WO2007004652A1 - Procédé de production d'un liquide de dispersion de nanotubes de carbone - Google Patents

Procédé de production d'un liquide de dispersion de nanotubes de carbone Download PDF

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Publication number
WO2007004652A1
WO2007004652A1 PCT/JP2006/313325 JP2006313325W WO2007004652A1 WO 2007004652 A1 WO2007004652 A1 WO 2007004652A1 JP 2006313325 W JP2006313325 W JP 2006313325W WO 2007004652 A1 WO2007004652 A1 WO 2007004652A1
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Prior art keywords
carbon nanotube
container
carbon nanotubes
organic solvent
dispersion
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PCT/JP2006/313325
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English (en)
Japanese (ja)
Inventor
Atsushi Ikeda
Jun-Ichi Kikuchi
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National University Corporation NARA Institute of Science and Technology
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Priority to JP2007524079A priority Critical patent/JP5109129B2/ja
Publication of WO2007004652A1 publication Critical patent/WO2007004652A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • 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
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/28—Solid content in solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a dispersion containing carbon nanotubes, and more specifically, a dispersion in which carbon nanotubes are stably dispersed from a bundle of carbon nanotubes (or a carbon nanotube mixture). It relates to a method of manufacturing. Furthermore, the present invention also relates to a member manufactured using the carbon nanotube dispersion obtained by the method of the present invention.
  • a carbon nanotube (hereinafter also abbreviated as "CNT”) is one of carbon allotropes having a structure in which a graphite sheet having a hexagonal network of carbon atoms arranged in a cylindrical shape. The diameter is on the order of nanometers.
  • Two types of carbon nanotubes are known: single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs).
  • SWNTs single-walled carbon nanotubes
  • MWNTs multi-walled carbon nanotubes
  • Single-walled carbon nanotubes are a single graphite sheet rolled into a cylindrical shape, whereas multi-walled carbon nanotubes are concentric circles of graphite sheets that overlap in multiple layers at approximately equal intervals. It is.
  • Such carbon nanotubes have unique functions due to their unique structures, and are expected to be applied in various fields.
  • single-walled carbon nanotubes have a relatively large specific surface area, and thus are considered suitable for applications such as gas storage materials such as hydrogen or
  • purifying carbon nanotubes produced by a conventional production method is not always convenient for various applications.
  • purification of carbon nanotubes generally the force that can be obtained by sonicating carbon nanotubes in an acidic solution (see, for example, Non-Patent Document 1) and then neutralizing and diluting such a mixture
  • Non-Patent Document 2 In order to obtain an alcohol dispersion of single-walled carbon nanotubes, a method using berylviridine as a solubilizing agent is disclosed, and it is impractical because sonication for 6 hours is required (for example, Non-Patent Document 2). In addition, a method for producing an amide polar organic solvent dispersion of single-walled carbon nanotubes using polyvinylbiridone as a solubilizing agent has been disclosed, but a nonionic surfactant is an essential component, and it is produced. Requires one hour of sonication (see, for example, Patent Document 1).
  • a method using a polythiophene polymer to obtain a dispersion of carbon nanotubes is also disclosed.
  • a method for obtaining a dispersion (l) CNT is preliminarily dispersed in a solvent under ultrasonic irradiation, and then a conjugated polymer is added and dispersed. (2) CNT and a conjugated polymer are dissolved in a solvent. (3) a method of adding and dispersing CNT in a molten conjugated polymer (see, for example, Patent Document 2 and Paragraph 0016). .
  • Non-patent literature l Jie Liu, Andrew G. Rinzler, etc, “Fullerene PipesJ, Scien ce, 1998. 5. 22, No. 280, pl253-1256
  • Non-Patent Document 2 Jason H. Rouse, “Polymer—Assisted Dispersion of 3 ⁇ 4 mgl e— Walled Carbon Nanotubes in Alcohols and Applicability toward Carbon Nanotube / Sol— Gel Composite Formation J, Langmuir 2005, 21, pl055- 1061
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-154630
  • Patent Document 2 JP-A-2005-089738
  • the present invention provides:
  • a method for producing a dispersion comprising carbon nanotubes comprising:
  • step (i) subjecting the carbon nanotube and the cyclic organic compound to vibration pulverization at a frequency of 5 to 120 s _1 to obtain a carbon nanotube mixture (hereinafter also referred to as “step (i)”), and
  • step (ii) A step of adding an organic solvent to the carbon nanotube mixture to obtain a dispersion containing carbon nanotubes (hereinafter also referred to as “step (ii)”)
  • step (i) is soluble in the organic solvent used in step (ii).
  • the term “vibrating crushing” refers to mechanical shearing on carbon nanotubes by directly applying a mechanical impact to force-bonded nanotubes. This means that the force is applied directly.
  • the method of the present invention has a feature that a dispersion containing carbon nanotubes can be obtained by carrying out such vibration pulverization.
  • the step (ii) of obtaining a dispersion containing carbon nanotubes is additionally characterized by centrifugal separation and Z or filter filtration.
  • the bundle of carbon nanotubes can be at least partially dissociated.
  • dispersions stably contain is subjected to about 5.
  • carbon nano A carbon nanotube dispersion liquid containing a tube, an alcohol, an ether organic solvent or an amide organic solvent as an organic solvent, and polybutylpyrrolidone as a cyclic organic compound is provided.
  • a carbon nanotube dispersion containing carbon nanotubes, an amide organic solvent, a sulfoxide or halogen organic solvent as an organic solvent, and polythiophene as a cyclic organic compound is provided.
