WO2004099072A1 - Procede et dispositif de fabrication pour nanotube de carbone a couche unique - Google Patents

Procede et dispositif de fabrication pour nanotube de carbone a couche unique Download PDF

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Publication number
WO2004099072A1
WO2004099072A1 PCT/JP2004/002491 JP2004002491W WO2004099072A1 WO 2004099072 A1 WO2004099072 A1 WO 2004099072A1 JP 2004002491 W JP2004002491 W JP 2004002491W WO 2004099072 A1 WO2004099072 A1 WO 2004099072A1
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WO
WIPO (PCT)
Prior art keywords
reaction vessel
net
walled carbon
carbon nanotubes
arc discharge
Prior art date
Application number
PCT/JP2004/002491
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English (en)
Japanese (ja)
Inventor
Yoshinori Ando
Masato Okochi
Xinluo Zhao
Sakae Inoue
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Japan Science And Technology Agency
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Publication of WO2004099072A1 publication Critical patent/WO2004099072A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes

Definitions

  • the present invention provides a method and a device for producing single-walled carbon nanotubes which are expected to be developed as functional materials such as electronic materials, hydrogen storage materials, and nanostructured materials, and purifying the carbon nanotubes in situ.
  • Carbon nanotubes are attracting attention as high-performance materials because their electrical properties change semiconductingly or metallically depending on the crystallographic structure and diameter.
  • the carbon nanotubes are divided into multi-walled carbon nanotubes (MWNTs) in which two or more layers of graphene sheet are stacked at equal intervals, and single-walled carbon nanotubes (SWNTs) with only one layer.
  • MWNTs multi-walled carbon nanotubes
  • SWNTs single-walled carbon nanotubes
  • Single-walled carbon nanotubes are expected to have a quantum effect derived from a smaller diameter than multi-walled carbon nanotubes, and are of interest for physical properties.
  • Arc discharge, laser evaporation, CVD, etc. are used for the production of carbon nanotubes.
  • the CVD method is suitable for mass production, and the arc discharge is suitable for improving crystallinity.
  • a graphite rod mixed with a metal catalyst is used as the anode, and the graphite rod is evaporated by arc heat.
  • the evaporated graphite is generated as a net-like soot that is wrapped in a spider web around the electrodes and the entire interior of the container. This net-like soot contains single-walled carbon nanotubes.
  • the present inventors investigated and examined various conditions for producing a large amount of net-like soot containing single-walled carbon nanotubes, and arranged the anode and the carbon rod cathode including the Ni-Y catalyst at an acute angle of 30 degrees. Was reported to be effective ("Materials", Vol. 50, No. 7, pp. 357-360).
  • the proportion of single-walled carbon nanotubes in the deposited net soot is not necessarily high Therefore, it is necessary to refine the net soot to increase the purity of the single-walled carbon nanotube.
  • purification of the single-walled carbon nanotubes is not easy due to insufficient mechanical and chemical strength. Insufficient mechanical and chemical strength is considered to be due to poor crystallinity of single-walled carbon nanotubes synthesized using Ni-Y catalyst.
  • the catalyst contains S, so the single-walled carbon nanotube has low mechanical and chemical strength and is easy to purify.
  • the present invention overcomes problems due to low mechanical strength by purifying single-walled carbon nanotubes generated by arc discharge in the same reaction vessel without moving them to another location, and achieves high purity.
  • the purpose is to produce single-walled carbon nanotubes with high productivity.
  • At least two electrodes containing Fe catalyst are opposed to at least two graphite rods on the anode side in a tubular reaction vessel in a direction orthogonal to the tube axis, and H 2 , X
  • An arc discharge is generated between the electrodes while feeding the mixed gas of (inert gas), and at least the carbon vapor evaporated from the anode is placed on the flow of the mixed gas.
  • a reaction vessel wall are deposited as a net-like single-walled carbon nanotube.
  • the arc discharge is stopped, and the atmosphere gas in the reaction vessel is switched from a mixed gas of H 2 and X to a mixed gas of O 2 and X.
  • the inert gas X a rare gas such as He, Ne, Ar, Kr, or Xe or N 2 can be used.
