CN102320593B - Controllable preparation method of high-oxidation-resistance high-purity single/double-wall carbon nanotube - Google Patents
Controllable preparation method of high-oxidation-resistance high-purity single/double-wall carbon nanotube Download PDFInfo
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Abstract
The invention relates to the field of the controllable preparation of high-oxidation-resistance single/double-wall carbon nanotubes, in particular to a controllable preparation method of high-oxidation-resistance high-purity single/double-wall carbon nanotubes. The controllable preparation method comprises the following steps of: introducing carbon-source gas by utilizing a floating-catalyst chemical vapor-deposition method and using ferrocene as a catalyst precursor and sulfur powder as a growth promoter at a higher temperature, growing the high-oxidation-resistance carbon nanotubes under a high hydrogen-gas carrier-gas flow quantity, and simultaneously realizing the controlled growth of the single-wall or double-wall carbon nanotubes by regulating and controlling the quantity of the added growth promoter for sulfur to obtain the high-purity high-oxidation-resistance single/double-wall carbon nanotubes, wherein the single-wall or double-wall carbon nanotubes account for more than 90 percent of the total content of carbon tubes, and the highest oxidation-resisting temperatures of the single-wall and double-wall carbon nanotubes are respectively 770 DEG C and 785 DEG C. The single/double-wall carbon nanotubes with high crystallization degrees, fewer structural defects and high purity are obtained by the method, have the characteristics of excellent electrical conductivity, high elasticity, high strength and the like and are expected to be applied to transparent conductive films and the related devices of the transparent conductive films.
Description
Technical field
The present invention relates to the controlled preparation field of high antioxidant list/double-walled carbon nano-tube, be specially the controllable method for preparing of a kind of high antioxidant, high-purity, single/double-walled carbon nano-tube, utilize floating catalytic agent chemical Vapor deposition process, under high hydrogen carrier gas flow, grow the high antioxidant carbon nanotube, the amount that adds simultaneously growth promoter of sulfur by regulation and control has realized the control growth of single wall or double-walled carbon nano-tube.
Background technology
Utilizing carbon nanotube assembling transparent conductive film (Transparent Conductive Films, TCFs), is one of main application direction of carbon nanotube; Flexibility is that carbon nano tube transparent conductive thin-film is than the sharpest edges of conventional oxide transparent conductive film.The main preparation methods of carbon nanotube has arc process (A-SWCNTs), laser evaporation method (L-SWCNTs) and chemical Vapor deposition process.The growth temperature of A-SWCNTs and L-SWCNTs is higher, usually has high crystalline and less defect concentration, and its carrier mobility is high, is conducive to improve the conductivity of nesa coating.But the efficient of preparing carbon nano tube by arc process is on the low side, and it is higher to be difficult to the foreign matter content removed in the sample; The equipment that the laser evaporation method needs is comparatively complicated, expensive.This is so that above two kinds of methods and be not suitable for the large-scale production of high quality carbon nanotube.And chemical Vapor deposition process has that controllability is strong, equipment simple, the carbon nanotube quality is high, can produce semicontinuous or continuously and low cost and other advantages, has become the main method for preparing in batches Single Walled Carbon Nanotube.
What of its degree of crystallinity and defective are the intrinsic conductivity of carbon nanotube depend primarily on, but when carbon nanotube is assembled into transparent conductive film, not only require this film to have preferably electroconductibility, also require this film to have higher light transmission.The number of plies of carbon nanotube directly affects light transmission and the contact resistance by its transparent conductive film that assembles; The degree of crystallinity of carbon nanotube and diameter directly affect the electroconductibility by its transparent conductive film that assembles.(document 1, N Saran, K Parikh, DS Suh, E Munoz, H Kolla, SK Manohar.J.Am.Chem.Soc.126 (14): 4462-44633 (2004); Document 2, DH Zhang, K Ryu, XL Liu, E Polikarpov, JLy, ME Tompson, CW Zhou.Nano Lett.6 (9): 1880-1886 (2006); Document 3, Geng HZ, Lee DS, Kim KK, Kim SJ, Bae JJ, Lee YH, J.Korean Chem.Soc.53 (2): 979-985 (2008)).Therefore, for obtaining the high-performance flexible transparent conductive film, selectivity prepares high antioxidant, the controlled list/double-carbon nanotube of the number of plies is crucial.List/double-walled carbon nano-tube that the oxidation-resistance of report is the highest at present is by the arc process preparation, and its oxidation resistance temperature is about 800 ℃; List/the double-walled carbon nano-tube that yet there are no the chemical Vapor deposition process preparation has the report of so high oxidation resistance temperature.
