CN1749156A - Arc method for synthesizing controllable single wall carbon nano tube - Google Patents
Arc method for synthesizing controllable single wall carbon nano tube Download PDFInfo
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- CN1749156A CN1749156A CN 200510015495 CN200510015495A CN1749156A CN 1749156 A CN1749156 A CN 1749156A CN 200510015495 CN200510015495 CN 200510015495 CN 200510015495 A CN200510015495 A CN 200510015495A CN 1749156 A CN1749156 A CN 1749156A
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Abstract
The present invention discloses electric arc process of synthesizing single wall carbon nanotube. The DC arc discharging process of synthesizing carbon nanotube is performed with graphite as cathode, composite electrode containing carbon material and catalyst components as anode, and inert gas with 0.01-20vol% weak oxidative gas as reaction gas, and in the conditions of gas pressure of 500-600 mmHg, voltage of 15-35 V and current of 80-120 A. The synthesis process can control the growth of single wall carbon nanotube for length and diameter of the single wall carbon nanotube maintained in certain range, reduce amorphous carbon impurity produced in the synthesis process, and raise the application performance of carbon nanotube.
Description
Technical field
The present invention relates to the technology of preparing of Single Walled Carbon Nanotube (SWNTs), the Single Walled Carbon Nanotube preparation method of particularly a kind of Single Walled Carbon Nanotube tube bank diameter and length controlled.
Background technology
Carbon nanotube (CNT) is to be found by Iijima in 1991, and it is the nano level coaxial clyinder of the seamless hollow that is rolled into of the graphite by laminated structure.In recent years, along with deepening continuously of carbon nanotube and nano materials research, its broad prospect of application also constantly displayed.Experiment has proved that carbon nanotube has high intensity and Young's modulus, is called as super fiber, can be used for the enhancing body of advanced composite material; Carbon nanotube has unique electronics band structure, is ideal One-dimensional Quantum lead; In addition, carbon nanotube also has potentiality as emtting electrode, absorbing material, hydrogen storage material etc.And have the smaller tube bank length and the Single Walled Carbon Nanotube of diameter, in properties still is that application facet all has more its unique significance: when the tube bank length of carbon nanotube little of below 1 micron, carbon nanotube is more prone to be scattered in the organic solvent, material for the preparation of physical blending method can obtain better properties; In near the homogeneous reaction system, the carbon nanotube that length is little is more prone to modify with functionalization, participate in chemical reaction better.In addition, length is that several microns Single Walled Carbon Nanotube tube bank also can be used to carry out covalent linkage with biomacromolecule and is connected or twines, simultaneously because its high electroconductibility, the polymer composite that is usually used in making high-grade, precision and advanced technique articles such as bioprobe, transmitter and has good mechanical property.
But, the present carbon nanotube that synthesizes with the whole bag of tricks, its tube bank length and diameter be at random, uncontrollable.When needing length and diameter to be in the carbon nanotube of certain scope, can only obtain by separation method.If adopt the method for membrane sepn, equipment cost height not only, and the carbon nanotube that loses in the filtration procedure is many.If adopt the method for centrifugation, though cost decreases, separating effect is bad and can not remove impurity such as decolorizing carbon in the product.
So,, make its length and diameter remain on certain limit and then have very important significance if when the preparation carbon nanotube, can control length and the diameter that generates the carbon nanotube tube bank.
2004, the inventor discloses a kind of electric arc synthetic method (Carbon of new Single Walled Carbon Nanotube, 2005,43,2020-2022, Synthesis of high quality single-walled carbon nanotubes at large scaleby electric arc using metal compounds), this method has adopted combined electrode that a kind of new catalyst system makes as anode, arc-over manufacture order wall carbon nano tube under inert atmosphere once can be produced low-cost by successive, in a large number, high purity, stay-in-grade Single Walled Carbon Nanotube.
