WO2018123796A1 - Méthode de production de composition contenant des nanotubes de carbone à paroi unique - Google Patents

Méthode de production de composition contenant des nanotubes de carbone à paroi unique Download PDF

Info

Publication number
WO2018123796A1
WO2018123796A1 PCT/JP2017/045896 JP2017045896W WO2018123796A1 WO 2018123796 A1 WO2018123796 A1 WO 2018123796A1 JP 2017045896 W JP2017045896 W JP 2017045896W WO 2018123796 A1 WO2018123796 A1 WO 2018123796A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
compound
carbon nanotube
containing composition
carrier gas
Prior art date
Application number
PCT/JP2017/045896
Other languages
English (en)
Japanese (ja)
Inventor
宮浦健志
西野秀和
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2018500756A priority Critical patent/JPWO2018123796A1/ja
Publication of WO2018123796A1 publication Critical patent/WO2018123796A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • C01B32/159—Carbon nanotubes single-walled
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present invention relates to a method for producing a single-walled carbon nanotube-containing composition.
  • the structure of the carbon nanotube is a hollow tube (tube) in which a carbon hexagonal mesh surface called graphene is wound around a cylinder having a diameter of nanometer order.
  • Carbon nanotubes are classified into single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes depending on the number of graphene layers constituting the cylindrical structure. Also, depending on how the graphene is wound, carbon nanotubes can have interesting electrical and mechanical properties such as being metallic and semiconducting. By controlling the diameter, the number of layers, and the length of the carbon nanotube, it is expected to improve the performance and expand the applicability.
  • single-walled carbon nanotubes have ballistic conduction that allows the electric charge to move without receiving any scattering, whereas multi-walled carbon nanotubes cause current to flow through multiple layers, causing diffusion of charge between the layers. It is conduction.
  • Single-walled carbon nanotubes have properties superior to double-walled carbon nanotubes and multi-walled carbon nanotubes, such as thermal conductivity exceeding that of diamond and tough mechanical properties, while having flexibility that is extremely difficult to break. Therefore, single-walled carbon nanotubes are next-generation nanocarbon materials that are expected to be applied in the future for applications such as conductive inks, semiconductor devices, antistatic agents, and capacitor conductive members. is there.
  • the semiconductor single-walled carbon nanotube has a band gap in inverse proportion to the diameter, it can be separated from the metal single-walled carbon nanotube using a chemical method.
  • the semiconductor single-walled carbon nanotubes thus separated are expected to be applied to an excellent semiconductor device that can be bent transparently by taking advantage of its flexibility.
  • the semiconductor property becomes higher as the diameter becomes thinner, the single-walled carbon nanotube with a smaller diameter is expected to be a higher performance semiconductor material.
  • the crystallinity of carbon nanotubes is important for application to devices and the like.
  • the electrical conduction of carbon nanotubes is due to the movement of carriers on the surface of the carbon nanotubes, but this is scattered by structural defects and impurities, resulting in an increase in electrical resistance. Therefore, carbon nanotubes with high crystallinity are required for application to devices.
  • the CVD method (Chemical vapor deposition method), which is a highly efficient method for synthesizing single-walled carbon nanotubes, is roughly classified into two types from the viewpoint of the catalyst used.
  • the gas-phase flow method is excellent as a method that can continuously supply raw materials and continuously obtain single-walled carbon nanotubes.
  • Patent Document 1 discloses a method for producing single-walled carbon nanotubes using toluene as a carbon source and supplying hydrogen gas, ferrocene and thiophene at 1 to 50 m / s.
  • methods for producing single-walled carbon nanotubes using a plurality of carbon compounds such as aromatic compounds and aliphatic compounds as raw materials are known (Patent Documents 2 to 4).
  • the manufacturing method which improved the supply amount of the carbon source using the single carbon source is known (patent document 5).
  • the carbon nanotube synthesis methods described in Patent Documents 1 to 5 have a low yield of single-walled carbon nanotubes, and have not been put to practical use.
  • the production methods disclosed in Patent Documents 2 to 4 have problems that the concentration of carbon source in the gas phase to be supplied is low and the yield of single-walled carbon nanotubes is low.
  • the yield of carbon nanotubes is low, and this is also difficult to say as an efficient production method.
  • only hydrogen gas is often used as the carrier gas, and there are problems in terms of safety and cost.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a carbon nanotube-containing composition capable of obtaining highly crystalline single-walled carbon nanotubes with high efficiency.
  • a method for producing a carbon nanotube-containing composition wherein a catalytic carbon source solution containing a carbon compound, an iron compound, and a sulfur compound is introduced into a reaction tube in a mixed carrier gas of hydrogen and an inert gas, and the mixed carrier gas in a standard state
  • the carbon atom molar concentration in the carbon compound is 0.16 mmol / L or more and 0.53 mmol / L or less, and the ratio of the number of sulfur atoms in the sulfur compound to the number of iron atoms in the iron compound is 0.7 to 2.4.