  • the rare gases the heavier ones produce better results, and the same net-like deposits of single-walled carbon nanotubes are produced when N2 is used.
  • Ar a representative of the inert gas X will be described.
  • the apparatus used in this method has a tubular reaction vessel having a base end connected to a pre-chamber and an exhaust pipe open at the tip, and extending in a horizontal direction, and is opposed to the reaction vessel in a direction perpendicular to the tube axis.
  • At least the anode side is provided with a pair of Daraphite electrodes made of Fe catalyst-containing carbon, a discharge power source to which the graphite electrode is connected, and a heating mechanism arranged around the reaction vessel.
  • the pre-chamber has a gas supply pipe that opens the H 2 , Ar mixed gas during the arc discharge and the 02, Ar mixed gas to the exhaust pipe with the heating mechanism turned on after the arc discharge. I have.
  • the net-like sediment from which the impurity carbon has been removed by thermal oxidation is collected by a collecting device arranged on the exhaust pipe side in the reaction vessel.
  • a collecting device arranged on the exhaust pipe side in the reaction vessel.
  • both are made from Fe catalyst-containing carbon
  • the pair of graphite electrodes described above is used.
  • Fig. 1 is a schematic plan view of a single-walled carbon nanotube manufacturing apparatus according to the present invention. SEM photo showing net deposits
  • Figure 4 shows an SEM image of a net-like deposit of single-walled carbon nanotubes treated with hydrochloric acid.
  • Fig. 5 is a TEM photograph showing a net-like deposit of single-walled carbon nanotubes from which Fe fine particles have disappeared after hydrochloric acid treatment.
  • Fig. 6 is a Raraf spectrum showing the Raman spectrum of the obtained single-walled carbon nanotube.
  • a reactor which deposits single-walled carbon nanotubes by evaporating carbon from graphite electrodes by arc discharge.
  • Either direct current arc discharge or alternating current arc discharge can be used.
  • a cylindrical reaction vessel 10 such as a quartz tube is connected to a pre-chamber 11.
  • FIG. 1 One side of the pre-chamber 11 is connected to a vacuum pump 12, and a gas supply pipe 13 for feeding a mixed gas of H 2 and Ar is opened.
  • the gas supply pipe 13 incorporates a pressure control device 19 for adjusting the atmospheric pressure of the reaction vessel 10.
  • a vacuum valve 12a is provided in a pipeline from the pre-champer 11 to the vacuum pump 12.
  • Reaction vessel 10 extends horizontally from pre-chamber 11 to improve operability Preferably.
  • a heating mechanism 14 such as a resistance heater or a radiant heater for heating the net-like deposit of single-walled carbon nanotubes is arranged around the reaction vessel 10, and an exhaust pipe 15 is opened on the opposite side of the prechamber 11. I have.
  • Exhaust pipe 15 is an exhaust pump
  • the flow rate of the mixed gas of H2 and Ar flowing through the exhaust pipe 15 and the flow rate of the mixed gas in the reaction vessel 10 are adjusted by a flow control valve 17 provided on the way.
  • a thermocouple 18 By inserting a thermocouple 18 into the exhaust pipe 15, the ambient temperature of the reaction vessel 10 can be measured.
  • two graphite electrodes 20R and 20L connected to an AC power supply 21 by lead wires 22R and 22L are arranged opposite to each other in a direction orthogonal to the tube axis.
  • the graphite electrodes 20R and 20L can be moved in the reaction vessel 10 in the direction perpendicular to the tube axis by the feeder 23.
  • Graphite electrodes 20R and 20L are prepared by blending carbon with Fe catalyst and molding.
  • the Fe catalyst a fine-particle Fe simple catalyst having a particle size of ⁇ or less, which is produced from an oxide or carbide of Fe, is preferable from the viewpoint of improving the mechanical and chemical strength and the yield of the single-walled carbon nanotube.
  • the Fe fine particles contained in the graphite electrodes 20R and 20L become ultrafine particles of 10 nm or less when evaporated by arc discharge.
  • the vacuum degree in the vacuum pump 12: 13 ⁇ : 1.3X was evacuated to 10- 3 Pa or so, more to feed the mixed gas from the gas supply pipe 13 H2, Ar, 1.3 ⁇
  • the atmosphere pressure is maintained at about 6.7 ⁇ 10 4 Pa. After the atmosphere is adjusted, if an AC voltage of 20 to 30 V is applied between the graphite electrodes 20R and 20L with the heating mechanism 14 turned off, an AC arc discharge A is generated, and carbon evaporates from the graphite electrodes 20R and 20L.