This method is being carried out in the more detailed research, the inventor passes through number of research projects, found in the preparation carbon nanotube and can control length and the diameter that generates the carbon nanotube tube bank, made its length and diameter remain on the synthetic method of certain limit.
Simultaneously, in the process of traditional arc process single-wall carbon nanotube synthesizing, inevitably with the generation of a large amount of agraphitic carbons (impurity), and agraphitic carbon wrapped up metal catalyst, behind the end of synthesis, will make this two kinds of impurity are all more difficult and remove.And the existence of agraphitic carbon and metal catalyst all produces detrimentally affect to the character and the application of carbon nanotube.The inventor also considers the problem of a large amount of agraphitic carbon impurity that the minimizing synthesis phase produces simultaneously when screening method and condition.Thereby use the inventive method and not only can obtain restraining the carbon nanotube that length and diameter are in certain limit, and the content of impurity agraphitic carbon reduces in the products obtained therefrom.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic method that can control the Single Walled Carbon Nanotube growth, can reduce the agraphitic carbon impurity of building-up process generation simultaneously again.
The present invention adds partial oxygen voltinism gas as reaction gas, with the growth of controlling carbon nanotube by the atmosphere of living in of the growth system of change carbon nanotube in rare gas element.
The present invention is achieved through the following technical solutions:
Adopt graphite as negative electrode, carbonaceous material and catalyzer are that the combined electrode of component is as anode, (v) (v) the oxidizing gas of % is as reaction gas for % to 20 to add 0.01 in rare gas element, maintenance air pressure is 500-600mmHg, at voltage 15-35V, carry out the direct current arc discharge under the condition of electric current 80-120A.
The component of combined electrode of the present invention is carbonaceous material and catalyzer, and wherein carbonaceous material is graphite, coal, pitch, carbon fiber or their mixture, preferred carbon fiber or carbon fiber and graphite; Catalyzer be iron, nickel, yttrium, they oxide compound and/or their carbonate at least a.
Rare gas element of the present invention comprises helium, argon gas, nitrogen or their gas mixture. body.Described oxidizing gas comprises carbon dioxide, oxygen or their mixed gas.
Graphite combined electrodes that adopt in the technical program and preparation method thereof etc., the contriver once had detailed description in document (Synthesis ofhigh quality single-walled carbon nanotubes at large scale by electric arc usingmetal compounds.Carbon 43 (2005) 2020-2022).
Advantage of the present invention and characteristics are:
1, output is big, once can successive mass production high purity, stay-in-grade Single Walled Carbon Nanotube.
2, reduced cost, can control the length and the diameter of prepared Single Walled Carbon Nanotube tube bank, satisfied various experimental studies and application needs for carbon nanotube with certain tube bank length and diameter.
3, reduced the agraphitic carbon composition that contains in the product, helped removing the metal catalyst in the product simultaneously, effect is very remarkable.
Should it should be noted that: the inventor is at " adopting the synthetic high quality Single Walled Carbon Nanotube of the extensive arc process of metallic compound " (Carbon, 2005,43,2020-2022, Synthesis of high quality single-walled carbonnanotubes at large scale by electric arc using metal compounds) disclosed technical scheme in should be considered as the disclosed part of technical solution of the present invention.
Embodiment
Adopt the technical solution of the present invention synthesizing carbon nanotubes, the product of acquisition is:
1) (v) (v) under the reaction atmosphere of % oxidizing gas, the tube bank mean length of gained carbon nanotube is 1.5 to 1.35 microns to % to 1, and mean diameter is 6 to 5.8 nanometers, and agraphitic carbon content is about 22～20% containing 0.01;
2) (v) (v) under the reaction atmosphere of % oxidizing gas, the tube bank mean length of the carbon nanotube of production is 1.35 to 1.2 microns to % to 5, and mean diameter is 5.8 to 5.3 nanometers, and agraphitic carbon content is about 20～18% containing 1;
3) (v) (v) under the reaction atmosphere of % oxidizing gas, the tube bank mean length of the carbon nanotube of production is 1.2 to 0.8 microns to % to 10, and mean diameter is 5.3 to 5 nanometers, and agraphitic carbon content is about 18～10% containing 5;
4) (v) (v) under the reaction atmosphere of % oxidizing gas, the tube bank mean length of the carbon nanotube of production is 0.8 to 0.5 micron to % to 20, and mean diameter is 5 to 4 nanometers, and agraphitic carbon content is about 10～3% containing 10.