  • the method for producing a carbon nanotube-containing composition wherein the hydrogen concentration in the mixed carrier gas is 50% by volume to 90% by volume in a standard state, and the carbon compound contains an aromatic compound.
  • single-walled carbon nanotubes with high crystallinity can be obtained with high efficiency.
  • FIG. 1 is a schematic view of an apparatus for synthesizing a single-walled carbon nanotube-containing composition used in Examples of the present invention.
  • the present invention is a method for producing a carbon nanotube-containing composition in which a catalytic carbon source solution containing a carbon compound, an iron compound, and a sulfur compound is introduced into a reaction tube in a mixed carrier gas of hydrogen and an inert gas, and the standard state
  • the carbon atom molar concentration in the carbon compound is 0.16 mmol / L or more and 0.53 mmol / L or less, and the ratio of the number of sulfur atoms in the sulfur compound to the number of iron atoms in the iron compound is 0. 7 to 2.4
  • a method for producing a carbon nanotube-containing composition in which the hydrogen concentration in the mixed carrier gas is 50% by volume to 90% by volume in a standard state, and the carbon compound contains an aromatic compound.
  • a carbon compound containing an aromatic compound is used as a carbon source.
  • the time when the carbon compound starts to be supplied to the reaction tube is set as the start of synthesis.
  • the reaction tube is heated to a high temperature by a heating furnace, and the supplied carbon compound is decomposed at a high temperature to become a carbon nanotube-containing composition.
  • Any carbon compound may be used as long as it can serve as a carbon source, but an aromatic compound that is liquid at room temperature and relatively difficult to decompose at high temperature is preferable.
  • aromatic compound for example, benzene, toluene, xylene, cumene, ethylbenzene, diethylbenzene, trimethylbenzene, naphthalene and the like can be used.
  • benzene, toluene, ethylbenzene, and xylene are particularly preferable, and benzene is most preferable.
  • an aromatic compound containing a hetero atom can be used as the raw material hydrocarbon, an aromatic hydrocarbon compound containing no hetero atom is more preferable.
  • the iron compound is decomposed in a reaction tube to become iron particles, thereby acting as a catalyst for producing a carbon nanotube-containing composition.
  • a preferable shape of the iron particles is spherical or elliptical nanoparticles. Because of the characteristics of the nanoparticles, the phase transition temperature and the like fluctuate, so that the carbon nanotube-containing composition can be synthesized at a high temperature during the growth of the carbon nanotubes while changing the shape in a specific shape or fluidly.
  • the carbon nanotube-containing composition grows starting from iron particles derived from the iron compound. At this time, the carbon nanotube-containing composition grows by the precipitation of carbon atoms dissolved in the iron particles.
  • the amount of carbon atoms dissolved in the iron particles and the degree of the precipitation depend on the diameter and layer of the obtained carbon nanotubes. Affects number and length. Since the carbon nanotube-containing composition is thus grown from the iron particles, the size of the iron particles is preferably several nanometers to several tens of nanometers, and most preferably several nanometers to ten nanometers.
  • ferrocene or a ferrocene derivative as the iron compound because the carbon nanotube-containing composition can be continuously produced with high purity.
  • thermally decomposing an organometallic compound such as ferrocene or a ferrocene derivative in a heating furnace iron particles as a catalyst can be efficiently generated.
  • Ferrocene or a ferrocene derivative is preferred because the decomposition rate of the skeleton around the iron atom of the molecule having a ferrocene skeleton and the rate of formation of iron particles accompanying the decomposition are within the carrier gas mixing ratio and the preferred temperature range set in the present invention. This is considered to be reasonably preferable.
  • ferrocene having a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an acetyl group, a carboxyl group, a hydroxyl group, an amino group, and an epoxy group
  • ferrocene having a phenyl group, anisyl group, phenol group, or a heterocyclic compound containing a hetero atom as a substituent can also be used.
  • the purity of an iron compound is preferable.
  • the sulfur compound acts as a promoter for promoting the synthesis of the carbon nanotube-containing composition.
  • Sulfur compounds can interact with iron particles as a catalyst to promote and control the growth of the carbon nanotube-containing composition. The reason why the sulfur compound is necessary in the growth mechanism of the carbon nanotube-containing composition is not clear, but sulfur atoms are unevenly mixed in the iron particle catalyst, so that the sulfur atoms are localized in or on the iron particles, It is presumed that the diameter and directionality of the carbon nanotubes grown on the iron particle catalyst are determined.
  • the ratio of the iron compound and the sulfur compound introduced into the reaction tube is such that the ratio of the number of sulfur atoms in the sulfur compound to the number of iron atoms in the iron compound is 0.7 to 2.4, more preferably 0. .7 to 1.8, most preferably 1.0 to 1.8.
  • the ratio of the iron compound and the sulfur compound so as to achieve this atomic ratio, the amount of carbon in which sulfur atoms can be dissolved in the iron particles can be controlled, and a carbon nanotube-containing composition having a thin average diameter can be obtained.
