CN1517458A - Method of preparing carbon fiber and nanometer carbon pipe - Google Patents
Method of preparing carbon fiber and nanometer carbon pipe Download PDFInfo
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- CN1517458A CN1517458A CNA031108504A CN03110850A CN1517458A CN 1517458 A CN1517458 A CN 1517458A CN A031108504 A CNA031108504 A CN A031108504A CN 03110850 A CN03110850 A CN 03110850A CN 1517458 A CN1517458 A CN 1517458A
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Abstract
A process for preparing the carbon nanotubes, carbon nanofibres, or spiral carbon fibres features the low-temp reaction between H2 as carrier gas, acetylene as carbon source, foam, nickel as catalyst and S-contained growth promoter. It can be used in microelectronic device and wave absorbing material. Its advantages are simple process, low cost, and high output rate and purity.
Description
Technical field
The present invention relates to carbon fiber/CNT (carbon nano-tube), specifically a kind of method for preparing carbon fiber and CNT (carbon nano-tube).
Background technology
Carbon fiber/CNT (carbon nano-tube) has excellent properties such as high ratio modulus, high specific strength, high conduction, is expected to be used for catalyst and catalyst carrier, lithium rechargeable battery anode material, electric double layer electrical electrode, high-efficiency adsorbent, release agent, structural reinforcement material etc.Chemical vapour deposition technique (CVD) is generally adopted in the preparation of carbon current fiber and CNT (carbon nano-tube), is raw material with the lower carbon number hydrocarbons compound, and hydrogen is carrier, and Fe, Co, Ni and alloy thereof are catalyst, can prepare carbon fiber/CNT (carbon nano-tube) under 873K～1473K.Specifically can be divided into matrix method, spray process and floating catalytic agent method.So-called matrix method is that graphite or pottery are made matrix, makes " seed " with the nm-class catalyst particle, and high temperature feeds hydrocarbon compound gas down, decomposes and separates out carbon fiber in catalyst one side.Though this method can be prepared high-quality product, catalyst sprays inhomogeneous on matrix, because carbon fiber only grows having on the matrix of catalyst, thereby output is not high.It is generally acknowledged the internal diameter and the catalyst granules equal diameters of carbon fiber and CNT (carbon nano-tube), people always try every possible means to obtain the less catalyst of granularity, and minor diameter Preparation of catalysts difficulty big, cost an arm and a leg, its application is subjected to certain restriction.
Spray process provides the possibility of a large amount of preparation carbon nano-fibers, but because the ratio of hydrocarbon and catalyst is difficult to optimize, catalyst distribution is inhomogeneous in the sprinkling process, and the catalyst granules that sprays is difficult to exist with nano level form, therefore generates with a large amount of carbon blacks in the process of preparation fiber.
For floating catalytic agent method, the metallorganic that generally will contain catalytic action volatilizees at a certain temperature, enters high temperature reaction zone with gaseous form, decomposes, generation has the metallic particles of catalytic action, and the carbon that the organic matter decomposition produces deposits to the metal surface and grows into carbon nano-fiber.The metallic that this method produces mutual collision in gaseous state is gathered into big metallic particles easily, therefore prepares carbon nano-fiber/CNT (carbon nano-tube) difficult parameters control, the operation relative complex.
Summary of the invention
The purpose of this invention is to provide the method that a kind of operation is simple relatively, the high and low cost of output prepares CNT (carbon nano-tube) and carbon fiber.
To achieve these goals, technical scheme of the present invention is: employing hydrogen is that carrier gas, acetylene are that carbon source, nickel foam (need not to pulverize) are catalyst, when adding carbon source, add and contain growth promoter of sulfur, under 873K～1173K temperature, react, prepare CNT (carbon nano-tube), carbon nano-fiber or helical carbon fiber (comprising single, double helical carbon fiber); Wherein: hydrogen is 3～5: 1 with the ratio of acetylene flow; Containing the growth promoter of sulfur addition is 0.3～1mol%; The diameter of product and form are mainly controlled by regulating technological parameters such as flow, temperature;
The described growth promoter of sulfur that contains is for being thiophene phenol or hydrogen sulfide, in order to its output of effective raising; Before reaction described nickel foam was soaked in 5～10% diluted acid 1～10 hour, use dry back.
