WO2007007594A1 - Procédé de préparation d’une solution aqueuse contenant un nanotube de carbone - Google Patents

Procédé de préparation d’une solution aqueuse contenant un nanotube de carbone Download PDF

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Publication number
WO2007007594A1
WO2007007594A1 PCT/JP2006/313324 JP2006313324W WO2007007594A1 WO 2007007594 A1 WO2007007594 A1 WO 2007007594A1 JP 2006313324 W JP2006313324 W JP 2006313324W WO 2007007594 A1 WO2007007594 A1 WO 2007007594A1
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Prior art keywords
container
carbon nanotubes
aqueous solution
hard
carbon nanotube
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PCT/JP2006/313324
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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 JP2007524585A priority Critical patent/JP5050207B2/ja
Publication of WO2007007594A1 publication Critical patent/WO2007007594A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • 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 an aqueous solution containing carbon nanotubes, and more particularly to a method for producing an aqueous solution containing carbon nanotubes stably from bundle-like carbon nanotubes. Furthermore, the present invention relates to a member produced using an aqueous solution containing a carbon nanotube obtained by the method of the present invention.
  • a carbon nanotube 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, and has an order of nanometer in diameter.
  • 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 force Single-bonn nanotubes are a single graphite sheet wound in 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 a thing.
  • Such carbon nanotubes are expected to be applied in various fields because of their unique functions due to their unique structure.
  • single-walled carbon nanotubes are considered to be suitable for applications such as gas storage materials such as hydrogen or electrode members because of their relatively large specific surface area.
  • single-walled carbon nanotubes produced by a conventional production method are not always convenient for various applications.
  • the single-walled carbon nanotubes are not stably dispersed in time with respect to the aqueous solvent, and the single-walled carbon nanotubes aggregate over time. / It will settle.
  • a precipitate of carbon nanotubes can be seen in 2 to 3 days at the longest. Therefore, it is difficult to treat such a mixture containing single-walled carbon nanotubes with poor stability as a solution, and as a result, the response of single-walled carbon nanotubes.
  • the range of use is inevitably limited.
  • Non-Patent Document 1 Jie Liu, Andrew G. Rin zler, 13 others, "Fullerene Pipes", Science May 22, 1998, No. 280, pl253—1256
  • Non-Patent Document 2 Ikeda, Ikeda, A., Hayashi, K., Koishi, Konishi, T., Kikuchi, J. “Chemical” Communiqué “Chemi. Commun. 2004", pl334— 1335
  • the present invention provides:
  • This method of the present invention is characterized in that the carbon nanotube bundle is at least partially dissociated by subjecting it to a vibration operation, and a nucleotide having a purine ring as a solubilizer. Is used and has characteristics in terms of points.
  • an aqueous solution stably containing about 1. OX 10 — 2 wt% to about 15 X 10 — 2 wt% carbon nanotubes is provided.
  • a member comprising a base material having a carbon nanotube film on the surface.
  • the carbon nanotube film of the member is characterized in that it is a film formed by applying a force-bonbon nanotube aqueous solution obtained by the production method of the present invention to the surface of the substrate and then drying it.
  • an aqueous solution containing carbon nanotubes stably can be obtained. Therefore, in the aqueous solution, the carbon nanotubes are dispersed stably in time in the aqueous medium, and the long-term stability is excellent. Therefore, it is possible to handle such a liquid as a solution (which is the basis for the “aqueous solution” in this specification).
  • such an aqueous solution stably containing carbon nanotubes includes at least the carbon nanotubes from which the bundles are dissociated, so that the specific surface area of the carbon nanotubes is increased as compared with the case where the carbon nanotubes are bundled.
  • the gas occlusion amount increases as compared with the case of using bundle-like carbon nanotubes, and approaches the theoretical value.