  • Usable sulfur compounds include sulfur-containing compounds such as thiophene, ethanethiol, propanethiol, butanethiol, thiophenol, and more preferably thiophene.
  • a mixed carrier gas of hydrogen and inert gas is used. Nitrogen gas, helium, argon or the like is used as the inert gas.
  • hydrogen is thought to activate iron particle surfaces by reducing iron.
  • the amount of hydrogen in the mixed carrier gas is too large, the amount of hydrogen adsorbed on the surface of the iron particles is too large and the catalytic capacity of the iron particles is reduced. There is a risk of doing. Therefore, it is preferable to dilute hydrogen with an inert gas to such an extent that the reaction is not hindered while securing the amount of hydrogen necessary for activation.
  • the reaction can be controlled by adjusting the hydrogen concentration in the mixed carrier gas.
  • nitrogen gas is used as the inert gas, it is preferable because it is inexpensive and can reduce manufacturing costs.
  • nitrogen gas, helium, argon, and the like have different thermal conductivities, it is preferable to select the type of inert gas and the hydrogen concentration according to the production conditions of the carbon nanotube-containing composition.
  • the hydrogen concentration in the mixed carrier gas is preferably 50% by volume or more and 90% by volume or less in the standard state.
  • the standard state means 0 ° C. and 1 atm. This range is preferable particularly when nitrogen gas is used as the inert gas. More preferably, they are 60 volume% or more and 90 volume% or less, Most preferably, they are 60 volume% or more and 80 volume% or less.
  • the hydrogen concentration in the mixed carrier gas is preferably 55% by volume or more and 90% by volume or less in the standard state.
  • helium is used as the inert gas, since the thermal conductivity is as high as hydrogen, the hydrogen concentration in the mixed carrier gas only needs to be higher than the concentration contributing to the reaction, and is preferably 50% by volume or higher.
  • the carbon compound, iron compound and sulfur compound are preferably mixed and introduced into the reaction tube as a catalytic carbon source solution.
  • a catalytic carbon source solution can be supplied to the reaction tube by spraying or the like.
  • the spraying method include a method in which a catalytic carbon source solution is supplied to a two-fluid nozzle together with a carrier gas and sprayed.
  • a catalytic carbon source solution can be obtained by dissolving it in the carbon compound in the liquid state even if the iron compound or sulfur compound is solid.
  • the carbon compound When the carbon compound is solid at normal temperature and normal pressure, the carbon compound may be heated and melted and mixed with the iron compound and sulfur compound.
  • a mechanism for mixing so that the ratio of the carbon compound, iron compound and sulfur compound is kept constant in the synthesizer. It is good to synthesize after providing the inside.
  • the carbon compound is solid, it is preferably supplied after being melted or sublimated. Carbon compounds, iron compounds, and sulfur compounds have different decomposition temperatures and decomposition rates. Therefore, if the heating method of the reaction tube is different, the decomposition temperature and decomposition rate change, so the ratio can be finely adjusted. It may be preferable.
  • the molar concentration of carbon atoms in the carbon compound is 0.16 mmol / L or more and 0.53 mmol / L based on the mixed carrier gas in the standard state (0 ° C., 1 atm).
  • the carbon compound concentration in the carrier gas is controlled to be L or less.
  • the carbon compound concentration is too high, decomposition of the carbon compound proceeds excessively, and amorphous carbon called amorphous carbon tends to be generated.
  • Amorphous carbon adheres to the surface and inside of single-walled carbon nanotubes as impurities, which causes the purity of single-walled carbon nanotubes to decrease.
  • the iron particles that serve as a catalyst are coated with amorphous carbon, which hinders the growth of single-walled carbon nanotubes, which causes a decrease in yield. If the carbon atom molar concentration based on the mixed carrier gas is larger than the predetermined concentration, double-walled carbon nanotubes grow as described in Patent Document 3, and the selectivity of single-walled carbon nanotube growth may be reduced. Are known. On the other hand, when the concentration of the carbon compound in the carrier gas is too low, the carbon atom that becomes the growth source of the carbon nanotubes becomes insufficient, resulting in a decrease in yield.
  • the carbon atom molar concentration in the carbon compound is 0.16 mmol / L or more and 0.53 mmol / L or less based on the mixed carrier gas in the standard state. More preferably, it is 0.20 mmol / L or more and 0.50 mmol / L or less, and most preferably 0.25 mmol / L or more and 0.50 mmol / L or less.
  • the carbon compound preferably contains an aromatic compound.
  • the yield of the carbon nanotube-containing composition increases as the synthesis temperature increases.
  • chain-type saturated hydrocarbons or chain-type unsaturated hydrocarbons are used as the carbon compound, they react even at relatively low temperatures. Therefore, when the synthesis temperature is raised, excessive decomposition occurs and side reactions are likely to occur. There are drawbacks.
  • an aromatic compound is used as the carbon compound, by-products can be suppressed in the reaction at a high temperature, which is preferable in terms of improving the yield of the carbon nanotube-containing composition.
  • side reactions may occur due to the complicated reaction, and the yield of the resulting carbon nanotube-containing composition may be reduced.