Present subject matter is: how by regulating and control the growth conditions of carbon nanotube, list/double-walled carbon nano-tubes that directly a large amount of preparations are high-purity, oxidation-resistance is high, the number of plies is controlled.
Summary of the invention
The object of the present invention is to provide the floating catalytic agent chemical gaseous phase depositing process of list/double-walled carbon nano-tube that a kind of direct preparation is a large amount of, high-purity, the number of plies is controlled, oxidation-resistance is high; Realized first the chemical Vapor deposition process preparation of high-purity, high antioxidant list or double-walled carbon nano-tube, overcome the high antioxidant list of existing arc process preparation or double-walled carbon nano-tube purity low, be difficult to the problem such as large-scale production.
Technical scheme of the present invention is:
The controllable method for preparing of a kind of high antioxidant, high-purity, single/double-walled carbon nano-tube, take ferrocene as catalyst precursor, an amount of sulphur powder as growth stimulant, large flow hydrogen as carrier gas, pass into carbon-source gas at a certain temperature, the specified temp district (160-240 ℃ of humidity province) that catalyzer and growth stimulant is pushed Reaktionsofen simultaneously locates, and carries out the carbon nanotube controllable growth; Low temperature, long-time oxidation are to remove the impurity such as amorphous carbon under air atmosphere with the carbon nanotube sample for preparing, and temperature is: 200-500 ℃ (being preferably 350-380 ℃), and oxidization time is: 3-20 hour (being preferably 5-10 hour); Use again hydrochloric acid soln (concentration is 15-35wt%) to soak above-mentioned sample to remove metal catalyst particles and repeatedly to clean and vacuum-drying with deionized water; Finally obtained the list of a large amount of, high-purity, high anti-oxidation/double-walled carbon nano-tube sample, wherein the content of carbon nanotube in sample is more than 99wt%, and single wall or the double-walled carbon nano-tube radical per-cent in carbon nanotube is more than 90%.
The controllable method for preparing of described a kind of high antioxidant, high-purity, Single Walled Carbon Nanotube, concrete steps are as follows: take organic gas hydrocarbon (as: methane, acetylene, ethene or propylene etc.) as carbon-source gas, take hydrogen as carrier gas, ferrocene is catalyst precursor, take a certain proportion of sulphur powder (weight ratio of ferrocene and sulphur powder as: 180-220) as growth stimulant, (flow is: 6000-50000ml/min), the chemical gas phase furnace temperature is risen to 1100-1200 ℃ under large flow hydrogen shield; (the carbon source flow is: 10-30ml/min), and shift simultaneously ferrocene and sulphur powder onto furnace temperature and be 190-240 ℃ and locate that carry out chemical vapor deposition growth high anti-oxidation conductive single-walled carbon nanotubes, growth time is 5-60 minute to pass into carbon-source gas again.
The controllable method for preparing of described a kind of high antioxidant, high-purity, double-walled carbon nano-tube, concrete steps are as follows: take organic gas hydrocarbon (as: methane, acetylene, ethene or propylene etc.) as carbon-source gas, take hydrogen as carrier gas, ferrocene is catalyst precursor, take a certain proportion of sulphur powder (weight ratio of ferrocene and sulphur powder as: 80-120) as growth stimulant, (flow is: 4000-20000ml/min), the chemical gas phase furnace temperature is risen to 1100-1200 ℃ under large flow hydrogen shield; (the carbon source flow is: 10-50ml/min), and shift simultaneously ferrocene and sulphur powder onto furnace temperature and be 160-200 ℃ and locate that carry out chemical vapor deposition growth high anti-oxidation conductive single-walled carbon nanotubes, growth time is 5-60 minute to pass into carbon-source gas again.