Below by embodiment the present invention is specifically described, present embodiment only is used for the present invention is further detailed, and is not limited to following embodiment.
Embodiment 1:
Take by weighing 1.16 gram carbon fibers, 18.68 gram graphite adhesives, 4.12 gram nickel oxide powders, 1.48 gram yttrium oxide powder stir with mixing tank, are pressed into electrode then in mould, become sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, under the condition that contains the helium condition of 10% carbonic acid gas, 500-600mmHg, 120 amperes in electric current carries out arc-over in the scope of voltage 25-30 volt, 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 20g.0.8 micron of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 5 nanometers.Dispersiveness for organic solvent is very outstanding.
Embodiment 2:
Take by weighing 1.16 gram carbon fibers, 18.68 gram graphite adhesives, 3.23 gram nickel powders, 1.48 gram yttrium oxide powder stir with mixing tank, are pressed into electrode then in mould, become sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, in containing the helium reaction atmosphere of 20% carbonic acid gas, under the condition of 500-600mmHg, 120 amperes in electric current, carry out arc-over in the scope of voltage 25-30 volt, in 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 18g.0.5 micron of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 4 nanometers.The product for preparing very easily is scattered in organic solvent.
Embodiment 3:
Take by weighing 1.16 gram carbon fibers, 9 gram graphite, 10 gram graphite adhesives, 4.12 gram nickel oxide powders, 1.17 gram yttrium powder stir with mixing tank, are pressed into electrode then in mould, become sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, in containing the helium reaction atmosphere of 0.1% carbonic acid gas, under the condition of 500-600mmHg, 120 amperes in electric current, carry out arc-over in the scope of voltage 25-30 volt, in 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 19g.1.5 microns of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 6 nanometers.Dispersive ability in organic solvent is very poor.
Embodiment 4:
Take by weighing 3.2 gram carbon fibers, 38 gram graphite adhesives, the 2.1 sour nickel powders of restraining oneself, 0.5 gram yttrium carbonate powder stirs with mixing tank, is pressed into electrode then in mould, becomes sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, in containing the helium reaction atmosphere of 1% carbonic acid gas, under the condition of 500-600mmHg, 120 amperes in electric current, carry out arc-over in the scope of voltage 25-30 volt, in 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 35g.1.35 microns of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 5.8 nanometers.Dispersive ability in organic solvent is relatively poor.
Embodiment 5:
Take by weighing 2 gram carbon fibers, 19 gram graphite adhesives, 0.94 gram carbonic acid nickel powder, 0.24 gram yttrium carbonate powder stirs with mixing tank, is pressed into electrode then in mould, becomes sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, in containing the helium reaction atmosphere of 5% carbonic acid gas, under the condition of 500-600mmHg, 120 amperes in electric current, carry out arc-over in the scope of voltage 25-30 volt, in 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 20g.1.2 microns of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 5.3 nanometers.The dispersiveness of the product for preparing in organic solvent is enhanced.
Embodiment 6:
Take by weighing 1.2 gram carbon fibers, 19 gram graphite adhesives, 4.12 gram nickel oxide powders, 1.48 gram yttrium oxide powder stir with mixing tank, are pressed into electrode then in mould, become sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, in containing the helium reaction atmosphere of 15% carbonic acid gas, under the condition of 500-600mmHg, 120 amperes in electric current, carry out arc-over in the scope of voltage 25-30 volt, in 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 20g.0.65 micron of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 4.5 nanometers.The product for preparing dispersed very good in organic solvent.