  • a member including a substrate having a carbon nanotube film on the surface
  • the carbon nanotube film is a film formed by applying a dispersion containing carbon nanotubes obtained by the method of the present invention to the surface of a substrate and then drying it. .
  • a dispersion in which carbon nanotubes are stably dispersed can be obtained in a shorter time and more simply.
  • the carbon nanotubes are dispersed stably in time in an organic solvent, and the long-term stability is excellent.
  • a dispersion can be considered substantially a solution.
  • the dispersion in which the carbon nanotubes are stably dispersed contains at least one bon nanotube having a dissociated force of the bundle, so that the carbon nanotubes are bundled in the solvent.
  • the specific surface area of the carbon nanotube increases. Therefore, when a member manufactured using such a dispersion is used as a gas occlusion product, the gas occlusion amount increases as compared with the case of using bundle-like carbon nanotubes, and approaches the theoretical value.
  • the carbon nanotubes from which the bundles are dissociated have a larger contact area with the electrode surface than the bundles, the members manufactured using the dispersion obtained by the method of the present invention are used as the electrodes. The one used is highly efficient and approaches its theoretical value.
  • the “theoretical value” here is based on the assumption that all of the carbon nanotubes contained in the strong member are dissociated bundles. ⁇ ⁇ Ideal hydrogen storage capacity or electrode efficiency.
  • FIG. 1 shows the appearance of a dispersion obtained by the production method of the present invention, and the appearance of a dispersion of polybulurpyrrolidone (PVP) single-walled carbon nanotubes (SWNT) under various solvent conditions. Is shown.
  • PVP polybulurpyrrolidone
  • SWNT single-walled carbon nanotubes
  • FIG. 2 shows a visible ultraviolet absorption spectrum of the dispersion obtained by the production method of the present invention, and polybutylpyrrolidone (PVP) single-walled carbon nanotube (SWNT) under various solvent conditions. And a visible ultraviolet absorption spectrum of a dispersion of multi-walled carbon nanotubes (MWNT).
  • PVP polybutylpyrrolidone
  • SWNT single-walled carbon nanotube
  • FIG. 3 shows the Raman absorption spectrum of the dispersion obtained by the production method of the present invention.
  • the dispersion contains polyvinylpyrrolidone (PVP) single-walled carbon nanotubes (SWNT) (organic solvent: 2 shows the Raman absorption spectrum of (isopropanol).
  • PVP polyvinylpyrrolidone
  • SWNT single-walled carbon nanotubes
  • organic solvent: 2 shows the Raman absorption spectrum of (isopropanol).
  • FIG. 4 shows the appearance of the dispersion obtained by the production method of the present invention.
  • PMET (2-methoxyethoxy) ethoxymethylthiophene
  • SWNT carbon nanotube
  • FIG. 5 shows a visible ultraviolet absorption spectrum of the dispersion obtained by the production method of the present invention.
  • PMET (2-methoxyethoxy) ethoxymethylthiophene under various solvent conditions ) Visible UV absorption spectrum of single-walled carbon nanotube (SWNT) dispersion.
  • FIG. 6 shows the near-infrared absorption spectrum of the dispersion obtained by the production method of the present invention.
  • PMET (2-methoxyethoxy) ethoxymethylthio under various solvent conditions Fen
  • SWNT single-walled carbon nanotube
  • FIG. 7 is a schematic diagram showing an embodiment of a preferred vibration crushing process step of the present invention.
  • FIG. 8 schematically shows a container and a hard sphere (center cut view) that can be used in the production method of the present invention.
  • the longitudinal length L and the lateral length of the hollow part in the container are shown.
  • Fig. 9 is contained in the carbon nanotube dispersion obtained by the production method of the present invention.
  • 2 is a TEM photograph showing a single-walled carbon nanotube.
  • Figure 9 (a) is CHC1
  • Figure 9 (b) is
  • NMP is used as the organic solvent.
  • carbon nanotubes are, for example, arc discharge method, laser evaporation method, laser exposure method, and CVD method (or It means a bundle-like carbon nanotube produced by a conventional method such as chemical vapor deposition or chemical vapor deposition.
  • arc discharge method laser evaporation method
  • laser exposure method laser exposure method
  • CVD method or It means a bundle-like carbon nanotube produced by a conventional method such as chemical vapor deposition or chemical vapor deposition.
  • the dispersed carbon nanotubes aggregate and settle with the passage of time when the long-term stability is poor.
  • a precipitate of carbon nanotubes can be seen in a few days at the latest.
  • the carbon nanotubes that are subjected to vibration pulverization may be purified or those that have been subjected to freeze-drying after purification, but more simply are commercially available carbon nanotubes.
  • the carbon nanotubes subjected to vibration pulverization can be either single-walled carbon nanotubes or multi-walled carbon nanotubes, and a dispersion can be easily obtained in a short time. Will be expensive
  • the cyclic organic compound as the dispersant used in the present invention is soluble in the organic solvent used in the step (ii). This cyclic organic compound can disperse the obtained carbon nanotubes, and therefore contributes to obtaining a dispersion containing the carbon nanotubes stably.
  • the cyclic organic compound is, for example, polyvinyl pyrrolidone (PVP), polystyrene sulfonate, and at least one synthetic polymer in which a group force that is also polythiophene power is selected. It is preferable.
  • PVP polyvinyl pyrrolidone
  • polystyrene sulfonate polystyrene sulfonate
  • synthetic polymer in which a group force that is also polythiophene power is selected. It is preferable.
  • the cyclic organic compound is a ⁇ -based compound.