  • the use of only one carbon compound as the carbon source is preferable in that the synthesis temperature can be increased while suppressing side reactions, and this is suitable for mass production.
  • the aromatic compound may be a compound having a substituent such as a methyl group, an ethyl group or an ethylene group.
  • a substituent such as a methyl group, an ethyl group or an ethylene group.
  • preferred aromatic compounds include benzene, toluene, ethylbenzene, xylene and the like, and more preferred is benzene.
  • the linear velocity of the mixed carrier gas is preferably 500 cm / min or more and 1500 cm / min or less.
  • the linear velocity of the mixed carrier gas affects the heat conduction during the synthesis and the decomposition behavior of the carbon compound resulting therefrom.
  • the synthesis temperature is relatively high, the carbon compound may be excessively decomposed. Therefore, it is preferable to adjust the linear velocity of the mixed carrier gas so as to shorten the reaction time.
  • the synthesis temperature is relatively low, in order to promote the decomposition of the carbon compound, it is preferable to adjust the linear velocity of the mixed carrier gas so as to increase the reaction time to adjust the decomposition of the carbon compound.
  • the linear velocity is increased when the thermal conductivity of the mixed carrier gas increases due to the composition of the mixed carrier gas, and the linear velocity is decreased when the thermal conductivity decreases.
  • the linear velocity is too high, the reaction time is short and the yield of the carbon nanotube-containing composition is low.
  • the linear velocity of the mixed carrier gas is 500 cm / min or more and 1500 cm / min or less.
  • the lower limit of the linear velocity is more preferably 600 cm / min or more, and most preferably 700 cm / min or more.
  • the upper limit of the linear velocity is more preferably 1400 cm / min or less, and most preferably 1300 cm / min or less.
  • the yield of the carbon nanotube-containing composition increases as the synthesis temperature increases.
  • the synthesis temperature of the carbon nanotube-containing composition refers to the temperature of the heated reaction tube.
  • the reaction tube temperature may be measured by inserting a thermocouple into the electric furnace and placing the tip of the thermocouple at a distance of about 1 mm from the reaction tube surface.
  • the temperature of the reaction tube is preferably 1100 ° C. or higher and 1500 ° C. or lower.
  • the lower limit of the temperature of the reaction tube is more preferably 1150 ° C or higher, and most preferably 1200 ° C or higher.
  • the upper limit of the temperature of the reaction tube is more preferably 1450 ° C. or less, and most preferably 1400 ° C. or less.
  • a carbon nanotube-containing composition having an average diameter of 2.0 nm or less, a ratio of single-walled carbon nanotubes of 70% or more, and a G / D ratio of 50 or more can be synthesized.
  • the average diameter of the carbon nanotube-containing composition refers to an average diameter calculated by least square average of 100 carbon nanotubes observed with a transmission electron microscope.
  • the ratio of single-walled carbon nanotubes of 70% or more means that when 100 carbon nanotubes are observed, 70 or more are single-walled carbon nanotubes.
  • the diameter and the number of layers were observed with a transmission electron microscope at a magnification of 300,000 times or more, and the field of view in which the diameter and the number of layers of three or more carbon nanotubes in one field of view can be judged was observed over 35 fields of view. It was calculated by counting the number and diameter of carbon nanotube layers in the field of view.
  • the G / D ratio the ratio of the peak height of D band derived from the G band derived from graphite observed around 1590 cm -1 in the Raman spectrum, the defect of the amorphous carbon or graphite observed around 1350 cm -1 Say.
  • a carbon nanotube with a higher G / D ratio has higher crystallinity and higher quality.
  • the reaction tube 102 is a reaction tube for synthesizing carbon nanotubes and is a mullite vertical reaction tube having an inner diameter of 52 mm, an outer diameter of 60 mm, a length of 1500 mm, and an effective heating length of 1100 mm.
  • the electric furnace 101 is provided on the outer periphery of the reaction tube 102, generates heat when energized, and heats the reaction tube 102 with the generated heat.
  • the catalytic carbon source solution spray two-fluid nozzle 103 is a device that jets a catalytic carbon source solution 106 in which a carbon compound, an iron compound, and a sulfur compound are mixed into the reaction tube 102 in the form of a mist.
  • the micro feeder 107 adjusts the supply amount of the catalytic carbon source solution 106 supplied to the catalytic carbon source solution spray two-fluid nozzle 103.
  • the mass flow controller 105 adjusts the flow rates of the inert gas and the hydrogen gas that are carrier gases.
  • the inert gas is supplied from an inert gas cylinder 109, and the hydrogen gas is supplied from a hydrogen gas cylinder 110, respectively.
  • the collection container 104 is provided in the lower part of the reaction tube 102 and collects the carbon nanotube-containing composition synthesized in the reaction tube 102.
  • the synthesized carrier gas is discharged from the exhaust pipe 108.
  • Example 1 A carbon nanotube-containing composition was produced using the vertical carbon nanotube production apparatus shown in FIG.
  • the electric furnace set temperature in the heating region of the reaction tube was set to 1290 ° C., and a total of 26 L / min of nitrogen gas 13 L / min and hydrogen gas 13 L / min were supplied as carrier gases to replace the inside of the reaction tube with carrier gas.