Adopt in the resulting product of the inventive method, the characterization technique of estimating the high antioxidant of list/double-walled carbon nano-tube is: thermogravimetric/differential thermal analysis, and high anti-oxidation temperature refers to the concentrated oxidizing temperature of sample; The high anti-oxidation temperature of Single Walled Carbon Nanotube is 770 ℃, and the high anti-oxidation temperature of double-walled carbon nano-tube is 785 ℃.Generally speaking, the oxidation resistance temperature of Single Walled Carbon Nanotube is 700-770 ℃, and the oxidation resistance temperature of double-walled carbon nano-tube is 720-785 ℃.
Adopt in the resulting product of the inventive method, the high-purity ratio (purity 1) of carbon nanotube in sample that comprise, and list or the ratio (purity 2) of double-walled carbon nano-tube in carbon nanotube, the content of carbon nanotube (purity 1) 〉=99wt%, and single wall or the double-walled carbon nano-tube radical per-cent (purity 2) 〉=90% in total carbon nanotube, purity 1 is according to thermogravimetric/differential thermal curve quantitative Analysis, purity 2 is according in the high-resolution-ration transmission electric-lens photo, and the number of plies of carbon nanotube statistics obtains (as: numbers of plies of 100 carbon nanotubes of statistics).
Since the floating catalytic chemical Vapor deposition process be a kind of can continuous or semicontinuous production process, thereby be expected to realize in the future commercial scale production.
Advantage of the present invention is:
1; the present invention sets up a kind of floating catalytic agent chemical gaseous phase depositing process of direct preparation high antioxidant list/double-walled carbon nano-tube; take ferrocene as catalyst precursor; an amount of sulphur powder is growth stimulant; large flow hydrogen is carrier gas; pass at a certain temperature carbon-source gas; simultaneously catalyzer and growth stimulant are pushed in the specified temp district of Reaktionsofen; carry out the growth of carbon nanotube; the final high antioxidant that obtains; high-purity; the controllable growth of list/double-walled carbon nano-tube; wherein single wall or double-walled carbon nano-tube account for more than 90% of total carbon pipe content; the high anti-oxidation temperature of single wall and double-walled carbon nano-tube is respectively 770 ℃ and 785 ℃, prepares high quality list/double-walled carbon nano-tube and is difficult to the problems such as large-scale production thereby overcome existing arc process.
2, ratio, both residing temperature and the carbon source flow of growth stimulant sulphur powder in catalyzer is the key that selective control prepares list or double-walled carbon nano-tube, and the high flow capacity hydrogen carrier gas is the key that obtains high antioxidant list/double-walled carbon nano-tube.The inventive method has realized the selectivity of single wall and double-walled carbon nano-tube, controlled preparation, and the carbon nanotube of Floating catalyst method preparation is easy to purify, and high quality list/double-walled carbon nano-tube of having broken through existing arc process preparation is difficult to the problem of purifying.
3, since Floating catalyst method have simply, a large amount of, be easy to the characteristics such as mass-producing, the high quality, the list/double-walled carbon nano-tube high-purity, that the number of plies is controlled that are therefore prepared by the inventive method have good prospects for commercial application.
4, the present invention has realized control growth high-purity, high antioxidant list/double-walled carbon nano-tube, list/double-walled carbon nano-tube that this degree of crystallinity is high, textural defect is few, purity is high has the characteristics such as excellent electroconductibility, snappiness, high strength, is expected to obtain to use at transparent conductive film and related device thereof.
Description of drawings
Fig. 1. the high-resolution-ration transmission electric-lens photo of list/double-walled carbon nano-tube.Wherein, a figure is Single Walled Carbon Nanotube; B figure is double-walled carbon nano-tube.
Fig. 2. the stereoscan photograph of list/double-walled carbon nano-tube.Wherein, a figure is Single Walled Carbon Nanotube; B figure is double-walled carbon nano-tube.
