WO2010024459A1 - Procédé de production d’un nanotube de carbone - Google Patents

Procédé de production d’un nanotube de carbone Download PDF

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Publication number
WO2010024459A1
WO2010024459A1 PCT/JP2009/065379 JP2009065379W WO2010024459A1 WO 2010024459 A1 WO2010024459 A1 WO 2010024459A1 JP 2009065379 W JP2009065379 W JP 2009065379W WO 2010024459 A1 WO2010024459 A1 WO 2010024459A1
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WIPO (PCT)
Prior art keywords
catalyst
cnt
carbon
liquid
iron
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PCT/JP2009/065379
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English (en)
Japanese (ja)
Inventor
横井裕之
オムルザク ウル エミル
真下茂
岩崎秀治
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国立大学法人 熊本大学
クラレルミナス株式会社
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Priority to JP2010526820A priority Critical patent/JP5534456B2/ja
Publication of WO2010024459A1 publication Critical patent/WO2010024459A1/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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/166—Preparation in liquid phase

Definitions

  • the present invention relates to a method for producing carbon nanotubes.
  • Carbon nanotubes are substances composed of a three-dimensional structure in which graphene sheets (sheets in which carbon atoms are arranged in a hexagonal network) corresponding to one layer of graphite are rolled into a cylindrical shape. It is known that there are single-walled CNTs composed of one cylindrical graphene sheet and multi-walled CNTs in which a plurality of cylindrical graphene sheets are concentrically overlapped. In general, it has been found that the tip of the CNT immediately after synthesis is usually closed by a hemispherical graphite layer called a “cap”.
  • CNTs have a diameter on the order of nm and a length on the order of ⁇ m to cm, have an extremely large aspect ratio (a value obtained by dividing the length of CNT by the diameter of the same unit), and have a radius of curvature at the tip of several nm. It has a feature that it is extremely small, ⁇ several tens of nm.
  • CNT is physically and mechanically strong, has excellent chemical and thermal stability, and has the characteristics that it can be a metal or a semiconductor depending on the helical structure of the cylindrical portion. Therefore, CNTs are expected to be applied to electronic wiring materials for light-emitting devices, heat dissipation materials, fiber materials, electron emission sources for flat panel displays, transistor materials, electron emission sources (point light sources) for electron microscopes, etc. Yes.
  • JP 2002-201014 A Japanese Patent Laid-Open No. 10-273308 JP 2000-86217 A JP 2000-86218 A
  • CNTs obtained by the synthesis methods (1) and (2) are both in a state of being intertwined in a completely random direction. Moreover, it may contain a large amount of carbon nanocapsules, amorphous particles, and the like. In addition, high energy is required to generate arc discharge and high pulsed light, and high temperature is required, resulting in high manufacturing costs.
  • CNT can be produced by a relatively stable method, but the raw material is stored as a hazardous and explosive substance such as acetylene or carbon monoxide, or as a high-pressure gas such as methane.
  • a hazardous and explosive substance such as acetylene or carbon monoxide
  • a high-pressure gas such as methane.
  • problems such as the use of substances that require high risk of ignition.
  • ancillary equipment is large and a complicated process needs to be taken.
  • an object of the present invention is to provide a method capable of producing CNTs stably on an industrial scale.
  • CNT can be obtained by generating pulsed plasma between carbon metal electrodes in the presence of a catalyst in a liquid. It came.
  • [1] A method for producing carbon nanotubes, characterized by performing pulsed plasma discharge between carbon electrodes in the presence of a catalyst in a liquid; [2] The production method according to [1], wherein the catalyst is at least one selected from the group consisting of metals of Group 6 to Group 10 in the long-period periodic table and compounds thereof; Is provided.
  • CNT can be produced with relatively low energy (for example, low voltage) by the production method of the present invention. That is, since the diffusion of energy is suppressed and the energy efficiency is increased by carrying out in a liquid, the target product can be obtained at a higher reaction rate with a lower energy than in the prior art.
  • relatively low energy for example, low voltage
  • the method for producing carbon nanotubes of the present invention is characterized in that pulse plasma discharge is performed between carbon electrodes in a liquid in the presence of a catalyst.
  • a catalyst any carbon material such as graphite, amorphous carbon, and glassy carbon can be used.
  • the electrode may have any shape such as a rod, wire, or plate. Regarding the size of both poles, it may have a shape such that one of the sizes is different. Moreover, both poles may use the same carbon material or a different material, and may use what was shape
  • CNTs are generated in a liquid.
  • the liquid (solvent) that can be used is not particularly limited as long as it does not affect the reaction.
  • the liquid may be a mixture of two or more compounds.
  • Liquids that can be used include saturated hydrocarbons such as hexane, octane, decane, cyclohexane, cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene, and naphthalene, water, methanol, ethanol, propanol, butanol, ethylene glycol, Alcohols such as propylene glycol and 1,4-butanediol, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl benzoate and dimethyl phthalate, tetrahydrofuran, tetrahydropyran, dipropyl ether, dibutyl ether, diethylene glycol, t
  • the amount of liquid used is not particularly limited as long as both electrodes are in the liquid. More preferably, it is sufficient that the liquid scatters due to the generation of plasma or the diffusibility of the liquid is not lost depending on the product concentration.
  • CNT is produced in the presence of a catalyst.
  • a catalyst metals of Group 6 to Group 10 in the long-period periodic table and compounds thereof are used.