  • a catalytic carbon source solution mixed at a ratio of benzene: ferrocene: thiophene 75: 5: 2.5 in terms of weight was supplied at 145 mg / min to synthesize a carbon nanotube-containing composition for 30 minutes.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state (0 ° C., 1 atm) was 0.39 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 1.1.
  • the product was allowed to cool sufficiently, and the carbon nanotube-containing composition was taken out from the collection container.
  • the obtained carbon nanotube-containing composition had an average diameter of 1.4 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 96%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.40 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 1.1.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.3 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 74%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.38 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 1.1.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.3 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 88%.
  • Example 4 A carbon nanotube-containing composition was produced in the same manner as in Example 1, except that the carrier gas was 9 L / min nitrogen gas and 9 L / min hydrogen gas, and the catalyst carbon source solution was supplied at 101 mg / min.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.39 mmol / L.
  • the obtained carbon nanotube-containing composition had an average diameter of 1.4 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 90%.
  • Example 5 A carbon nanotube-containing composition was produced in the same manner as in Example 1 except that toluene was used as the carbon compound.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.38 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 1.1.
  • the obtained carbon nanotube-containing composition had an average diameter of 1.4 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 90%.
  • Example 6 A carbon nanotube-containing composition was produced in the same manner as in Example 1, except that the carrier gas was 10.4 L / min of nitrogen gas and 26 L / min in total of hydrogen gas 15.6 L / min.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.38 mmol / L.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.5 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 91%.
  • Example 7 A carbon nanotube-containing composition was produced in the same manner as in Example 1 except that the carrier gas was changed to a total of 26 L / min of nitrogen gas 7.8 L / min and hydrogen gas 18.2 L / min.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.38 mmol / L.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.5 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 95%.
  • Example 8 A carbon nanotube-containing composition was produced in the same manner as in Example 1 except that the carrier gas was changed to a total of 26 L / min of nitrogen gas 5.2 L / min and hydrogen gas 20.8 L / min.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.37 mmol / L.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.5 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 95%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.37 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalyst carbon source solution was 1.7.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.5 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 89%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.37 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalyst carbon source solution was 2.2.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.4 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 82%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.4 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 0.66.
  • the average diameter of the obtained carbon nanotube-containing composition was 2.1 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 93%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.40 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 0.22.
  • the average diameter of the obtained carbon nanotube-containing composition was 2.1 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 92%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.20 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 0.22.
  • the obtained carbon nanotube-containing composition had an average diameter of 2.2 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 90%.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 1.05 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 0.22.
  • the obtained carbon nanotube-containing composition had an average diameter of 2.2 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 22%.
  • a carbon nanotube-containing composition was produced in the same manner as in Example 1 except that decalin was used as the carbon compound.
  • the carbon atom molar concentration in the carbon compound based on the mixed carrier gas in the standard state at this time was 0.35 mmol / L.
  • the ratio of the number of sulfur atoms to the number of iron atoms contained in the catalytic carbon source solution was 1.1.
  • the average diameter of the obtained carbon nanotube-containing composition was 1.4 nm, and the single-walled carbon nanotube ratio in the carbon nanotube-containing composition was 82%.
  • the G / D ratio indicating the crystallinity of the carbon nanotube-containing composition was 9, it is considered that a carbon nanotube-containing composition with many defects or carbon by-products was obtained.
  • highly crystalline single-walled carbon nanotubes can be produced with high efficiency and high yield.
  • the single-walled carbon nanotubes obtained by the present invention are expected to be widely applied in various technical fields such as conductive inks, semiconductor devices, antistatic agents, capacitor conductive members, etc. by utilizing the characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