Require high with the carbon fiber/CNT (carbon nano-tube) of traditional CVD method preparation to catalyst and complex process, the higher the present invention of comparing of cost have more following beneficial effect:
1. technology is simple, cheap.The present invention is a kind of a kind of new method that the matrix method is different from floating catalytic agent method again that promptly is different from, it proposes with the nickel foam is catalyst, can reduce cost, and with hydrogen as carrier gas, acetylene is carbon source, add a kind of growth promoter of sulfur that contains, can be at a lower temperature (prepare comparatively pure nano carbon pipe and carbon fiber in a large number as 873K～1173K), easy to operate, technology is simple.
2. output height.It is catalyst that the present invention adopts nickel foam, hydrogen is carrier gas and adds a spot of sulfur containing promoter can efficiently be easy to prepare on a large scale carbon fiber and CNT (carbon nano-tube) when reducing cost, and productive rate height (can up to more than 600%) is a kind of novel preparation method who has the commercial Application potentiality.Show the degree of purity of production height through electronic microscope photos.Utilize this material can also carry out CNT (carbon nano-tube) and properties of carbon (mechanics, electricity etc.) test easily.
3. have broad application prospects.The present invention can be applicable to structure enhancing, microelectronic component, absorbing material etc.
Description of drawings
Fig. 1 prepares CNT (carbon nano-tube), carbon fiber equipment therefor structural representation for the present invention.
Fig. 2 a is the stereoscan photograph of the embodiment of the invention 1 carbon fiber.
Fig. 2 b is the transmission electron microscope photo of one embodiment of the invention 1 carbon pipe.
Fig. 3 a is the transmission electron microscope photo of the embodiment of the invention 2 single-screw carbon fibers.
Fig. 3 b is the stereoscan photograph of the embodiment of the invention 2 another single-screw carbon fibers.
Fig. 4 a is the transmission electron microscope photo of the embodiment of the invention 3 single-screw carbon fibers.
Fig. 4 b is the transmission electron microscope photo of the embodiment of the invention 3 another single-screw carbon fibers.
Fig. 5 a is the stereoscan photograph of the embodiment of the invention 4 double helix carbon fibers.
Fig. 5 b is the stereoscan photograph of the embodiment of the invention 4 another double helix carbon fibers.
The specific embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
As shown in Figure 1, equipment therefor of the present invention is made up of hydrogen gas tank 1, acetylene cylinder 2, flowmeter 3, temperature controller 4, reacting furnace 5, temperature by temperature controller 4 control reacting furnaces 5 adds hydrogen or acetylene by hydrogen gas tank 1, acetylene cylinder 2 in reacting furnace 5, its flow is by flowmeter 3 controls; Present embodiment reacting furnace 5 adopts tube furnace.
Before the reaction 0.574g nickel foam is placed on the flat-temperature zone of tube furnace, under nitrogen atmosphere, reaction is warmed up to 953K, feeding acetylene adds simultaneously and contains growth promoter of sulfur thiophene phenol, addition is (0.6mol%), the ratio of hydrogen and acetylene flow is that (wherein: acetylene was 75ml/min in 3.7: 1, hydrogen is 277.5ml/min), the reaction constant temperature time is 60min, carries out pyrolytic reaction; Reaction naturally cools to room temperature after finishing.Can obtain carbon nano-fiber (referring to Fig. 2 a) and CNT (carbon nano-tube) (referring to Fig. 2 b), the productive rate 600% of 3.4456 g.
