WO2014084042A1 - Complexe contenant des nanotubes de carbone à double paroi - Google Patents

Complexe contenant des nanotubes de carbone à double paroi Download PDF

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WO2014084042A1
WO2014084042A1 PCT/JP2013/080607 JP2013080607W WO2014084042A1 WO 2014084042 A1 WO2014084042 A1 WO 2014084042A1 JP 2013080607 W JP2013080607 W JP 2013080607W WO 2014084042 A1 WO2014084042 A1 WO 2014084042A1
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carbon nanotube
double
walled carbon
carbon nanotubes
resin
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PCT/JP2013/080607
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English (en)
Japanese (ja)
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史郎 本田
佐藤　謙一
秀和 西野
真史 須藤
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東レ株式会社
ザ・ユニバーシティ・オブ・マンチェスター
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Priority to JP2013555673A priority Critical patent/JPWO2014084042A1/ja
Publication of WO2014084042A1 publication Critical patent/WO2014084042A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C01B2202/04—Nanotubes with a specific amount of walls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a composite containing a double-walled carbon nanotube.
  • a carbon nanotube is a substance having a structure in which a graphite sheet having a hexagonal network of carbon atoms arranged in a cylindrical shape is wound.
  • a single-walled carbon nanotube is a single-walled carbon nanotube, and a multi-walled carbon is wound in multiple layers. It is called a nanotube.
  • multi-walled carbon nanotubes those wound in two layers are called double-walled carbon nanotubes.
  • Carbon nanotubes have excellent conductivity and high mechanical strength, and are expected to be used as conductive materials and reinforcing materials.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a composite having a high affinity between a double-walled carbon nanotube and a resin and a high mechanical strength.
  • a double-walled carbon nanotube-containing composite includes a double-walled carbon nanotube comprising an inner-layer side carbon nanotube and an outer-layer side carbon nanotube, and a resin
  • a ratio of the slope of the straight line derived from the inner-wall-side carbon nanotube to the slope of the straight line derived from the nanotube is from 0.5 to 1.5.
  • the double-walled carbon nanotube-containing composite according to the present invention is characterized in that, in the above invention, the double-walled carbon nanotube is modified with a functional group containing oxygen.
  • the double-walled carbon nanotube-containing composite according to the present invention is characterized in that, in the above invention, the functional group is a hydroxyl group or a carboxyl group.
  • the double-walled carbon nanotube-containing composite according to the present invention is characterized in that, in the above-mentioned invention, a ratio of oxygen atoms to carbon atoms in the double-walled carbon nanotube is 0.1 at% or more and 20 at% or less. To do.
  • the double-walled carbon nanotube-containing composite according to the present invention is the value of the ratio of the G-band height to the D-band height when the double-walled carbon nanotube is subjected to Raman spectroscopic analysis at a wavelength of 633 nm. Is 20 or more.
  • the double-walled carbon nanotube-containing composite according to the present invention is characterized in that, in the above invention, the resin is a thermosetting resin.
  • the double-walled carbon nanotube-containing composite according to the present invention is characterized in that, in the above invention, the resin is an epoxy resin.
  • the double-walled carbon nanotube-containing composite according to the present invention is characterized in that, in the above invention, the double-walled carbon nanotube is contained in an amount of 0.001 wt% to 10 wt% with respect to the resin. To do.
  • double-walled carbon nanotube-containing composite of the present invention in the above invention, the absolute value of the slope of the line from the outer side carbon nanotubes, is 10 cm -1 /% or more 50 cm -1 /% or less It is characterized by that.
  • the affinity between the double-walled carbon nanotube and the resin is high, and furthermore, the inner layer and the outer layer of the double-walled carbon nanotube propagate stress.
  • a composite exhibiting good mechanical properties can be obtained.
  • FIG. 1 is a diagram for explaining Raman spectroscopic analysis for a double-walled carbon nanotube-containing composite according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a configuration example of a carbon nanotube production apparatus for producing a carbon nanotube of a double-walled carbon nanotube-containing composite according to an embodiment of the present invention.
  • FIG. 3 is a graph showing the relationship between strain and G ′ band shift in carbon nanotubes of a double-walled carbon nanotube-containing composite according to an example of the present invention.
  • FIG. 4 is a graph showing the relationship between strain and G ′ band shift in carbon nanotubes of a double-walled carbon nanotube-containing composite according to an example of the present invention.
  • FIG. 1 is a diagram for explaining Raman spectroscopic analysis for a double-walled carbon nanotube-containing composite according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a configuration example of a carbon nanotube production apparatus for producing a carbon nanotube
  • FIG. 5 is a graph showing the relationship between strain and G ′ band shift in carbon nanotubes of a double-walled carbon nanotube-containing composite according to an example of the present invention.