  • “ ⁇ -based compound” refers to a compound having a wide conjugated system and a stronger ⁇ - ⁇ interaction.
  • Force At least one selected compound is preferred.
  • the cyclic organic compound is a ⁇ -based compound, since the carbon nanotube is a ⁇ -based compound, a ⁇ - ⁇ interaction occurs between the cyclic organic compound and the carbon nanotube. Since a force attracting each other with the cyclic organic compound is generated, an effect of assisting the dissociation of the bundle of carbon nanotubes can be provided.
  • the cyclic organic compound may be a synthetic polymer and a ⁇ -based compound. For example, 3- (2-methoxyethoxy) -ethymethylthiophene ( ⁇ ) It can be illustrated.
  • any compound that is soluble in an organic solvent and stably disperses carbon nanotubes can be used in the present invention.
  • the dispersant is not particularly limited.
  • Nafion registered trademark, Nafion
  • polyethylene glycol can be used as a dispersant.
  • the mass ratio between the cyclic organic compound and the carbon nanotube will be described.
  • the mass ratio between the cyclic organic compound provided in the container and the dried carbon nanotube is About 10: 1 to about 1: 200, preferably about 5: 1 to about 1: 100, more preferably about 1: 1 to about 1:50.
  • the organic solvent used in the present invention is preferably an alcohol, an ether organic solvent, an amide organic solvent, a sulfoxide or a halogen organic solvent.
  • the alcohol includes at least one selected from the group consisting of methanol, primary alcohols such as ethanol, secondary alcohols such as isopropanol, and tertiary alcohols such as tert-butanol. Preferred to be alcohol.
  • the ether organic solvent is preferably at least one ether organic solvent selected from the group power consisting of jetyl ether and tetrahydrofuran. With amide organic solvent Therefore, it is preferable that the amide organic solvent is at least one selected from the group consisting of 1-methyl 2-pyrrolidone and N, N dimethylformamide.
  • the sulfoxide is preferably dimethyl sulfoxide.
  • the halogen-based organic solvent at least one kind of halogen-based organic solvent in which the group strength including black-mouth form, methylene chloride, and 1,1,2,2-tetrachloro-tank etanca is also selected is preferable. Mouth Holm is preferred.
  • the carbon nanotube dispersion of the present invention may contain other components as necessary.
  • the organic solvent or the cyclic organic compound is as exemplified above, a highly dispersible carbon nanotube dispersion can be obtained.
  • a combination of a preferable organic solvent and a cyclic organic compound is exemplified.
  • an organic solvent either alcohol, 1-methyl-2-pyrrolidone or N, N dimethylformamide, and polybylpyrrolidone as a cyclic organic compound are used.
  • the organic solvent includes a combination of 1-methyl-2-pyrrolidone, N, N dimethylformamide, dimethyl sulfoxide, or black mouth form, and polythiophene as the cyclic organic compound.
  • a combination of polythiophene as a cyclic organic compound, 1-methyl-2-pyrididone as an organic solvent, or polybutyrrolidone (PVP) as a cyclic organic compound, and isopronool V as an organic solvent is preferred, so that a suitable force can be obtained.
  • the carbon nanotubes and the cyclic organic compound are charged into the container together with the hard balls, and then the hard balls are vibrated against the container. It is preferable to perform vibration pulverization. More specifically, the carbon nanotube, the cyclic organic compound, and the hard sphere are provided to the hollow part of the container body (hereinafter also referred to as “container hollow part”), and the hard sphere is shaken with respect to the container. .
  • “vibrating a hard sphere with respect to a container” substantially refers to an aspect in which the collision between the hard sphere and the wall surface of the hollow portion of the container is repeated over time. Therefore, “vibrating the hard ball with respect to the container” means not only a mode in which the container itself is reciprocated and the hard ball contained therein is reciprocated, but the hard ball is externally applied with the container itself fixed. Including a reciprocating mode. In the case of reciprocating the container (see FIG. 7), it is generally preferred that the reciprocating direction is the longitudinal direction of the container hollow part. The longitudinal direction of the container hollow part is the horizontal direction.
  • the container when the container is installed on the vibrator, it is preferable to move the container so as to reciprocate left and right in the horizontal direction.
  • the vibration direction of the container itself.
  • the form of the container and Z or the container hollow part or the container installed on the vibrator The direction of vibration may be changed as appropriate according to the way, for example, the reciprocating direction may change over time.
  • a hard sphere made of a magnetic material or a container made of a non-magnetic material is used, and a magnetic force is applied to the hard sphere from the outside of the container.
  • a mode in which the hard ball is reciprocated in the container is conceivable.
  • vibration generally means a phenomenon of reciprocating around a certain point, but “vibration” used in this specification is not necessarily limited to a mode in which the container reciprocates only in a certain direction. If the collision between the hard sphere and the wall of the hollow portion of the container is repeated over time (i.e., mechanical impact is directly applied to the carbon nanotubes and mechanical shearing force is applied to the carbon nanotubes). If it acts on the container), it does not matter if the container is in rotational and Z or rocking motion. When the container rotates
  • the base on which the container is installed also rotates, and the rotation direction of the container changes with time (for example, “inverted”), and the rotation direction of the base is also independent of the container. It is preferable that it changes with time.
  • the container generally has a container body and a lid, and is preferably a container that seals the carbon nanotube, the cyclic organic compound, and the hard sphere provided in the hollow portion of the container by shielding them from the ambient atmosphere.