Embodiment 2
Difference from Example 1 is:
Before the reaction nickel foam is soaked 1h in 10% watery hydrochloric acid, dry back 0.593g nickel foam is placed on the flat-temperature zone of tube furnace, under nitrogen atmosphere, reaction is warmed up to 973K, feed acetylene, add simultaneously and contain growth promoter of sulfur thiophene phenol (addition is 0.5mol%), hydrogen is 4: 1 (wherein: acetylene is 58ml/min, and hydrogen is 232ml/min) with the ratio of acetylene flow.The reaction constant temperature time is 45min, and reaction naturally cools to room temperature after finishing.Can obtain the single-screw shape carbon fiber (referring to Fig. 3 a, Fig. 3 b) of 2.5451g, productive rate is 429%.
Embodiment 3
Difference from Example 1 is:
Before the reaction nickel foam is soaked 6h in 5% watery hydrochloric acid, dry back 0.425g nickel foam is placed on the flat-temperature zone of tube furnace, under nitrogen atmosphere, reaction is warmed up to 993K, feed acetylene, add simultaneously and contain growth promoter of sulfur thiophene phenol (addition is 0.9mol%), hydrogen is 4.5: 1 (wherein: acetylene is 65ml/min, and hydrogen is 292.5ml/min) with the ratio of acetylene flow.The reaction constant temperature time is 35min.Reaction naturally cools to room temperature after finishing.Can obtain the single-screw shape carbon fiber (seeing Fig. 4 a, Fig. 4 b) of 0.8523g, productive rate 200%.
Embodiment 4
Difference from Example 1 is:
Before the reaction nickel foam is soaked 2h in 8% watery hydrochloric acid, dry back 0.376g nickel foam is placed on the flat-temperature zone of tube furnace, under nitrogen atmosphere, reaction is warmed up to 1023K, feed acetylene, add simultaneously and contain growth promoter of sulfur thiophene phenol (addition is 0.75mol%), hydrogen is 4.2: 1 (wherein: acetylene is 60ml/min, and hydrogen is 252ml/min) with the ratio of acetylene flow.The reaction constant temperature time is 30min.Reaction naturally cools to room temperature after finishing.Can obtain the double helix carbon fiber (seeing Fig. 5 a, Fig. 5 b) of 0.9455g.Productive rate 251%.
The growth promoter of sulfur that contains of the present invention also can adopt hydrogen sulfide.
Claims (5)
1. method for preparing carbon fiber and CNT (carbon nano-tube), it is characterized in that: employing hydrogen is that carrier gas, acetylene are that carbon source, nickel foam are catalyst, add when adding carbon source and contain growth promoter of sulfur, CNT (carbon nano-tube), carbon nano-fiber or helical carbon fiber are prepared in reaction at a lower temperature.
2. according to the described method for preparing carbon fiber and CNT (carbon nano-tube) of claim 1, it is characterized in that: described reaction temperature is 873K～1173K.
3. according to the described method for preparing carbon fiber and CNT (carbon nano-tube) of claim 1, it is characterized in that: described hydrogen is 3～5: 1 with the ratio of acetylene flow.
4. according to the described method for preparing carbon fiber and CNT (carbon nano-tube) of claim 1, it is characterized in that: the described growth promoter of sulfur that contains is thiophene phenol or hydrogen sulfide, and its addition is 0.3～1mol%.
