube of example 1 preparation;

Fig. 3 is the high power transmission electron microscope photo of the carbon nano-tube bundle of example 1 preparation.

Embodiment

Below by embodiment the present invention is further detailed, the raw materials used analytical pure that is of embodiment, specific embodiment is as follows.

Embodiment 1

(1) take by weighing 30g ethanol, the 0.15g thiophene, the 0.60g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 1140 ℃; stop to the logical argon gas of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 8ml/h, 50ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

The few-wall carbon nanotube material of the present invention preparation, about characterizing method and characterization result as follows:

Morphology characterization: adopt JSM-6700F EOL awkward silence at a meeting emission scan electron microscope and Dutch Tecnai G2F20 type field transmission electron microscope observation product pattern.

Fig. 1 is the electron scanning micrograph of the carbon nanotube of embodiment 1 preparation.The product pattern is more even, and the carbon nanotube length-to-diameter ratio is larger, and being interweaved reticulates structure.

Fig. 2 is the transmission electron microscope photo of the carbon nanotube of embodiment 1 preparation.Product is relatively more uniform thin straight carbon nanotube, carbon nanotube outer wall smoother, and catalyst particle size is more even, has a small amount of granules of catalyst to adhere to part carbon nanotube outer wall.

Fig. 3 is the transmission electron microscope photo of the carbon nanotube of embodiment 1 preparation.Product is double-walled carbon nano-tube, and diameter is 2-3nm, and catalyst particle size is 5-7nm.

Embodiment 2

(1) take by weighing 30g ethanol, the 0.13g thiophene, the 0.45g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 1000 ℃; stop to the logical argon gas of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 20ml/h, 100ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Embodiment 3

(1) take by weighing 30g ethanol, the 0.03g thiophene, the 0.15g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 1200 ℃; stop to the logical argon gas of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 2ml/h, 40ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Embodiment 4

(1) take by weighing 30g ethanol, the 0.63g thiophene, the 0.95g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under nitrogen protection atmosphere, reactor being warmed up to 1050 ℃; stop to the logical nitrogen of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 8ml/h, 60ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Embodiment 5

(1) take by weighing 30g benzene, the 0.20g thiophene, the 0.50g ironic oxalate, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 600 ℃, stop to the logical argon gas of reactor, with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 6ml/h, 50ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Embodiment 6

(1) take by weighing the 30g normal hexane, the 0.15g thiophene, the 0.60g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 1150 ℃; stop to the logical argon gas of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 8ml/h, 50ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Embodiment 7

(1) take by weighing the 30g hexanaphthene, the 0.13g thiophene, the 0.50g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 800 ℃; stop to the logical argon gas of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 12ml/h, 70ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Embodiment 8

(1) take by weighing 30g ethanol, the 0.15g thiophene, 0.15g water, the 0.60g ferrocene, ultrasonic 30min mixes it, is transferred in the syringe.

When (2) under argon shield atmosphere, reactor being warmed up to 1100 ℃; stop to the logical argon gas of reactor; with precursor mixed solution in the step (1) and methyl alcohol respectively with the speed of 15ml/h, 80ml/h simultaneously in the injecting reactor, continuous synthesizing carbon nanotubes.

Above-mentioned description to embodiment is to be convenient to those skilled in the art can understand and apply the invention.The person skilled in the art easily makes various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.

Claims (3)

1. the method for chemical gas-phase method continuous production few-wall carbon nanotube under the no carrier gas condition, concrete steps are as follows:
(1) configuration precursor solution
Mix carbon source, catalyzer and promotor are ultrasonic, be made into precursor solution;
Described carbon source is carbonaceous organic material: any one or multiple mixture in ethanol, acetone, hexanaphthene, ether, benzene, the normal hexane account for the 95-99% of reactant total mass;
Described catalyzer is any one or multiple mixture in ferrocene, nickelous oxalate, ironic oxalate, Cobaltous diacetate, the ammonium molybdate, accounts for the 0.5-3% of reactant total mass;
Described promotor is the mixture of any one or two kinds of thiophene and water, accounts for the 0.1-2% of reactant total mass;
(2) high temperature building-up reactions
Under inert atmosphere protection, reactor is warmed up to 600-1200 ℃, stop to reactor ventilation body, with the precursor solution that obtains in the step (1) and methyl alcohol respectively in the speed injecting reactor with 2-20ml/h and 40-100ml/h, continuously synthetic few-wall carbon nanotube material under the no carrier gas hot conditions;
Described rare gas element is the gas mixture of any one or two kinds of argon gas and nitrogen.
2. the method for chemical gas-phase method continuous production few-wall carbon nanotube under according to claim 1 the no carrier gas condition is characterized in that, described step (2) preferred range that reactor heats up under inert atmosphere protection is 1000-1200 ℃.
3. the method for chemical gas-phase method continuous production few-wall carbon nanotube under according to claim 1 the no carrier gas condition is characterized in that the precursor solution of described step (2) and the preferred rate in the methyl alcohol injecting reactor are respectively 5-12ml/h and 40-70ml/h.
CN2012100639463A 2012-03-12 2012-03-12 Chemical vapor deposition method for continuously preparing carbon nanotubes with few walls under condition of no carrier gas CN102557012B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1458966A (en) * 2000-09-19 2003-11-26 埃勒凯姆欧洲股份有限公司 Device and method for converting carbon containing feedstock into carbon containing materials, having defined nanostructure
JP3953928B2 (en) * 2002-09-26 2007-08-08 キヤノン株式会社 Aggregate of carbon fibers and method for producing the same
CN102173408A (en) * 2010-12-30 2011-09-07 北京理工大学 Method for synthesizing carbon nano tube and cadmium sulphide core-shell structure with controllable shell thickness by wet chemical method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1458966A (en) * 2000-09-19 2003-11-26 埃勒凯姆欧洲股份有限公司 Device and method for converting carbon containing feedstock into carbon containing materials, having defined nanostructure
JP3953928B2 (en) * 2002-09-26 2007-08-08 キヤノン株式会社 Aggregate of carbon fibers and method for producing the same
CN102173408A (en) * 2010-12-30 2011-09-07 北京理工大学 Method for synthesizing carbon nano tube and cadmium sulphide core-shell structure with controllable shell thickness by wet chemical method

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