Fig. 3. the thermogravimetric curve of list/double-walled carbon nano-tube.Wherein, a figure is Single Walled Carbon Nanotube; B figure is double-walled carbon nano-tube.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1.
(1) ferrocene that a slice is contained 0.5wt% sulphur powder is placed on chemical vapor deposition stove (CVD stove, diameter is 50mm, flat-temperature zone length is 8cm) cold zone, temperature rise rate with 30 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, hydrogen flowing quantity is heightened to 12000ml/min, passed into the methane of 20ml/min, and shift simultaneously the ferrocene of sulfur-bearing powder onto furnace temperature and be 215 ℃ and locate, carry out the growth of carbon nanotube, growth time is 30 minutes.Chemical vapour deposition is closed methane after finishing, and drops to room temperature in low hydrogen flowing quantity (hydrogen flowing quantity is 100ml/min) protection.
(2) it is 50mm that the carbon nanotube 30mg that step (1) is prepared evenly places diameter, and flat-temperature zone length is in the heating furnace tube of 8cm, at 370 ℃ of lower oxidation 10h.Behind the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%), 80 ℃ of lower cleanings repeatedly, until hydrochloric acid soln is no longer till the variable color.Until pH is 7, at 120 ℃ of these samples of lower vacuum-drying, example weight is: 6mg with this sample of washed with de-ionized water.
(3) sample after step (2) processing being carried out respectively transmission electron microscope, scanning electron microscope and thermogravimetric analysis characterizes, transmission electron microscope results shows, the carbon nanotube for preparing under this condition be Single Walled Carbon Nanotube (such as Fig. 1 a), under transmission electron microscope the number of plies of 100 carbon nanotubes is measured and added up, wherein 95 is Single Walled Carbon Nanotube.Scanning electron microscope shows that (Fig. 2 a), this Single Walled Carbon Nanotube sample is very pure, can calculate according to thermogravimetric curve that (Fig. 3 a), the content＞99wt% of carbon nanotube, the oxidation resistance temperature of this sample are 770 ℃.
Embodiment 2.
(1) ferrocene that a slice is contained 1wt% sulphur powder is placed on chemical vapor deposition stove (CVD stove, diameter is 50mm, flat-temperature zone length is 8cm) cold zone, temperature rise rate with 30 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, hydrogen flowing quantity is heightened to 10000ml/min, passed into the methane of 30ml/min, and shift simultaneously the ferrocene of sulfur-bearing powder onto furnace temperature and be 180 ℃ and locate, carry out the growth of carbon nanotube, growth time is 30 minutes.Chemical vapour deposition is closed methane after finishing, and drops to room temperature in low hydrogen flowing quantity (hydrogen flowing quantity is 100ml/min) protection.
(2) evenly to place diameter be 50mm to the carbon nanotube 30mg for preparing of step (1), and flat-temperature zone length is in the heating furnace tube of 8cm, at 370 ℃ of lower oxidation 10h.Behind the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%), 80 ℃ of lower cleanings repeatedly, until hydrochloric acid soln is no longer till the variable color.Until pH is 7, at 120 ℃ of these samples of lower vacuum-drying, example weight is: 6mg with this sample of washed with de-ionized water.
(3) sample after step (2) processing being carried out respectively transmission electron microscope, scanning electron microscope and thermogravimetric analysis characterizes, transmission electron microscope results shows, the carbon nanotube for preparing under this condition is double-walled carbon nano-tube (such as Fig. 1 b), under transmission electron microscope the number of plies of 100 carbon nanotubes is measured and added up, wherein 91 is double-walled carbon nano-tube.Scanning electron microscope shows (Fig. 2 b), and this double-walled carbon nano-tube sample is very pure, can calculate (Fig. 3 b) according to thermogravimetric curve, and the content＞99wt% of carbon nanotube, the oxidation resistance temperature of this sample are 785 ℃.
Embodiment 3.