  • the container is preferably formed mainly of a hard material force such as stainless steel, but an impact caused by vibration, for example, a hard ball reciprocating in the container hollow part collides with the hollow part wall surface (that is, the container hollow part wall part). Any kind of material cover may be formed as long as it can withstand the impact generated by the process.
  • the container hollow portion has, for example, a cylindrical shape, and while being subjected to vibration crushing, the hard sphere reciprocates in the longitudinal direction of the hollow portion from one end portion of the cylindrical hollow portion to the other end portion. It preferably has a shape and size that can be formed. As long as the hard sphere moves and reciprocates substantially in the hollow portion of the container, the hollow portion of the container may be in the shape and size of deviation.
  • the end of the container hollow part in the longitudinal direction that is, the top and bottom of a cylindrical container hollow part
  • description will be made on the assumption that the shape of the container hollow portion is a cylindrical shape having a hemispherical top and bottom.
  • the hard sphere reciprocates in the hollow portion of the container, and as a result, preferably the frequency at which the carbon nanotube and the cyclic organic compound are mixed, and Z or the carbon nanotube between the reciprocating hard sphere and the wall of the hollow portion. It is preferable to reciprocate the container at such a frequency that the powder is crushed. If the frequency is 5 s _ 1 or less, the vibration time may be very long.On the other hand, if the frequency is 120 s _ 1 or more, the carbon nanotubes cause a chemical reaction to disperse the carbon nanotubes. The degree may decrease. Therefore, frequency is 5 ⁇ 120S _1, is _1 preferably 10 ⁇ 60S _1, more preferably vibration number 20 to 50 s.
  • the container is reciprocated, and the rotational speed of the container is preferably 5 to 120 times Zs. Yes, more preferably 10 to 60 times Zs, more preferably 20 to 50 times Zs.
  • the vibration time is preferably about 1 minute to 5 hours, more preferably about 1.5 minutes to 3 hours, and still more preferably about 2 minutes to 2 hours. If the vibration time is too short, the dispersibility of the carbon nanotubes decreases, and if the vibration time is too long, the carbon nanotubes react with each other to reduce the dispersibility of the carbon nanotubes.
  • the vibration time may vary depending on vibration conditions such as frequency or amplitude. In addition to the preferable frequency and vibration time as described above, it is preferable to consider a suitable amplitude.
  • the hard sphere reciprocates in the hollow portion of the container, and as a result, the carbon nanotube and the cyclic It is preferable to vibrate the hard sphere with respect to the container with such an amplitude that the organic compound is mixed and an amplitude such that the carbon nanotube is crushed between the hard sphere that reciprocates and the wall surface of the hollow portion.
  • the amplitude w when the container is reciprocated and the container are reciprocated.
  • the ratio (W: L) with the length L of the hollow portion of the container is preferably 1: 1 to 50: 1, more preferably
  • the ratio is preferably 1: 1. 2 to 20: 1, more preferably 1: 1. 3 to 15: 1.
  • vibration refers to the length from the center point to the maximum displacement point when the container to be reciprocated is displaced to the maximum with respect to the center point of the reciprocation.
  • the container hollow part has a cylindrical shape, it is preferable to reciprocate the container in the longitudinal direction of the container hollow part.
  • the container hollow part length L in the direction of reciprocating the container is Yong
  • the amplitude is 5 to: preferably LOOm m, preferably 10 to 80 mm, more preferably 20 to 50 mm. Therefore, the container is reciprocated in the longitudinal direction of the hollow part.
  • the hard sphere provided in the container in the vibration pulverization process preferably has a spherical shape, but any shape suitable for the hard ball to reciprocate in the hollow portion while the hard sphere vibrates with respect to the container. Even if it is the shape of, it does not work.
  • the hard sphere is a sphere having a diameter of 2 to: LO mm, preferably 4 to 6 mm, more preferably 5 mm in diameter.
  • the hard sphere vibrates with respect to the container, the hard sphere reciprocates in the container hollow portion, and as a result, the hardness such that the carbon nanotube is preferably crushed between the hard ball and the wall surface of the container hollow portion.
  • the hard wall and the wall surface of the container hollow part have.
  • the hardness of the hard sphere and the hardness of the wall surface of the container hollow portion are Mohs hardness 4 or less, the deformation and mixing efficiency of the hard sphere are reduced. It may cause a decrease (decrease in mixing efficiency of carbon nanotube and cyclic organic compound).
  • the hardness of the hard sphere is preferably a Mohs strength of 4 to 9.5, more preferably a Mohs strength of 5 to 9.5, and even more preferably a Mohs hardness of 6 to 9.5.
  • Examples of the material of the hard sphere include at least one material selected from the group consisting of agate, slenless, alumina, zirconia, tungsten carbide, chromium steel, and Teflon (registered trademark).
  • examples of the material for the wall surface of the hollow portion of the container include at least one material selected from the group force consisting of agate, slenless, alumina, zircoure, tungsten carbide, chromium steel, and Teflon (registered trademark). be able to.
  • the number of hard balls provided to the container is 1 to 6, preferably 1 to 4, more preferably 2. However, the hard balls reciprocate in the hollow part of the container while the hard balls vibrate against the container.
  • the number of carbon nanotubes and the cyclic organic compound be mixed, and that the carbon nanotubes be crushed between the Z or reciprocating hard sphere and the wall of the container hollow. Any number can be used as long as it is a number. When two or more hard spheres are provided in the container, the carbon nanotubes are crushed even between the reciprocating hard spheres.