  • the two graphite electrodes 20R and 20L are consumed under the same conditions.
  • the generated carbon vapor is sent to the exhaust pipe 15 side on the mixed gas flow F, and is deposited as a net-like deposit in a space connecting the graphite electrodes 20R and 20L and the inner wall of the reaction vessel 10.
  • the graphite electrodes 20R, 20L are retracted along the tube axis direction D (leftward in FIG. 1) as the deposition progresses, a net-like deposit with a very long length in a predetermined area extending in the tube axis direction D is formed in the reaction vessel 10. Accumulate inside.
  • the arc discharge is terminated and the reaction vessel 10 Vacuum suction is performed by the exhaust pump 16 and the gas fed into the reaction vessel 10 from the gas supply pipe 13 is switched from a mixed gas of H 2 and Ar to a mixed gas of O 2 and Ar.
  • the heating mechanism 14 is turned on, and a mixed gas of O 2 and Ar is sent at a flow rate of 4.0 to 6.0 ⁇ 10 ° CCM to supply oxygen to the reaction vessel 10. maintaining the partial pressure 2.0 ⁇ 4.0X 10 4 Pa, heating the net-like deposits 380 ⁇ 440 ° C while continuing to feed the gas mixture of 0 2, Ar.
  • the net-like sediment from which the impurity carbon has been removed is collected from the exhaust pipe 15 side of the reaction vessel 10 by a collection device 25 disposed inside the reaction vessel 10 slightly.
  • the trapping device 25 has a built-in cooling mechanism that circulates cooling water W to cool the net-like sediment heated to remove impurity carbon and improve trapping efficiency. After collecting the net-like sediment, the reaction vessel 10 is opened, and the collector 25 is taken out of the reaction vessel 10, whereby the single-walled carbon nanotube net-like sediment is collected.
  • Example Fe particles with a particle size of ⁇ or less were used as catalysts, and 1.0% by weight of Fe particles were mixed with graphite, and heated and pressed to prepare graphite electrode 20R, 20L having a diameter of 6 mm and a length of 20 mm.
  • the distance between the tips of the graphite electrodes 20R and 20L was set to 1.5 mm, and the graphite electrodes 20R and 20L were set in a quartz reaction vessel 10 having an inner diameter of 65 mm.
  • Net-like deposit 0 2 has been reduced to llmg in heat treatment in a mixed gas atmosphere of Ar, carbon nanoparticles, impurities carbon such as amorphous carbon is significantly removed contained in the net-like deposits was. Removal of the impurity carbon was due to the low-contrast amorpha bubbles observed in the net-like sediment before the heat treatment (SEM photograph: Fig. 2) and the net-like sediment after the heat treatment (SEM photograph: Fig. 3). It is also confirmed by the disappearance. The heat-treated net-like sediment was collected by a collector 25 and observed with a scanning electron microscope. As a result, it was confirmed that single-walled carbon nanotube bundles had been formed (Fig. 3). In addition, Fe fine particles mixed in the net-like sediment were converted to iron oxide by heat treatment, bonded together and increased in particle size, and were observed as particles with high contrast.
  • the change in the intensity of the D band and G band means that the purification removed amorphous carbon and the abundance of single-walled carbon nanotubes increased significantly.
  • peaks were detected in the radial breathing mode corresponding to the very fine diameter, although there were slight differences in distribution before and after purification.
  • the resulting single-walled carbon nanotubes had high crystallinity, high electrical conductivity, and excellent mechanical-chemical strength.
  • a string taken out of the net-like single-walled carbon nanotube was subjected to a tensile test, a string having a cross-sectional area of about 0.1 mm 2 withstood a load exceeding 100 g.
  • net-like deposits of single-walled carbon nanotubes generated by AC arc discharge are directly heat-treated in a mixed gas atmosphere of 02 and Ar.
  • carbon impurities such as carbon nanoparticles and amorphous carbon contained in the net-like sediment are gasified and removed, and single-wall carbon nanotubes with high purity can be obtained.
  • Ar SWNTs fabrication reactor was switched to a mixed gas of 0 2, Ar from the gas mixture, from a mechanical 'that chemical strength is low The purification difficulty is overcome, and high-purity single-walled carbon nanotubes are produced with high productivity.