  • a catalyst may be used individually by 1 type and may use 2 or more types simultaneously or in steps.
  • the Group 6 to Group 10 metals include iron group metals (that is, iron, cobalt, nickel), chromium, molybdenum, ruthenium, rhodium, iridium, palladium, and platinum.
  • the catalyst shape any of a plate shape, a linear shape, and a particle shape may be used. However, in consideration of the generation efficiency of CNT, it is preferable to use a granular shape.
  • the particle size of the granular material to be used is not particularly limited. However, since the use of fine particles leads to the improvement of CNT production, particles with a particle size of 1 nm to 100 ⁇ m are usually used, but consideration is given to avoiding aggregation and production efficiency.
  • the thickness is preferably 2 nm to 50 ⁇ m, more preferably 5 nm to 10 ⁇ m.
  • the metal compound of Group 6 to Group 10 is not particularly limited.
  • carbides such as iron carbide, nickel carbide, and cobalt carbide, chromium chloride, molybdenum chloride, iron chloride, nickel chloride, cobalt chloride, ruthenium chloride, rhodium chloride, Palladium chloride, platinum chloride, chromium bromide, molybdenum bromide, iron bromide, nickel bromide, cobalt bromide, ruthenium bromide, rhodium bromide, palladium bromide, platinum bromide, iron sulfate, nickel sulfate, cobalt sulfate Mineral acids such as iron acetate, nickel acetate, cobalt acetate, palladium acetate, iron butyrate, nickel butyrate, cobalt butyrate, iron lactate, nickel lactate, cobalt lactate, iron tartrate, nickel tartrate, cobalt tartrate Salt, chromium ace
  • the catalyst may be dispersed or dissolved in the liquid or may be dispersed in the carbon electrode. Considering the efficiency of the reaction, it is preferable that it is dispersed in the carbon electrode, but it is not particularly limited because it is affected by the type of catalyst used and the reaction conditions.
  • the amount of catalyst used is not particularly limited as long as it exists at a concentration that does not affect the generation of plasma.
  • the catalyst is dispersed or dissolved in the liquid, it is preferably in the range of 0.001 mol / L to 5 mol / L, and when mixed in the electrode, it is 0.01 wt% to 10 wt%. It is preferable to mix within a range.
  • the temperature at which the pulse plasma discharge is performed is not particularly limited and is usually in the range of room temperature to 300 ° C., although it depends on the type of liquid used. If the temperature exceeds 300 ° C., the vapor pressure of the solvent to be used increases, which may cause ignition by plasma, which is not preferable. If the temperature is lower than room temperature, the viscosity of the solvent increases and the diffusibility of the product tends to be impaired. This is not preferable.
  • the voltage for generating plasma in the present invention is not particularly limited, and is usually in the range of 50V to 500V, preferably in the range of 60V to 400V, considering the necessity of safety and special equipment, and 80V to The range of 300V is more preferable.
  • the current for generating plasma is not particularly limited, and is usually in the range of 0.1 to 20 A, and preferably in the range of 0.2 to 10 A in consideration of energy efficiency.
  • the pulse interval of the pulse plasma discharge is not particularly limited, but is preferably 5 to 100 milliseconds, and more preferably 6 to 50 milliseconds.
  • the duration per pulsed plasma discharge also varies depending on the voltage and current that generate the plasma, but is usually in the range of 1 to 50 microseconds, and in the range of 2 to 30 microseconds considering the discharge efficiency. Is preferred.
  • vibration may be applied to the electrode.
  • the method for applying vibration is not particularly limited, and either a method for applying vibration periodically or a method for applying vibration intermittently may be used.
  • an electric actuator it is more preferable to use an electric actuator as means for applying vibration, because the amplitude of vibration and the distance between electrodes can be stabilized.
  • the atmosphere for carrying out the present invention can be carried out under reduced pressure, under pressure or under normal pressure, but usually under an inert gas such as nitrogen or argon in consideration of safety and operability. It is preferable to implement.
  • the CNT produced by the method of the present invention is deposited in the liquid, it is possible to obtain the CNT by removing the liquid used in a general method, for example, a filtration operation after performing a filtration operation. it can.
  • the CNTs obtained as described above are usually in the range of 0.7 to 50 nm in tube diameter and in the range of 50 nm to 10 ⁇ m in tube length, but sizes outside these ranges can be obtained depending on conditions.
  • the aspect ratio of the CNT and the curvature of the tip can be changed by appropriately adjusting the plasma generation voltage, the plasma generation current, the discharge pulse interval, and the duration per pulse plasma discharge.
  • Example 1 the same operation as in Example 1 was performed, except that iron (III) acetate was not used as a catalyst, and graphite containing 1% by weight of iron was used as an electrode.
  • a TEM photograph of the obtained black powder is shown in FIG. 2 (magnification: 100,000 times). From the TEM photograph, it was judged that the obtained black powder was CNT having a tube diameter of about 4 nm.
  • Example 3
  • Example 1 the same operation as in Example 1 was performed except that 0.001 g of molybdenum acetylacetonate was used instead of 0.001 g of iron (III) acetate.
  • a TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. From the TEM photograph, it was judged that the obtained black powder was CNT having a tube diameter of about 6 nm.
  • Example 4
  • Example 1 the same operation as in Example 1 was performed except that 200 g of ion-exchanged water was used instead of 200 g of anhydrous ethanol as a solvent.
  • a TEM photograph (magnification: 100,000 times) of the obtained black powder is shown in FIG. From the TEM photograph, it was judged that the obtained black powder was CNT having a tube diameter of about 4 nm.
  • carbon nanotubes can be produced with a low energy such as a relatively low voltage, which is highly industrially useful.