5. according to the described method for preparing carbon fiber and CNT (carbon nano-tube) of claim 1, it is characterized in that: before reaction described nickel foam was soaked in 5～10% diluted acid 1～10 hour, use dry back.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03110850 CN1216192C (en) | 2003-01-13 | 2003-01-13 | Method of preparing carbon fiber and nanometer carbon pipe |
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| CN 03110850 CN1216192C (en) | 2003-01-13 | 2003-01-13 | Method of preparing carbon fiber and nanometer carbon pipe |
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| CN1216192C CN1216192C (en) | 2005-08-24 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358803C (en) * | 2006-06-07 | 2008-01-02 | 西北工业大学 | Method of growing carbon nanometer pipe on carbon cloth base |
| CN100471792C (en) * | 2007-01-19 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Method for preparing spiral nanometre carbon tube |
| CN101209834B (en) * | 2006-12-27 | 2010-07-07 | 北京化工大学 | Method for preparing spiral nano carbon tube rope |
| CN101210355B (en) * | 2006-12-27 | 2010-11-10 | 北京化工大学 | Method for preparing fishbone-shaped nano carbon fibre for filling nano metal |
| CN101585526B (en) * | 2008-05-21 | 2011-05-11 | 中国科学院金属研究所 | Preparation method of cup-stack carbon nano-tube |
| CN109046461A (en) * | 2018-08-07 | 2018-12-21 | 四川理工学院 | The method that a kind of preparation method of sulfur-bearing complex compound catalyst and its catalysis prepare spiral nanometer carbon fiber |
| CN109642350A (en) * | 2017-01-04 | 2019-04-16 | Lg化学株式会社 | The method for controlling the intensity of carbon nano-tube fibre aggregation |
| CN109709187A (en) * | 2018-12-21 | 2019-05-03 | 中国人民解放军军事科学院军事医学研究院 | A kind of carbon fiber and the preparation method and application thereof |
| CN110483101A (en) * | 2019-08-14 | 2019-11-22 | 中国科学院合肥物质科学研究院 | The preparation method of carbon nano-fiber film without metallic catalyst |
| CN116081602A (en) * | 2023-02-08 | 2023-05-09 | 广东碳语新材料有限公司 | Method for preparing spiral carbon nano tube by using waste polyolefin |
-
2003
- 2003-01-13 CN CN 03110850 patent/CN1216192C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358803C (en) * | 2006-06-07 | 2008-01-02 | 西北工业大学 | Method of growing carbon nanometer pipe on carbon cloth base |
| CN101209834B (en) * | 2006-12-27 | 2010-07-07 | 北京化工大学 | Method for preparing spiral nano carbon tube rope |
| CN101210355B (en) * | 2006-12-27 | 2010-11-10 | 北京化工大学 | Method for preparing fishbone-shaped nano carbon fibre for filling nano metal |
| CN100471792C (en) * | 2007-01-19 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Method for preparing spiral nanometre carbon tube |
| CN101585526B (en) * | 2008-05-21 | 2011-05-11 | 中国科学院金属研究所 | Preparation method of cup-stack carbon nano-tube |
| CN109642350A (en) * | 2017-01-04 | 2019-04-16 | Lg化学株式会社 | The method for controlling the intensity of carbon nano-tube fibre aggregation |
| CN109642350B (en) * | 2017-01-04 | 2021-07-09 | Lg化学株式会社 | Method for controlling strength of carbon nanotube fiber aggregate |
| CN109046461A (en) * | 2018-08-07 | 2018-12-21 | 四川理工学院 | The method that a kind of preparation method of sulfur-bearing complex compound catalyst and its catalysis prepare spiral nanometer carbon fiber |
| CN109046461B (en) * | 2018-08-07 | 2021-07-20 | 四川理工学院 | Preparation method of sulfur-containing complex catalyst and method for preparing spiral carbon nanofibers through catalysis of sulfur-containing complex catalyst |
| CN109709187A (en) * | 2018-12-21 | 2019-05-03 | 中国人民解放军军事科学院军事医学研究院 | A kind of carbon fiber and the preparation method and application thereof |
| CN109709187B (en) * | 2018-12-21 | 2021-07-13 | 中国人民解放军军事科学院军事医学研究院 | Carbon fiber and preparation method and application thereof |
| CN110483101A (en) * | 2019-08-14 | 2019-11-22 | 中国科学院合肥物质科学研究院 | The preparation method of carbon nano-fiber film without metallic catalyst |
| CN116081602A (en) * | 2023-02-08 | 2023-05-09 | 广东碳语新材料有限公司 | Method for preparing spiral carbon nano tube by using waste polyolefin |
| CN116081602B (en) * | 2023-02-08 | 2023-10-24 | 广东碳语新材料有限公司 | Method for preparing spiral carbon nano tube by using waste polyolefin |
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| CN1216192C (en) | 2005-08-24 |
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