Abstract

Une décharge en arc A est générée entre deux électrodes de graphite (20R, 20L), opposées en suivant une direction perpendiculaire à l'axe du tuyau dans un récipient de réaction (10) placé dans une atmosphère de gaz de mélange H2-Ar de manière à produire un dépôt de type en filet d'un nanotube de carbone à couche unique dans un espace formé par la connexion des électrodes de graphite (20R, 20L) avec une paroi interne du récipient de réaction (10). Lorsqu'une température dans le récipient de réaction (10) est commutée sur un mélange O2-Ar, et que l'intérieur du récipient de réaction (10) est réchauffé par un mécanisme de réchauffement (14), des impuretés de carbone telles que les nanoparticules de carbone et le carbone amorphe contenues dans le dépôt de type en filet sont transformées en gaz et évacuées du dépôt de type de carbone. On peut ainsi fabriquer et raffiner un nanotube de carbone à couche unique en utilisant le même récipient de réaction (10) pour produire aisément des nanotubes haute pureté à couche unique.
PCT/JP2004/002491 2003-05-12 2004-03-01 Procede et dispositif de fabrication pour nanotube de carbone a couche unique WO2004099072A1 (fr)

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JP2003132770A JP3810756B2 (ja) 2003-05-12 2003-05-12 単層カーボンナノチューブの製造方法及び装置

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Cited By (2)

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EP1967492A4 (fr) * 2005-11-29 2010-07-07 Univ Meijo Procede de production d'un nanotube de carbone et procede de purification de ce dernier
CN111661843A (zh) * 2020-05-27 2020-09-15 富耐克超硬材料股份有限公司 活化的纳米石墨粉体及其制备方法

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JP4900946B2 (ja) * 2005-11-29 2012-03-21 学校法人 名城大学 カーボンナノチューブの製造方法および精製方法
KR100827387B1 (ko) 2006-09-04 2008-05-06 세종대학교산학협력단 볼을 이용한 탄소나노튜브의 정제방법
JP6449610B2 (ja) * 2013-10-07 2019-01-09 株式会社Ｓｏｋｅｎ カーボンスーツ発生装置およびカーボンスーツ発生方法
KR102107167B1 (ko) * 2018-12-21 2020-05-06 이한성 나노튜브 합성장치

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1967492A4 (fr) * 2005-11-29 2010-07-07 Univ Meijo Procede de production d'un nanotube de carbone et procede de purification de ce dernier
US9067793B2 (en) 2005-11-29 2015-06-30 Meijo University Method for production of carbon nanotube and method for purification of the same
CN111661843A (zh) * 2020-05-27 2020-09-15 富耐克超硬材料股份有限公司 活化的纳米石墨粉体及其制备方法
CN111661843B (zh) * 2020-05-27 2022-12-13 富耐克超硬材料股份有限公司 活化的纳米石墨粉体及其制备方法

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JP2004331477A (ja) 2004-11-25

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