La présente invention concerne une méthode de production d'une composition contenant des nanotubes de carbone, une solution source de carbone catalyseur contenant un composé de carbone, un composé de fer et un composé de soufre étant introduits dans un tube de réaction dans un gaz porteur mixte d'hydrogène et d'un gaz inerte. Selon la présente invention, la concentration molaire d'atomes de carbone dans le composé de carbone est de 0,16 mmol/L à 0,53 mmol/L (inclus) sur la base du gaz porteur mixte dans un état standard; le rapport du nombre d'atomes de soufre dans le composé de soufre au nombre d'atomes de fer dans le composé de fer est de 0,7 à 2,4; la concentration en hydrogène dans le gaz porteur mixte est de 50 % en volume à 90 % en volume (inclus) dans un état standard; et le composé carboné contient un composé aromatique. Selon la présente invention, des nanotubes de carbone à paroi unique ayant une cristallinité élevée peuvent être obtenus très efficacement.
PCT/JP2017/045896 2016-12-26 2017-12-21 Méthode de production de composition contenant des nanotubes de carbone à paroi unique WO2018123796A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018500756A JPWO2018123796A1 (ja) 2016-12-26 2017-12-21 単層カーボンナノチューブ含有組成物の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016250941 2016-12-26
JP2016-250941 2016-12-26
JP2017159910 2017-08-23
JP2017-159910 2017-08-23