  • the hard sphere is small (i.e., when the container is hollow, the length in the longitudinal direction, L force), the hard sphere is small
  • the container is large (i.e., the length in the longitudinal direction of the hollow part of the container), it may not be possible to mix well (mixing of carbon nanotubes and cyclic organic compounds) due to the small collision energy. If L is large), the amplitude will inevitably increase and the vibrator
  • the diameter R of the hard sphere and the longitudinal length of the hollow portion of the container Since it becomes shorter, the energy when the hard sphere collides with the wall surface of the hollow portion of the container is reduced, and mixing may be insufficient. Therefore, the diameter R of the hard sphere and the longitudinal length of the hollow portion of the container
  • the ratio (R: L) to the cutting is preferably 1: 1 ⁇ 5 to 1: 100, more preferably 1: 2 ⁇ 0 to 1: b a b
  • the diameter R of the hard sphere and the inside of the container 75, more preferably 1: 2.5 to 1:50 (see FIG. 8). Also, the diameter R of the hard sphere and the inside of the container
  • the ratio of b b (R: S) is preferably 1: 1: 1 to 1:30, more preferably 1: 1-2 to 1:20, and a b
  • the ratio is 1: 1.3 to 1:15 (see also FIG. 8).
  • the “diameter R" here means
  • the shape of the hard sphere is spherical.
  • the shape of the hard sphere is not particularly limited, and may be a shape other than a sphere. In that case, it is preferable that the hard sphere has an equivalent diameter corresponding to the “diameter” described above. This “equivalent diameter” means the diameter assumed when the shape of a non-spherical hard sphere is made spherical without changing the volume.
  • the preferable relationship between the total volume of the hard spheres and the volume of the container hollow portion is as follows. For example, if the number of hard spheres is 1 to 6, the total volume of hard spheres with respect to the container hollow volume V
  • step (ii) for obtaining a dispersion will be described.
  • the carbon nanotube mixture after being subjected to vibration grinding more specifically, a mixture containing carbon nanotubes and a cyclic organic compound after being subjected to vibration grinding.
  • this dispersion comprises the components of the organic solvent to be added, the carbon nanotubes and the cyclic organic compound.
  • an operation for removing precipitates (the precipitates substantially contain carbon nanotubes not dispersed in the organic solvent) from the obtained mixture as necessary. It may be additionally performed.
  • a centrifugal separation operation is performed to remove the carbon nanotubes that have not been dispersed, and the resulting supernatant can be collected to obtain a carbon nanotube dispersion.
  • the step of obtaining the dispersion in this manner is particularly suitable when polyvinylpyrrolidone (PVP) is used as the cyclic organic compound.
  • the organic solvent may be the same as the organic solvent added to the carbon nanotube mixture after being subjected to vibration pulverization, or may be a solvent having the same principal component as the organic solvent.
  • the membrane filter used for filter filtration has an average membrane pore size of preferably 0.02-5.
  • Carbon nanotubes contained in the supernatant are preferably 2 to 95%, more preferably Those that can be recovered 5 to 95% (recoverable from the supernatant) are preferred.
  • An example of such a membrane filter is a PTFE membrane filter (manufactured by Advantech, model: T020A025A [catalog number], pore size: 0.20 m).
  • the following operation can also be performed.
  • an organic solvent is added to a carbon nanotube mixture after being subjected to vibration grinding (more specifically, a mixture containing carbon nanotubes and a cyclic organic compound after being subjected to vibration grinding), and the resulting mixture is Subject to centrifugation.
  • the precipitate produced by centrifugation is collected, and a carbon nanotube dispersion can be obtained by adding a solvent to the precipitate.
  • the obtained dispersion is subjected to ultrasonic treatment and then subjected to centrifugation, and the resulting supernatant is separated to obtain a dispersion in which carbon nanotubes exist more stably. it can.
  • the step of obtaining the dispersion in this manner is particularly suitable when a ⁇ -based compound is used as the cyclic organic compound.
  • the “solvent added to the precipitate” may be an organic solvent added to the carbon nanotube mixture after being subjected to vibration pulverization, or may be a solvent having the same main component force as the organic solvent.
  • stable means that carbon nanotubes are stably dispersed in an organic solvent over time, and for at least 1 week, preferably at least 2 weeks, more preferably at least 3 weeks. This means that no aggregation or precipitation of carbon nanotubes occurs. in this way, Since the dispersion liquid contains carbon nanotubes stably, it can be considered that the carbon nanotubes are substantially dissolved in the solvent.
  • the dispersion containing the carbon nanotubes contains at least the carbon nanotubes from which the bundles are dissociated, it is considered that the specific surface area of the carbon nanotubes increases in proportion to the degree to which the bundles are dissociated. Therefore, a member having a carbon nanotube film having a larger specific surface area can be produced from a powerful dispersion, and the member can be used as, for example, a gas storage product or an electrode. Such gas storage products can be used for storing hydrogen gas fuel in, for example, cars and ships.
  • a specific example of the electrode for example, a negative electrode such as a lithium secondary battery can be considered.
  • the above-described member of the present invention is formed by applying a dispersion liquid containing a substrate and a carbon nanotube produced by the method of the present invention to the surface of the substrate and then drying the carbon nanotube film. It has.
  • the substrate is a substrate or a support plate suitable for, for example, a gas occlusion product or an electrode
  • the substrate may have a shifted shape or material force.
  • the dispersion containing carbon nanotubes produced by the method of the present invention the carbon nanotubes in which the bundles are dissociated at least partially exist in the organic solvent almost uniformly.