  • the carbon nanotubes in which the bundles are dissociated have a larger contact area with the electrode surface than the bundled ones, the members manufactured using the aqueous solution obtained by the method of the present invention are used as the electrodes. What has been obtained becomes highly efficient, and the efficiency is closer to the theoretical value.
  • the “theoretical value” here means that all of the carbon nanotubes contained in such a member are dissociated bundles! /, Based on the assumption that the hydrogen storage amount in the ideal state or Refers to electrode efficiency.
  • FIG. 1 schematically shows a method for producing an aqueous solution containing carbon nanotubes of the present invention. Shown in
  • FIG. 2 shows an aqueous solution containing carbon nanotubes obtained according to the method of the present invention.
  • Figure 3 shows the visible ultraviolet absorption spectra of liquids containing carbon nanotubes obtained using seven types of substances (GMP, ADP, ATP, AMP, R5P, CMP, and UMP) as solubilizers. Show.
  • FIG. 4 shows a Raman spectrum of an aqueous solution (that is, a solution containing a solubilizer and SWNT) obtained by the production method of the present invention.
  • FIG. 5 schematically shows the container and the hard sphere (center cut), and shows the length L in the longitudinal direction and the length S in the short direction of the hollow portion in the container, and the diameter R of the hard sphere.
  • FIG. 6 is a TEM photograph showing single-walled carbon nanotubes contained in an aqueous carbon nanotube solution obtained by the production method of the present invention.
  • Figure 6 (a) uses GMP
  • Figure 6 (b) uses ADP
  • Figure 6 (c) uses ATP as a solubilizer!
  • carbon nanotubes are, for example, arc discharge methods, laser evaporation methods, laser ablation methods, and CVD methods. (Or bundled carbon nanotubes manufactured by conventional methods such as chemical vapor deposition and chemical vapor deposition). A bundle of single-walled carbon nanotubes is preferred, but a bundle of multi-walled carbon nanotubes does not work.
  • Such “carbon nanotubes” are preferably used in a dry state (that is, a cotton-like form having voids inside), for example, carbon nanotubes that are generally sold on the market. Come on!
  • carbon nanotubes can be used without being subjected to purification treatment and lyophilization when used in the method of the present invention. This is advantageous. In other words, when using commercially available carbon nanotubes, the carbon nanotubes are sonicated in an acidic solution and then neutralized and diluted with water. Does not require lyophilization later
  • the method of the present invention intends that the carbon nanotubes can be used without being subjected to purification treatment and lyophilization.
  • step (i) after the carbon nanotube is provided in the container together with the solubilizer and the hard ball, the hard ball is vibrated with respect to the container. More specifically, the carbon nanotube, the soluble glaze agent, and the hard sphere are provided to the hollow part of the container body (hereinafter also referred to as “container hollow part”), and then the hard sphere is vibrated with respect to the container. .
  • container hollow part the hollow part of the container body
  • “vibrating the hard sphere with respect to the container” substantially refers to a state in which the collision between the hard sphere and the wall of the hollow portion of the container is repeated over time.
  • “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 also the hard ball is externally applied with the container itself fixed. A mode of reciprocal movement is also included.
  • “vibration” as used in this specification substantially means an operation in which a mechanical impact is directly applied to the carbon nanotubes by directly applying a mechanical impact to the carbon nanotubes! /, It was noted that!
  • the reciprocating direction is the long direction of the container hollow part, so that the longitudinal direction of the container hollow part is the horizontal direction.
  • the direction of vibration may be changed as appropriate according to the shape of the Z or the hollow part of the container or the manner in which the container is installed on the vibrator, 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, and “vibration” used in this specification is not necessarily limited to a mode in which the container reciprocates only in a certain direction.
  • 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.
  • the gantry on which the container is installed also rotates as the container rotates, and the rotation direction of the container changes with time (for example, “reverse”), and the rotation direction of the gantry also changes.
  • the container is preferably one that changes independently with time.