Abstract

Cette invention concerne un procédé de production stable d’un nanotube de carbone à l’échelle industrielle. L’invention concerne particulièrement un procédé de production d’un nanotube de carbone, une décharge plasma à impulsion étant causée entre des électrodes de carbone dans un liquide en présence d’un catalyseur. Le catalyseur est de préférence choisi dans le groupe constitué par les métaux des groupes 6 à 10 et leurs composés.
PCT/JP2009/065379 2008-08-28 2009-08-27 Procédé de production d’un nanotube de carbone WO2010024459A1 (fr)

Priority Applications (1)

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JP2010526820A JP5534456B2 (ja) 2008-08-28 2009-08-27 カーボンナノチューブの製造方法

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JP2008219565 2008-08-28
JP2008-219565 2008-08-28

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JP (1) JP5534456B2 (fr)
TW (1) TW201012747A (fr)
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013032258A (ja) * 2011-06-30 2013-02-14 Ulvac Japan Ltd グラフェンの製造方法
JP2014040352A (ja) * 2012-08-23 2014-03-06 Chube Univ グラフェンの製造方法
JP2014152095A (ja) * 2013-02-13 2014-08-25 Nagoya Univ グラフェンの製造方法
JP2014533973A (ja) * 2011-09-23 2014-12-18 パルティ、ヨーラム ナノチューブと人工肺とを備えるガス交換装置
JP2017222538A (ja) * 2016-06-15 2017-12-21 国立大学法人 熊本大学 グラフェン及び化学修飾グラフェンの製造方法
CN113233443A (zh) * 2021-04-22 2021-08-10 电子科技大学 氟化螺旋碳纳米管的制备方法及在锂一次电池中的应用

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JP2007504944A (ja) * 2003-09-10 2007-03-08 パランスキ ナフム ナノ粒子及びマイクロ粒子の製造方法
JP2007169159A (ja) * 2001-09-06 2007-07-05 Rosseter Holdings Ltd ナノ粒子及びナノチューブの生成装置及び生成方法、並びにガス貯蔵のためのこれらの使用

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JP2007169159A (ja) * 2001-09-06 2007-07-05 Rosseter Holdings Ltd ナノ粒子及びナノチューブの生成装置及び生成方法、並びにガス貯蔵のためのこれらの使用
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013032258A (ja) * 2011-06-30 2013-02-14 Ulvac Japan Ltd グラフェンの製造方法
JP2014533973A (ja) * 2011-09-23 2014-12-18 パルティ、ヨーラム ナノチューブと人工肺とを備えるガス交換装置
JP2014040352A (ja) * 2012-08-23 2014-03-06 Chube Univ グラフェンの製造方法
JP2014152095A (ja) * 2013-02-13 2014-08-25 Nagoya Univ グラフェンの製造方法
JP2017222538A (ja) * 2016-06-15 2017-12-21 国立大学法人 熊本大学 グラフェン及び化学修飾グラフェンの製造方法
CN113233443A (zh) * 2021-04-22 2021-08-10 电子科技大学 氟化螺旋碳纳米管的制备方法及在锂一次电池中的应用

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JPWO2010024459A1 (ja) 2012-01-26
JP5534456B2 (ja) 2014-07-02

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