  • the carbon nanotube film obtained by applying the dispersion to the surface of the substrate and drying it can contain carbon nanotubes substantially uniformly. Therefore, in such a carbon nanotube film, the specific surface area of the carbon nanotubes is large, and a gas storage product having a large gas storage amount or a highly efficient electrode force S is brought about.
  • the dispersion obtained by the method of the present invention is used for forming a member such as a gas occlusion product or an electrode as described above, or by subjecting the dispersion to a filtration treatment with a conventional membrane filter. Then, only the carbon nanotubes contained in the dispersion liquid are taken out alone, and the taken out carbon nanotubes are used as field emission display (FED) field emitters, photoelectric conversion elements, composite materials (including plastic and rubber). In other words, it can be used for applications such as cosmetics and other materials that can be mixed to reinforce the grease.
  • FED field emission display
  • the carbon nanotube dispersion liquid of the present invention is made of at least one kind selected from the group forces including polyamide, polyethylene, polybutyl alcohol, polymine, polyacrylic resin, polyepoxy resin, polyurethane and natural rubber.
  • an organic polymer material having the characteristics of carbon nanotubes that is, characteristics such as high elasticity, high strength, or high conductivity
  • Such organic polymer materials should be used as raw materials for urethane molded products, plastic molded products, rubber products, golf shafts, FRP molded products, chemical fibers, paper, etc. (or used in these materials). Can do.
  • a coating material can be obtained using a polymer material containing the dispersion of the present invention, which can be used as an antistatic agent.
  • the dispersion of the present invention is made of at least one organic polymer selected from the group power consisting of polyamide, polyethylene, polyvinyl alcohol, polyimine, polyacrylic resin, polyepoxy resin, polyurethane and natural rubber.
  • Members obtained by mixing with materials and molding by various methods can be used for various applications. For example, such a molded member can be used as an electrode because of its improved conductivity.
  • a method for producing a dispersion containing carbon nanotubes of the present invention will be described over time.
  • a carbon nanotube 1 (preferably a dry carbon nanotube) is prepared.
  • the carbon nanotube 1 dried together with the cyclic organic compound and the two hard spheres 2 is provided in the container body hollow portion of the container 3, and the container body is covered to seal the container 3. .
  • the hard sphere 2 reciprocates in the hollow portion of the container, and as a result, the frequency and amplitude such that the carbon nanotube 1 and the cyclic organic compound are mixed, and the Z or reciprocating hard sphere 2 and the wall surface of the hollow portion.
  • the container 3 is reciprocated in the longitudinal direction of the hollow portion with such a vibration frequency and amplitude that the carbon nanotubes 1 are crushed. Then, after reciprocating the container 3 for an appropriate time, the carbon nanotubes taken out from the container 3 are diluted with an organic solvent to obtain a dispersion liquid stably containing carbon nanotubes.
  • a method for producing a dispersion comprising carbon nanotubes comprising:
  • a method for producing a carbon nanotube dispersion wherein the cyclic organic compound used in step (i) is soluble in the organic solvent used in step (ii).
  • the first aspect is characterized in that after the carbon nanotube, the cyclic organic compound, and the hard ball are provided in the container, the vibration pulverization is performed by vibrating the hard ball in the container. how to.
  • the hard ball is vibrated with respect to the container by reciprocating the container in a certain direction.
  • the ratio of wrinkles to W: L is from 1: 1.3 to 15: 1.
  • the number force of hard spheres is 6 to 6, and the ratio of the total volume of the hard spheres to the volume of the hollow portion of the container is 0.5 to 10%. And how.
  • cyclic organic compound is a synthetic polymer selected from a group force including polyvinylpyrrolidone, polystyrene sulfonate, and polythiophene force.
  • Sixth aspect The method according to any one of the first to fourth aspects, wherein the cyclic organic compound is a ⁇ -based compound.
  • Seventh aspect The method according to the sixth aspect, characterized in that it is selected from the group consisting of ⁇ -based compound power porphyrin derivatives, pyrene derivatives, anthracene derivatives and polythiophene derivatives.
  • the organic solvent is an alcohol, It is an ether organic solvent, an amide organic solvent, a sulfoxide or a halogen organic solvent.
  • Ninth aspect The method according to the eighth aspect, wherein a group power including alcohol power methanol, ethanol, isopropanol and t-butanol power is also selected.
  • amide organic solvent is selected from the group consisting of 1-methyl-2-pyrrolidone and N, N-dimethylformamide.
  • Twelfth aspect The method according to the eighth aspect, wherein the sulfoxide is dimethyl sulfoxide.
  • Fifteenth aspect The method according to any one of the first to fourteenth aspects, wherein the vibration crushing is performed for 2 minutes to 2 hours.
  • Sixteenth aspect The method according to any one of the first to fifteenth aspects, wherein in the step (i) of obtaining the carbon nanotube mixture, a bundle of carbon nanotubes is at least partially dissociated.
  • step (ii) of obtaining a dispersion after adding organic solvent a to the carbon nanotube mixture, the resulting mixture is subjected to centrifugal separation.
  • the method further includes the step of filtering the supernatant obtained by subjecting to the centrifugation and adding a solvent having the same component power as the organic solvent a to the resulting residue.
  • the membrane filter used for filter filtration is contained in the supernatant A method characterized in that 5-95% of the tube is collected.
  • step (ii) of obtaining a dispersion organic solvent a is added to the carbon nanotube mixture, the resulting mixture is subjected to centrifugation, and then the precipitate in the mixture is precipitated. And adding an organic solvent composed of the same main component as the organic solvent a to the precipitate.