  • FIG. 6 is a graph showing the relationship between strain and G ′ band shift in a carbon nanotube of a double-walled carbon nanotube-containing composite according to an example of the present invention.
  • FIG. 7 is a graph showing the relationship between strain and G ′ band shift in a carbon nanotube of a double-walled carbon nanotube-containing composite according to an example of the present invention.
  • FIG. 8 is a graph showing the relationship between strain and G ′ band shift in a carbon nanotube of a double-walled carbon nanotube-containing composite according to an example of the present invention.
  • the double-walled carbon nanotube-containing composite according to the present invention includes a double-walled carbon nanotube in which two carbon nanotubes having different diameters (inner-wall side carbon nanotube and outer-layer side carbon nanotube) are concentrically overlapped, and a resin. Is the body.
  • the double-walled carbon nanotube is a graph showing the relationship between the distortion of the composite and the G ′ band shift obtained when a Raman spectroscopic analysis is applied to the composite.
  • the ratio of the slope of the straight line derived from the inner-layer-side carbon nanotube (the slope of the inner layer / the slope of the outer layer) is 0.5 or more and 1.5 or less.
  • the carbon nanotubes have a shape in which one surface of graphite is wound into a cylindrical shape, and a single-walled carbon nanotube is a single-walled carbon nanotube and a multi-walled carbon nanotube is a single-walled carbon nanotube.
  • multi-walled carbon nanotubes those wound in two layers are called double-walled carbon nanotubes.
  • the double-walled carbon nanotube used in the present invention means a total of a plurality of double-walled carbon nanotubes, and the form of existence thereof is not particularly limited, and each is independent or bundled or entangled. It may exist in the form or a mixed form thereof.
  • the impurity for example, catalyst
  • the thing comprised substantially by carbon is shown.
  • the thing of various diameter may be contained.
  • the morphology of carbon nanotubes can be examined with a high-resolution transmission electron microscope.
  • the graphite layer is preferred so that it can be seen straight and clearly in a transmission electron microscope, but the graphite layer may be disordered.
  • the carbon nanotubes used in the present invention may contain carbon nanotubes having various numbers of layers, but are mainly composed of double-walled carbon nanotubes.
  • the main component means that 50 or more (half or more) of the 100 carbon nanotubes are double-walled carbon nanotubes when observed with a transmission electron microscope. Furthermore, it is preferable that 70 or more of 100 carbon nanotubes are double-walled carbon nanotubes.
  • the number here refers to the evaluation of the number of double-walled carbon nanotubes by observing 100 arbitrary carbon nanotubes contained in the aggregate of carbon nanotubes.
  • the number of layers and the number of the arbitrary carbon nanotubes can be counted by, for example, observing with a transmission electron microscope at a magnification of 400,000, and in a visual field in which 10% or more of the visual field area is a carbon nanotube in a visual field of 75 nm square.
  • the number of layers is evaluated for 100 carbon nanotubes arbitrarily extracted from. When 100 lines cannot be measured in one field of view, measurement is performed from a plurality of fields until 100 lines are obtained. At this time, one carbon nanotube is counted as one if a part of the carbon nanotube is visible in the field of view, and both ends are not necessarily visible. In addition, even if it is recognized as two in the field of view, it may be connected outside the field of view and become one, but in that case, it is counted as two.
  • the carbon nanotubes used in the present invention are preferably those having an average outer diameter in the range of 1.0 nm to 3.0 nm.
  • the average value of the outer diameter was observed with the transmission electron microscope at a magnification of 400,000, and 100 pieces arbitrarily extracted from a field where 10% or more of the field area was a carbon nanotube in a field of view of 75 nm square. It is an arithmetic mean value when a sample is observed by the same method as that for evaluating the number of layers of carbon nanotubes and the outer diameter of the carbon nanotubes is measured.
  • the double-walled carbon nanotube used in the present invention is modified with a functional group containing oxygen.
  • the functional group containing oxygen includes a hydroxyl group, a carboxyl group, a carbonyl group, an ether group, and the like, but is not particularly limited as long as it contains oxygen. Among these, a hydroxyl group and a carboxyl group are preferable.
  • XPS X-ray photoelectron spectroscopy
  • the double-walled carbon nanotube of the present invention has a functional group containing oxygen as described above, and the ratio of the oxygen atom to the carbon atom in the double-walled carbon nanotube is 0.1 at% (atomic%) or more and 20 at%. % Or less.