  • the "container” used in step (i) generally comprises a container main body and a lid, and preferably contains carbon nanotubes, solubilizers and hard spheres provided in the container hollow portion in an ambient atmosphere.
  • This is a container that is sealed off from and sealed.
  • the container is preferably formed mainly of a hard material force such as stainless steel, but an impact caused by being subjected to vibration treatment, for example, a hard sphere reciprocating in the hollow part of the container has a hollow wall surface (that is, a container). Any kind of material force may be formed as long as it can withstand the impact caused by the collision with the inner hollow portion wall).
  • a gasket may be sandwiched between the contact surface between the container main body and the lid, and the container main body and the lid may be tightened with a clip or holder from the outside.
  • the container hollow portion has, for example, a cylindrical shape, and while being subjected to vibration treatment, the hard ball 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 the cylindrical container hollow part
  • the following description will be made on the assumption that the shape of the hollow portion of the container is a cylindrical shape having a hemispherical top and bottom.
  • the hard sphere reciprocates in the hollow portion of the container. It is preferable to reciprocate the container at a frequency such that the solubilizer is mixed and a frequency such that the carbon nanotubes are crushed between the z or reciprocating hard sphere and the hollow wall surface.
  • the term “pulverization” used in this specification substantially means the phenomenon of “dissociating the bundle of carbon nanotubes” rather than the phenomenon of “pulverizing”. Please note that. 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 and the solubility of the carbon nanotubes decreases. There is a possibility that.
  • frequency is 5 ⁇ 120S _1, preferably more preferably 10 ⁇ 60s " ⁇ a frequency 20 ⁇ 50s _ 1.
  • the container rotation speed is preferably 5 to 120 times / s, more preferably 10 to 60 times / s, more preferably vibration. It can be several 20-50 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. This is because if the vibration time is too short, the solubility of the carbon nanotubes decreases, and if the vibration time is too long, the carbon nanotubes react with each other and the solubility of the carbon nanotubes decreases.
  • 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 spheres reciprocate in the hollow part of the container, and as a result, the carbon nanotubes move between the Z and the hard spheres that reciprocate and the wall of the hollow part. It is preferable to vibrate the hard sphere with respect to the container with such an amplitude as to be crushed.
  • the ratio (W: L) of the container hollow portion length L in the direction is preferably 1: 1 to 50: 1, more preferably b b b
  • amplitude 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 reference to the center point of the reciprocation.
  • the container hollow part is cylindrical, it is preferable to reciprocate the container in the longitudinal direction of the container hollow part. Therefore, in that case, “the length L of the container hollow portion in the direction of reciprocating the container” is
  • LOOmm amplitude preferably 10 to 80 mm amplitude, more preferably 20 to 50 mm amplitude.
  • the container is reciprocated in the longitudinal direction of the hollow part.
  • the hard sphere provided in the container in step (i) preferably has a spherical shape
  • it may have a shape suitable for the hard sphere to reciprocate in the hollow portion while the hard sphere vibrates with respect to the container.
  • the shape may be shifted.
  • the hard sphere is a sphere having a diameter of 2 to: LO mm, preferably a diameter of 4 to 6 mm, more preferably a diameter of 5 mm.
  • the hard sphere vibrates with respect to the container, the hard sphere reciprocates in the container hollow portion, and as a result, the hardness that the carbon nanotubes are preferably crushed between the hard ball and the wall surface of the container hollow portion. It is preferable that the hard sphere and the wall surface of the container hollow part have.
  • the hardness of the hard sphere and the hardness of the wall of the hollow portion of the container are less than 4 Mohs hardness, it may cause deformation of the hard sphere and a decrease in mixing efficiency (decrease in mixing efficiency of carbon nanotube and solubilizer). There is sex. Therefore, 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 still more preferably a Mohs hardness of 6 to 9.5.
  • Examples of the material of the hard sphere may 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 spheres provided in the container is 1-6, preferably 1-4, more preferably 2.