(1) ferrocene that a slice is contained 1wt% sulphur powder is placed on chemical vapor deposition stove (CVD stove, diameter is 50mm, flat-temperature zone length is 8cm) cold zone, temperature rise rate with 30 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, hydrogen flowing quantity is heightened to 5000ml/min, passed into the methane of 30ml/min, and shift simultaneously the ferrocene of sulfur-bearing powder onto furnace temperature and be 180 ℃ and locate, carry out the growth of carbon nanotube, growth time is 30 minutes.Chemical vapour deposition is closed methane after finishing, and drops to room temperature in low hydrogen flowing quantity (hydrogen flowing quantity is 100ml/min) protection.
(2) it is 50mm that the carbon nanotube 30mg that step (1) is prepared evenly places diameter, and flat-temperature zone length is in the heating furnace tube of 8cm, at 370 ℃ of lower oxidation 10h.Behind the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%), 80 ℃ of lower cleanings repeatedly, until hydrochloric acid soln is no longer till the variable color.Until pH is 7, at 120 ℃ of these samples of lower vacuum-drying, example weight is: 6mg with this sample of washed with de-ionized water.
(3) sample after step (2) processing being carried out respectively transmission electron microscope, scanning electron microscope and thermogravimetric analysis characterizes, transmission electron microscope results shows, the carbon nanotube for preparing under this condition is double-walled carbon nano-tube, under transmission electron microscope the number of plies of 100 carbon nanotubes is measured and added up, wherein 91 is double-walled carbon nano-tube.Scanning electron microscope shows that this Single Walled Carbon Nanotube sample is very pure, can calculate the content＞99wt% of carbon nanotube according to thermogravimetric curve, and the oxidation resistance temperature of this sample is 740 ℃.
(1) ferrocene that a slice is contained 0.5wt% sulphur powder is placed on chemical vapor deposition stove (CVD stove, diameter is 50mm, flat-temperature zone length is 8cm) cold zone, temperature rise rate with 30 ℃/minute under hydrogen atmosphere is raised to 1100 ℃, hydrogen flowing quantity is heightened to 6000ml/min, passed into the methane of 20ml/min, and shift simultaneously the ferrocene of sulfur-bearing powder onto furnace temperature and be 215 ℃ and locate, carry out the growth of carbon nanotube, growth time is 30 minutes.Chemical vapour deposition is closed methane after finishing, and drops to room temperature in low hydrogen flowing quantity (hydrogen flowing quantity is 100ml/min) protection.
(2) it is 50mm that the carbon nanotube 30mg that step (1) is prepared evenly places diameter, and flat-temperature zone length is in the heating furnace tube of 8cm, at 370 ℃ of lower oxidation 10h.Behind the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 15-35wt%), 80 ℃ of lower cleanings repeatedly, until hydrochloric acid soln is no longer till the variable color.Until pH is 7, at 120 ℃ of these samples of lower vacuum-drying, example weight is: 6mg with this sample of washed with de-ionized water.
(3) sample after step (2) processing being carried out respectively transmission electron microscope, scanning electron microscope and thermogravimetric analysis characterizes, transmission electron microscope results shows, the carbon nanotube for preparing under this condition is Single Walled Carbon Nanotube, under transmission electron microscope the number of plies of 100 carbon nanotubes is measured and added up, wherein 93 is Single Walled Carbon Nanotube.Scanning electron microscope shows that this Single Walled Carbon Nanotube sample is very pure, can calculate the content＞99wt% of carbon nanotube according to thermogravimetric curve, and the oxidation resistance temperature of this sample is 720 ℃.
Embodiment result shows that the present invention can be by the proportioning of regulation and control temperature of reaction, carbon source add-on and catalyst precursor and growth stimulant, and selecting then, property prepares single wall or double-walled carbon nano-tube.In the identical situation of above-mentioned condition, use air flow hydrogen to be carrier gas, can prepare high-quality single wall and double-walled carbon nano-tube.Just can obtain high-purity list/double-walled carbon nano-tube after oxidation in the simple low temperature of carbon nanotube process of floating catalytic agent chemical Vapor deposition process preparation, the long-time air, the salt acid soak.