Embodiment 7:
Take by weighing 2 gram carbon fibers, 19 gram graphite adhesives, 4.12 gram nickel oxide powders, 1.48 gram yttrium oxide powder stir with mixing tank, are pressed into electrode then in mould, become sacrificial electrode in 1000 degree roastings.Do anode with this sacrificial electrode, Graphite Electrodes is done negative electrode, in containing the helium reaction atmosphere of 1% oxygen, under the condition of 500-600mmHg, 120 amperes in electric current carries out arc-over in the scope of voltage 25-30 volt, 2 hours reaction times, after reaction is finished, collect Single Walled Carbon Nanotube 20g.1.35 microns of the tube bank length average out to of preparation-obtained carbon nanotube, the tube bank diameter is 5.8 nanometers.Dispersive ability in organic solvent is relatively poor.
Claims (5)
1, a kind of electric arc synthetic method of Single Walled Carbon Nanotube, it is characterized in that adopting graphite as negative electrode, the combined electrode that carbonaceous material and catalyzer are formed is as anode, (v) (v) the oxidizing gas of % is as reaction gas for % to 20 to add 0.01 in rare gas element, maintenance air pressure is 500-600mmHg, at voltage 15-35V, carry out the direct current arc discharge under the condition of electric current 80-120A.
2,, it is characterized in that described carbonaceous material is graphite, coal, pitch, carbon fiber or their mixture, preferred carbon fiber or carbon fiber and graphite according to the electric arc synthetic method of the described Single Walled Carbon Nanotube of claim 1.
3, according to the electric arc synthetic method of the described Single Walled Carbon Nanotube of claim 1, it is characterized in that described catalyzer be iron, nickel, yttrium, they oxide compound and/or their carbonate at least a.
4,, it is characterized in that described rare gas element is helium, argon gas, nitrogen or their gas mixture according to the electric arc synthetic method of the described Single Walled Carbon Nanotube of claim 1. body.
5,, it is characterized in that described oxidizing gas is carbon dioxide, oxygen or their gas mixture according to the electric arc synthetic method of the described Single Walled Carbon Nanotube of claim 1. body.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481788A (en) * | 2008-03-04 | 2009-07-15 | 浙江大学 | Preparation of single wall carbon nano-tube film |
| CN102459073A (en) * | 2009-06-11 | 2012-05-16 | 同和控股（集团）有限公司 | Carbon nanotubes and process for producing same |
| CN102602911A (en) * | 2012-03-07 | 2012-07-25 | 上海交通大学 | Method for preparing single-walled carbon nanotube by adopting controllability of low-pressure reactant gas |
| CN102757033A (en) * | 2012-07-03 | 2012-10-31 | 清华大学 | Method for preparing carbon nanotube with specific quantities of walls and specific diameters |
-
2005
- 2005-10-18 CN CNB2005100154956A patent/CN100522804C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481788A (en) * | 2008-03-04 | 2009-07-15 | 浙江大学 | Preparation of single wall carbon nano-tube film |
| CN102459073A (en) * | 2009-06-11 | 2012-05-16 | 同和控股（集团）有限公司 | Carbon nanotubes and process for producing same |
| CN102459073B (en) * | 2009-06-11 | 2014-05-14 | 同和控股（集团）有限公司 | Carbon nanotubes and process for producing same |
| CN102602911A (en) * | 2012-03-07 | 2012-07-25 | 上海交通大学 | Method for preparing single-walled carbon nanotube by adopting controllability of low-pressure reactant gas |
| CN102757033A (en) * | 2012-07-03 | 2012-10-31 | 清华大学 | Method for preparing carbon nanotube with specific quantities of walls and specific diameters |
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| CN100522804C (en) | 2009-08-05 |
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