  • the hard sphere vibrates with respect to the container, the hard sphere reciprocates in the hollow portion of the container, and as a result, preferably the number suitable for mixing the carbon nanotube and the solubilizer and Z or reciprocate. Any number may be used as long as the carbon nanotubes are pulverized between the hard sphere and the wall surface of the hollow portion of the container. In addition, when two or more hard balls are provided in a container, the carbon nanotubes are crushed even between the reciprocating hard balls.
  • 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 collision energy may be small and mixing may not be possible (mixing of carbon nanotubes and solubilizer). If L is large), the amplitude will inevitably increase and negative
  • the energy when the hard sphere collides with the wall surface of the hollow portion of the container becomes small, and mixing may be insufficient. Therefore, the diameter R of the hard sphere and the longitudinal length L of the hollow portion of the container
  • the ratio of a b (R: L) is preferably 1: 1.5 ⁇ 1: 100, more preferably 1: 2.0 to 1:75, a b
  • the diameter R of the hard sphere and the hollow part of the container is 1: 2.5 to 1:50 (see FIG. 5).
  • the diameter R of the hard sphere and the hollow part of the container is 1: 2.5 to 1:50 (see FIG. 5).
  • R: S) is preferably 1: 1.1-1: 30, more preferably 1: 1.2-1: 20, even more preferred a b
  • diameter R here refers to hard balls
  • the shape of the hard sphere is not particularly limited, and may be a shape other than a sphere.
  • the hard sphere has an equivalent diameter corresponding to the above-mentioned “diameter”. It is preferable.
  • the “equivalent diameter” means a diameter assumed when the shape of a non-spherical hard sphere is changed to a spherical shape without changing the volume.
  • a 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
  • the "solubilizing agent" used in step (i) refers to the inside of a container together with carbon nanotubes and hard spheres in step (i) in order to obtain an aqueous solution containing carbon nanotubes stably in step (ii).
  • it is a substance that stably disperses carbon nanotubes in a solvent such as water.
  • the solubilizer provided in the container is preferably a water-soluble compound, for example, a nucleotide having a purine ring.
  • nucleotide having a purine ring examples include adenosine triphosphate (ATP), adenosine diphosphate (ADP), adenosine monophosphate (AMP), guanosine triphosphate (GTP), and guanosine phosphate (GDP). And guanosine monophosphate (GMP).
  • ATP, ADP, AMP, GTP, GDP or GMP may be in the form of salt or hydrate.
  • ATP, ADP, AMP, GTP, GDP, or GMP may be in a form containing not only a monomer but also a polymer such as a dimer or a trimer.
  • their derivatives may be used in place of ATP, ADP, AMP, GTP, GDP or GMP.
  • the "solubilizing agent" used in step (i) is not limited to "nucleotide having a purine ring” and has a wide conjugated system and has a stronger ⁇ - ⁇ interaction.
  • ⁇ -based compounds are also preferable.
  • the ⁇ -based compound for example, porphyrin and its derivatives may be used.
  • ⁇ 1,10,15,20 tetrakis (1-methyl 4 pyridi-o) porphyrin, tetra ( ⁇ -toluenesulfonate)
  • the “toluenesulfonate” moiety may be another cation such as ⁇ , C1-), 5, 10, 15, 20-tetrakis (4 trimethylamine-phenol) porphyrin, tetra ( ⁇ (Toluene sulfonate), 5, 10, 15, 20-tetrakis (4 sulfonate phenol) porphyrins and their metal complexes (metals include zinc, iron, magnesium, conoleto, nickel, copper, ruthenium, etc.) Can be mentioned.
  • the “solubilizing agent” used in step (i) may be pyrene and derivatives thereof, such as 1-pyrenepetitic acid, 1-pyrenemethylamine hydrochloride, 1-pyrenecarboxyl. Rick Acid and 1-Pyrenesulfonate Acid be able to.