  • a twentieth aspect is a member including a base material having a carbon nanotube film on the surface, wherein the carbon nanotube film is obtained by using the carbon nanotube dispersion obtained by the method according to any one of the first to nineteenth aspects as a base material.
  • Twenty-first aspect A component according to the twentieth aspect, wherein the part is used as a gas storage product.
  • Twenty-second aspect The member according to the twentieth aspect, which is used as an electrode.
  • Twenty-third aspect A polymer material containing a carbon nanotube dispersion obtained by the method according to any one of the first to twenty-second aspects.
  • Twenty-fourth aspect A member having the strength of an organic polymer material containing carbon nanotubes, wherein the carbon nanotube dispersion obtained by the method according to any one of the first to second aspects is mixed with another organic polymer material.
  • a carbon nanotube dispersion liquid comprising carbon nanotubes, polyvinylpyrrolidone, and the organic solvent according to the eighth aspect.
  • Twenty-sixth aspect A carbon nanotube dispersion comprising carbon nanotubes, 3- (2-methoxyethoxy) ethoxymethylthiophene and the organic solvent according to the eighth aspect.
  • a dispersion containing carbon nanotubes stably was produced using the production method of the present invention.
  • the obtained dispersion had no carbon nanotube aggregation or precipitation until at least 4 weeks.
  • Example 1 The same operation as in Example 1 was carried out with various solvents under the conditions using PVP (polybulurpyrrolidone) as a dispersant (it was also carried out under the conditions where PVP was not used).
  • the results are shown in Table 1 below.
  • the CNT concentration (mgZlmL) in the table means the mass (mg) of carbon nanotubes contained in 1 mL of the obtained dispersion.
  • the concentration of CNTs can be determined from the absorbance (A) at a wavelength of 500 nm in the visible absorption spectrum when using a 1 mm cell after diluting the dispersion 5 times.
  • SWNT1 is a single-walled carbon nanotube manufactured by Carbon Nanotechnologies, Inc.
  • SWNT2 is a single-walled carbon nanotube manufactured by CarboLex, In.
  • MWNT1 is a multiwall carbon nanotube made by Nanocyl S.A.
  • PVP polybulurpyrrolidone (average molecular weight 360,000).
  • the numbers in “Note” indicate that they are all dispersed or dissolved.
  • PVP plays an important role as a dispersant.
  • 'Alcohols such as methanol, ethanol and isopropanol used as the organic solvent contribute to the formation of the carbon nanotube dispersion in the present invention.
  • Amide organic solvents such as 1-methyl-2-pyrrolidone and N, N-dimethylformamide used as organic solvents contribute to the formation of the carbon nanotube dispersion in the present invention.
  • Example 2 The same operation as in Example 2 was carried out with various solvents under the conditions using PMET (3- (2-methoxyethoxy) -ethoxymethylthiophene) as a dispersant.
  • the results are shown in Table 2 below.
  • the CNT concentration (mgZlmL) in the table means the mass (mg) of carbon nanotubes contained in the obtained dispersion ImL.
  • the concentration of CNTs can be determined from the absorbance (A) at a wavelength of 700 nm in the visible absorption spectrum using a 1 mm cell after diluting the dispersion 10 times, as shown in the following formula. Extinction coefficient
  • SWNT1 is a single-walled carbon nanotube manufactured by Carbon Nanotechnologies, Inc.
  • PMET represents (3- (2-methoxyethoxy) ethoxymethylthiophene) used as a dispersant, and 5 mg was used for all.
  • 'PMET used as a dispersant contributes to the formation of the carbon nanotube dispersion in the present invention.
  • 'A halogen-based organic solvent such as black mouth form used as the organic solvent contributes to the formation of a strong bon nanotube dispersion in the present invention.
  • Dimethyl sulfoxide and other sulfoxide used as organic solvents are used in the present invention. This contributes to the formation of a carbon nanotube dispersion.
  • amide-based organic solvents such as 1-methyl-2-pyrrolidone and N, N-dimethylformamide used as organic solvents have the ability to use PVP as a dispersant. Regardless of this, it contributes to the formation of the carbon nanotube dispersion in the present invention.
  • lmg single-walled carbon nanotubes lOmg polybulurpyrrolidone (PVP: average molecular weight 360, 000) as dispersant and two agate balls (sphere diameter 5mm) 20mm bottom diameter, 65mm longitudinal length (The cylindrical hollow part formed in the said container: The cross-sectional diameter of the trunk
  • drum is 12 mm and the length of a longitudinal direction is 50 mm).
  • PVP polybulurpyrrolidone
  • FIG. 1 shows the appearance of a dispersion of PVP (polyvinylpyrrolidone) -single-walled carbon nanotubes (SWNT) obtained by the production method of the present invention performed under various solvent conditions.
  • the dispersion shows black, confirming that the carbon nanotubes are dispersed in the organic solvent used.
  • Figure 2 shows the visible-ultraviolet absorption of a dispersion of PVP (polyvinylpyrrolidone) single-walled carbon nanotubes (SWNT) and multi-walled nanotubes (MENT) obtained by the production method of the present invention under various solvent conditions. The spectrum is shown. Absorption by carbon nanotubes was observed in the entire measurement region of 250 to 800 nm, and it was confirmed that single-walled carbon nanotubes were dispersed.
  • PVP polyvinylpyrrolidone
  • FIG. 3 shows a Raman absorption spectrum of a dispersion (organic solvent: isopropanol) of PVP (polyvinylpyrrolidone) -single-walled carbon nanotube (SWNT) obtained by the production method of the present invention.