Publications (1)

Publication Number Publication Date
WO2018123796A1 true WO2018123796A1 (fr) 2018-07-05

Family

ID=62711124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/045896 WO2018123796A1 (fr) 2016-12-26 2017-12-21 Méthode de production de composition contenant des nanotubes de carbone à paroi unique

Country Status (2)

Country Link
JP (1) JPWO2018123796A1 (fr)
WO (1) WO2018123796A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577208A (zh) * 2019-08-18 2019-12-17 复旦大学 一种亲钠性导电碳纳米管骨架材料及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006213590A (ja) * 2005-01-04 2006-08-17 National Institute Of Advanced Industrial & Technology 極細単層カーボンナノチューブからなる炭素繊維集合体及びその製造方法
JP2007246316A (ja) * 2006-03-14 2007-09-27 National Institute Of Advanced Industrial & Technology 単層のカーボンナノチューブの製造方法
JP2014094869A (ja) * 2012-11-12 2014-05-22 National Institute Of Advanced Industrial & Technology カーボンナノチューブの製造方法、カーボンナノチューブおよび識別マーカー
JP2015048263A (ja) * 2013-08-30 2015-03-16 帝人株式会社 単層カーボンナノチューブ及び二層カーボンナノチューブを含有しているカーボンナノチューブ集合体、並びにその合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006213590A (ja) * 2005-01-04 2006-08-17 National Institute Of Advanced Industrial & Technology 極細単層カーボンナノチューブからなる炭素繊維集合体及びその製造方法
JP2007246316A (ja) * 2006-03-14 2007-09-27 National Institute Of Advanced Industrial & Technology 単層のカーボンナノチューブの製造方法
JP2014094869A (ja) * 2012-11-12 2014-05-22 National Institute Of Advanced Industrial & Technology カーボンナノチューブの製造方法、カーボンナノチューブおよび識別マーカー
JP2015048263A (ja) * 2013-08-30 2015-03-16 帝人株式会社 単層カーボンナノチューブ及び二層カーボンナノチューブを含有しているカーボンナノチューブ集合体、並びにその合成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577208A (zh) * 2019-08-18 2019-12-17 复旦大学 一种亲钠性导电碳纳米管骨架材料及其制备方法和应用
CN110577208B (zh) * 2019-08-18 2022-11-18 复旦大学 一种亲钠性导电碳纳米管骨架材料及其制备方法和应用

Also Published As

Publication number Publication date
JPWO2018123796A1 (ja) 2019-10-31

Similar Documents

Publication Publication Date Title
EP2025643B1 (fr) Méthode de préparation de nanotubes de carbone monoparoi
EP3053877B1 (fr) Procédé de fabrication de nanotubes de carbone de type faisceau à surface spécifique élevée
CA2559070C (fr) Nanotubes de carbone monoparoi, multiparois, fonctionnalises, dopes et composites de ces derniers
JP5550833B2 (ja) 高品質単層カーボンナノチューブ成長の方法および装置
JP5102633B2 (ja) 長いカーボン単層ナノチューブを成長させるための方法
US10758898B2 (en) Method for manufacturing carbon nanotube agglomerate having controlled bulk density
KR101864850B1 (ko) 탄소 나노구조체를 제조하는 방법 및 장치
JP6492598B2 (ja) カーボンナノチューブの製造方法
Dichiara et al. The growth of carbon nanotube multilayers on ceramic μ-particles by catalytic chemical vapour deposition
US9950926B2 (en) Method for production of germanium nanowires encapsulated within multi-walled carbon nanotubes
JP5364904B2 (ja) カーボンナノファイバー集合体の製造方法
Peng et al. Diameter-controlled growth of aligned single-walled carbon nanotubes on quartz using molecular nanoclusters as catalyst precursors
CN107614426B (zh) 含碳纳米管组合物的制造方法
WO2018123796A1 (fr) Méthode de production de composition contenant des nanotubes de carbone à paroi unique
Mansoor et al. Optimization of ethanol flow rate for improved catalytic activity of Ni particles to synthesize MWCNTs using a CVD reactor
Zhuang et al. Systematic investigation of the ball milling–annealing growth and electrical properties of boron nitride nanotubes
JP2018016521A (ja) 単層カーボンナノチューブ含有組成物の製造方法
JP4706058B2 (ja) 極細単層カーボンナノチューブからなる炭素繊維集合体の製造方法
Zhu et al. Synthesis of carbon coated silica nanowires
KR101580928B1 (ko) 코발트-구리계 촉매를 이용한 실리콘계 탄소나노섬유 합성방법
Sadeghian et al. Synthesis optimisation and characterisation of multiwalled carbon nanotubes produced by spray pyrolysis of hexane
JP6950939B2 (ja) カーボンナノチューブ集合体合成用触媒担持体及びカーボンナノチューブ集合体合成用部材
Khairurrijal et al. Structural characteristics of carbon nanotubes fabricated using simple spray pyrolysis method
RU2427423C1 (ru) Металлоксидный катализатор для выращивания пучков углеродных нанотрубок из газовой фазы
KR20110037757A (ko) 컵형 탄소나노튜브 및 그 제조방법

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018500756

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17886581

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17886581

Country of ref document: EP

Kind code of ref document: A1