  • the “solubilizing agent” used in the step (i) may be anthracene and its derivatives, and examples thereof include 9 anthracene carboxylic acid and 9 anthracene methanol.
  • the mass ratio of the solubilizer and the carbon nanotube provided in the container is, for example, about 1: 1 to about 5000: 1, preferably about 1: 1 when the soluble agent is 0.67 mmol.
  • the aqueous solution containing the carbon nanotubes stably in the step (ii) is converted into a mixture containing carbon nanotubes after being subjected to vibration treatment, more specifically carbon nanotubes after being subjected to vibration treatment. It can be obtained by adding water.
  • the aqueous solution thus comprises added water, carbon nanotubes, and solubilizer components.
  • step (ii) if necessary, after adding water, a precipitate is obtained from the resulting mixture (the precipitate substantially comprises carbon nanotubes that are soluble in water and have strong strength). An operation of removing the may be additionally performed.
  • the water added in step (ii) is generally composed mainly of water, and is, for example, purified water such as ultrapure water or tap water.
  • stable means that the carbon nanotubes are stably dispersed in an aqueous medium over time, and for at least 1 week, preferably at least 2 weeks, more preferably at least 3 weeks. Aggregation of carbon nanotubes Indicates that no Z precipitation occurs. Therefore, it will be understood that in such an aqueous solution, the carbon nanotubes are considered to be dissolved in the aqueous solution.
  • the aqueous solution obtained according to the method of the present invention is shown in FIG.
  • the four aqueous solutions shown in this figure use GMP (guanosine monophosphate), AMP (adenosine monophosphate), ADP (adenosine diphosphate) and ATP (adenosine triphosphate) as solubilizers, respectively. It was obtained by this. As shown in the figure, the obtained aqueous solution has a black transparent appearance. This indicates that the carbon nanotubes are stably dispersed in the obtained aqueous solution, and it can be confirmed that nucleotides having a purine ring are preferable as the solubilizer of the present invention.
  • GMP guanosine monophosphate
  • AMP adenosine monophosphate
  • ADP adenosine diphosphate
  • ATP adenosine triphosphate
  • the aqueous solution obtained using a nucleotide having a purine ring contains at least the force of dissociating the bundle.
  • the specific surface area of the carbon nanotube is increased. Therefore, a member having a carbon nanotube film having a larger specific surface area can be produced from such an aqueous solution, and the member can be used as, for example, a gas storage product or an electrode.
  • a gas storage product can be used to store 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 comprises a carbon nanotube film formed by applying a base material and an aqueous solution containing the carbon nanotube produced by the method of the present invention to the surface of the base material and then drying.
  • the base material may be made of a shifted shape or material as long as it is a substrate or a support plate suitable for a gas storage product or an electrode, for example.
  • the carbon nanotubes in which the bundles are dissociated at least partially exist in the aqueous medium almost uniformly.
  • the carbon nanotube film obtained by applying the aqueous solution to the substrate surface and drying can contain carbon nanotubes almost 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 aqueous solution obtained by the method of the present invention is subjected to a filtration treatment with a conventional membrane filter. Take out only the carbon nanotubes contained in the aqueous solution, and use the removed carbon nanotubes as field emission display (FED) emitters, photoelectric conversion elements, composite materials (plastic, rubber, resin, etc.) It is used for materials such as cosmetics).
  • FED field emission display
  • FIG. 1 schematically shows a method for producing an aqueous solution containing carbon nanotubes of the present invention.
  • a method for producing an aqueous solution containing carbon nanotubes of the present invention will be described over time.
  • carbon nanotubes 1 (preferably carbon nanotubes in a dry state) are prepared. To do.
  • the carbon nanotube 1 together with the solubilizer and the two hard spheres 2 is provided in the container body hollow portion of the container 3, and the container 3 is sealed by covering the container body.