Claims (5)
1. the controllable method for preparing of a high antioxidant, high-purity, single/double-walled carbon nano-tube is characterized in that, the concrete steps of preparation carbon nanotube are as follows: take hydrogen as carrier gas, ferrocene is catalyst precursor, and the sulphur powder is growth stimulant; Under hydrogen shield, the temperature of chemical vapor deposition stove is risen to 1100-1200 ℃; Hydrogen flowing quantity is heightened to 4000-50000ml/min, passed into carbon-source gas again, and shift simultaneously ferrocene and sulphur powder the place, 160-240 ℃ of humidity province of Reaktionsofen onto, carry out the chemical vapor deposition growth carbon nanotube, growth time is 5-60 minute;
The condition of growing high-quality Single Walled Carbon Nanotube is: the weight ratio of ferrocene and sulphur powder is: 180-220; The laying temperature interval of sulphur powder and ferrocene is: 190-240 ℃; The carbon source flow is: 10-30ml/min; Hydrogen flowing quantity is: 6000-50000ml/min;
The condition of growing high-quality double-walled carbon nano-tube is: the weight ratio of ferrocene and sulphur powder is: 80-120; The laying temperature interval of sulphur powder and ferrocene is: 160-200 ℃; The carbon source flow is: 10-50ml/min; Hydrogen flowing quantity is: 4000-20000ml/min;
Low temperature, long-time oxidation are to remove amorphous carbon impurity under air atmosphere with the carbon nanotube sample for preparing, and temperature is: 200-500 ℃, oxidization time is: 3-20 hour; Be that the hydrochloric acid soln of 15-35wt% soaks above-mentioned sample removing metal catalyst particles with concentration again, and repeatedly clean and vacuum-drying with deionized water; Finally obtained the list of a large amount of, high-purity, high antioxidant/double-walled carbon nano-tube sample;
High-purityly comprise the ratio of carbon nanotube in sample, and list or the ratio of double-walled carbon nano-tube in carbon nanotube, the content 〉=99wt% of carbon nanotube, and radical per-cent in total carbon nanotube of single wall or double-walled carbon nano-tube 〉=90%.
2. according to the controllable method for preparing of high antioxidant claimed in claim 1, high-purity, single/double-walled carbon nano-tube, it is characterized in that temperature is preferably: 350-380 ℃, oxidization time is preferably: 5-10 hour.
3. according to the controllable method for preparing of high antioxidant claimed in claim 1, high-purity, single/double-walled carbon nano-tube, it is characterized in that the oxidation resistance temperature of Single Walled Carbon Nanotube is 700-770 ℃, the oxidation resistance temperature of double-walled carbon nano-tube is 720-785 ℃.
4. according to the controllable method for preparing of high antioxidant claimed in claim 3, high-purity, single/double-walled carbon nano-tube, it is characterized in that, the high anti-oxidation temperature of Single Walled Carbon Nanotube or double-walled carbon nano-tube refers to the concentrated oxidizing temperature of sample, the high anti-oxidation temperature of Single Walled Carbon Nanotube is 770 ℃, and the high anti-oxidation temperature of double-walled carbon nano-tube is 785 ℃.
5. according to the controllable method for preparing of high antioxidant claimed in claim 1, high-purity, single/double-walled carbon nano-tube, it is characterized in that carbon-source gas is the organic gas hydrocarbon.
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| CN103910352A (en) * | 2014-04-08 | 2014-07-09 | 上海电机学院 | Method for preparing multi-walled carbon nano tube |
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| CN110155986B (en) * | 2018-02-13 | 2023-01-13 | 中国科学院金属研究所 | Preparation of single-walled carbon nanotube transparent conductive film with single or small tube bundle size |
| CN110040720B (en) * | 2019-04-22 | 2022-05-31 | 中国科学院金属研究所 | Preparation method of high-purity narrow-diameter-distribution small-diameter double-wall carbon nano tube |
| CN110357072B (en) * | 2019-07-10 | 2022-05-31 | 中国科学院金属研究所 | Macro and controllable preparation method of large-diameter and narrow-diameter distribution single-walled carbon nanotubes |
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