  • PVP polyvinylpyrrolidone
  • SWNT single-walled carbon nanotube
  • 150 to 300 cm _1 near radial breathing mode corresponds to the semiconductor single-walled carbon nanotubes, since the radial breathing mode in the vicinity 230 ⁇ 300Cm _1 corresponds to the metal monolayer carbon nano tube, and semiconducting SWNTs It is thought that both metallic single-walled carbon nanotubes are dispersed.
  • Figure 4 shows the appearance of a dispersion of PMET (3- (2-methoxyethoxy) -ethyoxymethylthiophene) single-walled carbon nanotubes (SWNT) obtained by the production method of the present invention performed under various solvent conditions. Is shown. As in FIG. 1, the dispersion liquid showed a black color, and it was confirmed that the carbon nanotubes were dispersed in the organic solvent used.
  • PMET 3- (2-methoxyethoxy) -ethyoxymethylthiophene
  • Figure 5 shows PMET (3- (2-methoxyethoxy) -ethoxymethylthiophene) single-walled carbon nanotubes (SWN) obtained by the production method of the present invention performed under various solvent conditions.
  • SWN single-walled carbon nanotubes
  • Figure 6 shows the proximity of a dispersion of PMET (3- (2-methoxyethoxy) -ethyoxymethylthiophene) single-walled carbon nanotubes (SWNT) obtained by the production method of the present invention performed under various solvent conditions. Infrared absorption spectrum is shown. Absorption by carbon nanotubes was observed in the entire near-infrared region of 800-1600 nm in this measurement region, and it was confirmed that single-walled carbon nanotubes were dispersed.
  • PMET 3- (2-methoxyethoxy) -ethyoxymethylthiophene
  • FIGS. 9 (a) and 9 (b) show TEM photographs of single-walled carbon nanotubes contained in the carbon nanotube dispersion obtained by the production method of the present invention.
  • Figures 9 (a) and (b) are TEM photographs when different organic solvents are used.
  • CHC1 CHC1
  • NMP (1-methyl-2-pyrrolidone) is used as the organic solvent.
  • the dispersion obtained by the production method of the present invention contains single-walled carbon nanotubes from which bundles are dissociated.
  • the effect of the vibration pulverization treatment performed by the production method of the present invention is only effective to dissociate the carbon nanotube bundles, if not completely (the carbon nanotubes are removed by the vibration treatment). It can be understood that the original form's shape force is also thin, so that the bundle is at least dissociated) and does not destroy the structure of the carbon nanotube itself.
  • NMP 1-methyl-2-pyrrolidone
  • DMF ⁇ , ⁇ dimethylformamide
  • CHC1 black mouth form
  • DMSO dimethylsulfoxide
  • a carbon nanotube dispersion (sample ⁇ ) was produced by the production method of the invention. Specifically, U lmg single layer carphone nanotub (Carbon Nanotechnologies Incorporat ed), 5 mg of a dispersant (specifically polythiophene) and two agate balls (sphere diameter 5 mm) in a cylindrical sealed container with a bottom diameter of 20 mm and a length in the longitudinal direction of 65 mm (the container The cylindrical hollow part formed in the body: the body part was charged with a cross-sectional diameter of 12 mm and a longitudinal length of 50 mm).
  • a dispersant specifically polythiophene
  • two agate balls sphere diameter 5 mm
  • the organic solvent is NMP (1-methyl-2-pyrrolidone), DMF (N, N-dimethylformamide), CHC1 (black mouth form), DMSO (dimethylsulfoxide), as in the production method of the present invention described above.
  • Sample B was prepared using each. Method of operation 'Experimental conditions are as follows.
  • sample A obtained by the production method of the present invention contains carbon nanotubes, whereas sample B contains carbon nanotubes except for the condition of CHC1.
  • the carbon nanotubes are dispersed only by the vibration pulverization process without the dispersion of the carbon nanotubes only with the dispersant and z or the organic solvent. It was understood that the effect was excellent. It should be noted that the vibration pulverization process has a particularly advantageous effect on the dissociation of the bundle of carbon nanotubes because, unlike the ultrasonic process, the shear force acts directly on the carbon nanotubes. Conceivable.
  • the carbon nanotube dispersion obtained by the production method of the present invention is a gas storage product (for example, a hydrogen storage medium for storing hydrogen gas fuel such as a car or a ship) or an electrode (a negative electrode used for a lithium secondary battery or the like). It can also be used for the manufacture of field emission display emitters, photoelectric conversion elements or cosmetics.
  • a gas storage product for example, a hydrogen storage medium for storing hydrogen gas fuel such as a car or a ship
  • an electrode a negative electrode used for a lithium secondary battery or the like. It can also be used for the manufacture of field emission display emitters, photoelectric conversion elements or cosmetics.

Abstract

La présente invention concerne un procédé de production d'un liquide de dispersion contenant des nanotubes de carbone, ledit procédé comprenant : (i) une étape d'obtention d'un mélange de nanotubes de carbone en soumettant des nanotubes de carbone et un composé organique cyclique à un broyage par oscillations à une fréquence d'oscillation de 5 à 120 s-1 ; et (ii) une étape d'obtention d'un liquide de dispersion contenant des nanotubes de carbone en ajoutant un solvant organique au mélange de nanotubes de carbone. Ce procédé est caractérisé par l'utilisation à l'étape (i) d'un composé organique cyclique qui est soluble dans le solvant organique utilisé à l'étape (ii).
PCT/JP2006/313325 2005-07-05 2006-07-04 Procédé de production d'un liquide de dispersion de nanotubes de carbone WO2007004652A1 (fr)

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