  • the hard sphere reciprocates in the hollow portion of the container, and as a result, preferably the frequency and amplitude such that the carbon nanotubes and the soluble additive are mixed, and the carbon between the Z or reciprocating hard sphere and the hollow wall surface.
  • the container 3 is reciprocated in the longitudinal direction of the hollow portion with such a frequency and amplitude that the nanotubes are crushed.
  • the carbon nanotubes taken out from the container 3 are diluted with water, whereby the aqueous solution 4 stably containing the carbon nanotubes is obtained.
  • the carbon nanotube before the carbon nanotube is subjected to a vibration operation, it may be prepared by previously mixing the soluble additive and the carbon nanotube. Further, as another preferred embodiment of the present invention, after adding a solubilizer to the carbon nanotubes, the carbon nanotubes may be subjected to drying under reduced pressure before being subjected to vibration.
  • a first aspect is a method for producing an aqueous solution containing carbon nanotubes
  • the hard ball is vibrated with respect to the container by reciprocating the container in a certain direction.
  • a hard ball is vibrated with respect to the container. And a method characterized in that the bundle of carbon nanotubes is at least partially dissociated in the container.
  • the solubilizer is adenosine triphosphate (ATP), adenosine diphosphate (ADP), adenosine monophosphate (AMP), guanosine triphosphate. (GTP), guanosine diphosphate (GDP), guanosine monophosphate (GMP), a salt thereof, and a group power consisting of the hydrate power thereof.
  • a method comprising at least one or more selected nucleotides.
  • a method of frequency is characterized 20 ⁇ 50S _1 der Rukoto.
  • Seventh aspect The method according to any one of the first to sixth aspects, wherein the time for which the hard sphere is vibrated with respect to the container is 2 minutes to 2 hours.
  • the number of hard spheres is 1 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%.
  • Tenth aspect The member according to the ninth aspect, wherein the member is used as a gas storage product.
  • JP 2005-28560 A DISCLOSURE OF THE INVENTION
  • This invention is a method for producing aqueous carbon nanotubes.
  • the disclosed invention is manufactured by sonication and centrifugation, and is hard as in the present invention.
  • a process that is essentially different from the vibration crushing process in which the container provided with the sphere is reciprocated is used.
  • oligonucleotides it only refers to general oligonucleotides, and not only specific examples of oligonucleotides but also suitable chemical structures of oligonucleotides. No mention is made at all. Therefore, it was noted in Japanese Patent Application Laid-Open No. 2005-28560 that teaching and suggestion should be made regarding nucleotides containing purine rings according to the present invention.
  • the production method of the present invention was carried out using various nucleotides as solubilizers.
  • the following operating procedure will be explained using GMP as a solubilizer as an example.
  • FIG. 3 shows a visible ultraviolet absorption spectrum of the liquid containing the obtained carbon nanotube.
  • the carbon nanotube concentration (mg / 1000 mg) in Table 1 means the mass (mg) of single-walled carbon nanotubes contained per lOOOmg of aqueous solution obtained.
  • the concentration of carbon nanotubes is determined from the absorbance (A) at a wavelength of 500 nm in the visible absorption spectrum when a 1 mm cell is used, and the CNT extinction coefficient ( ⁇
  • ⁇ -NMR spectrum measurement was performed. The results are shown in Table 2.
  • the “aqueous solution containing single-walled carbon nanotubes” used for the measurement was prepared in the same manner as described above (note that 3 mg and 15 mg of single-walled carbon nanotubes and soot were used, respectively).
  • JEOL type NM-LA600 was used as an analytical instrument.
  • the H-8 and H-2 protons of the purine ring have a relatively large magnetic field. It can be seen that there is a field shift. This is thought to be due to the shielding effect of the ⁇ -conjugated ring current of the single-walled carbon nanotube, indicating that the adenine site interacts with the sidewall of the single-walled carbon nanotube.
  • the protons ⁇ -1 ', 3-3' and ⁇ -4 'in the sugar moiety show a low magnetic field shift or a slight high magnetic field shift. This indicates that the sugar moiety is not significantly involved in the single-walled carbon nanotube surface. Based on the above results, the interaction between single-walled carbon nanotubes and ⁇ is considered to be due to the ⁇ - ⁇ interaction or hydrophobic interaction between single-walled carbon nanotubes and base sites.
  • Radial breathing mode 150 ⁇ 300Cm _1 corresponds to the semiconductor monolayer force one carbon nanotube
  • radial breathing mode 230 ⁇ 300cm _ 1 is a metal Therefore, it is considered that both the semiconductor single-walled carbon nanotube and the metal single-walled carbon nanotube are dissolved.
  • FIGS. 6 (a) to (c) show TEM photographs of single-walled carbon nanotubes (SWNT) contained in the carbon nanotube aqueous solution obtained by the production method of the present invention.
  • Figures 6 (a) to (c) are TEM photographs when different solubilizers are used.
  • Figure 6 (a) shows GMP
  • Figure 6 (b) shows ADP
  • Figure 6 (c) shows ATP. Used as a solubilizer. From the powerful TEM photographs, it can be understood that the aqueous solution obtained by the production method of the present invention contains single-walled carbon nanotubes from which the bundle is dissociated (particularly, see FIGS. 6 (b) and (c)).
  • the effect of the vibration treatment performed by the production method of the present invention is only to dissociate the carbon nanotube bundles, if not completely. It can be understood that the bundle has at least an effect of destroying the structure of the carbon nanotube itself, because the bundle is thin and the bundle is at least dissociated.
  • a carbon nanotube aqueous solution (sample A) was produced by the production method of the present invention using ATP and GMP as solubilizers, respectively.
  • ATP ATP
  • GMP solubilizer
  • Sample B was prepared using ATP and GMP, respectively, as in the production method of the present invention described above. Method of operation 'Experimental conditions are as follows.
  • sample A obtained by the production method of the present invention contains carbon nanotubes
  • sample B contains carbon nanotubes!
  • the aqueous solution obtained by the method of the present invention can be used for the production of gas storage products (for example, hydrogen storage media for storing hydrogen gas fuel in cars or ships) or electrodes (anode used for lithium secondary batteries). It can also be used in the manufacture of field emission display emitters, photoelectric conversion elements or cosmetics.
  • gas storage products for example, hydrogen storage media for storing hydrogen gas fuel in cars or ships
  • electrodes anode used for lithium secondary batteries
  • It can also be used in the manufacture of field emission display emitters, photoelectric conversion elements or cosmetics.

Abstract

La présente invention concerne un procédé de fabrication d’une solution aqueuse contenant un nanotube de carbone, comprenant les étapes d’approvisionnement en nanotube de carbone, un nucléotide comportant un noyau purique en tant qu’agent de solubilisation et une bille dure dans un récipient, d’application d’une vibration sur le récipient à une fréquence de vibration comprise entre 5 et 120 s-1 pour entraîner la vibration de la bille dure, et d’ajout d’eau au nanotube de carbone fourni après la vibration pour obtenir une solution aqueuse contenant le nanotube de carbone.
PCT/JP2006/313324 2005-07-11 2006-07-04 Procédé de préparation d’une solution aqueuse contenant un nanotube de carbone WO2007007594A1 (fr)

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JP2008300271A (ja) * 2007-06-01 2008-12-11 Nippon Oil Corp リチウムイオン貯蔵体及びリチウムイオン貯蔵方法
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WO2007075634A2 (fr) 2005-12-21 2007-07-05 Exxonmobil Research And Engineering Company Materiau resistant a la corrosion pour encrassement reduit, composant de transfert thermique ameliore en termes de resistance a la corrosion et a l’encrassement et procede pour reduire l’encrassement
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JP2012055814A (ja) * 2010-09-07 2012-03-22 Chiba Univ 機能性可溶化剤

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