  • a ratio of oxygen atoms to carbon atoms can be evaluated by using surface composition analysis of X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the ratio of oxygen atoms to carbon atoms is 0.1 at% or more and 20 at% or less, and the carbon nanotube assembly exhibiting excellent conductivity Since it becomes a body, it is preferable.
  • the ratio of oxygen atoms to carbon atoms is 1 at% or more and 15 at% or less.
  • the carbon nanotubes used in the present invention preferably have a ratio of the G band height to the D band height (G / D ratio) by Raman spectroscopy of 20 or more. More preferably, it is 40 or more and 200 or less, More preferably, it is 50 or more and 150 or less.
  • the G / D ratio is a value when carbon nanotubes are evaluated by Raman spectroscopy.
  • a microscopic laser Raman spectrophotometer analyzer JASCO NRS2100 manufactured by JASCO Corporation
  • the laser wavelength used in the Raman spectroscopic analysis method is 633 nm.
  • the Raman shift observed in the vicinity of 1590 cm ⁇ 1 in the Raman spectrum obtained by Raman spectroscopy is called a graphite-derived G band
  • the Raman shift observed in the vicinity of 1350 cm ⁇ 1 is derived from defects in amorphous carbon or graphite. Called the D band.
  • a carbon nanotube having a higher height ratio of G band and D band and a higher G / D ratio indicates a higher degree of graphitization and higher quality.
  • solid Raman spectroscopy such as carbon nanotubes may vary depending on sampling. Therefore, at least three places and another place are subjected to Raman spectroscopic analysis, and an arithmetic average thereof is taken.
  • a G / D ratio of 20 or more indicates a considerably high quality carbon nanotube.
  • the G / D ratio is 20 or less, the original double-walled carbon nanotubes are too low in graphite and the stress of the inner layer and the outer layer does not propagate well.
  • the resin used in the present invention may be either a thermosetting resin or a thermoplastic resin. Preferably, it is a thermosetting resin.
  • thermosetting resin is not particularly limited, and any thermosetting resin can be suitably used. Specifically, unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, urea resins, melamine resins, polyimides, copolymers thereof, modified products, and resins obtained by blending two or more types are used. be able to. Among these, an epoxy resin having an excellent balance of heat resistance, mechanical properties, and adhesiveness can be preferably used.
  • the epoxy resin is not particularly limited, and any epoxy resin can be suitably used. Specifically, it is obtained by oxidizing a glycidyl ether obtained from polyol, a glycidyl amine obtained from an amine having a plurality of active hydrogens, a glycidyl ester obtained from a polycarboxylic acid, or a compound having a plurality of double bonds in the molecule. Polyepoxides that can be used are used.
  • glycidyl ether examples include the following. First, bisphenol A type epoxy resin obtained from bisphenol A, bisphenol F type epoxy resin obtained from bisphenol F, bisphenol S type epoxy resin obtained from bisphenol S, tetrabromobisphenol A type epoxy resin obtained from tetrabromobisphenol A, etc. Bisphenol type epoxy resin.
  • bisphenol F type epoxy resins include “Epicoat” 806, “Epicoat” 807, “Epicoat” E4002P, “Epicoat” E4003P, “Epicoat” E4004P, “Epicoat” E4007P, “Epicoat” E4009P, “Epicoat” E4010P (Made by Japan Epoxy Resin Co., Ltd.), “Epiclon” 830 (Dainippon Ink Chemical Co., Ltd.), “Epototo” YDF-2001, “Epototo” YDF-2004 (above, manufactured by Toto Kasei Co., Ltd.) Can be mentioned.
  • bisphenol S-type epoxy resins include “Denacol (registered trademark, the same shall apply hereinafter)” EX-251 (manufactured by Nagase Kasei Kogyo Co., Ltd.) and “Epiclon” EXA-1514 (manufactured by Dainippon Ink & Chemicals, Inc.). Can be mentioned.
  • tetrabromobisphenol A type epoxy resins include “Epicoat” 5050 (manufactured by Japan Epoxy Resin Co., Ltd.), “Epicron” 152 (manufactured by Dainippon Ink & Chemicals, Inc.), and “Sumiepoxy” ESB-400T (Sumitomo Chemical). And “Epototo” YBD-360 (manufactured by Toto Kasei Co., Ltd.).
  • novolak type epoxy resins which are glycidyl ethers of novolac obtained from phenol derivatives such as phenol, alkylphenol and halogenated phenol, are “Epicoat” 152, “Epicoat” 154, “Epicoat” 157 (above, Japan).
  • Epoxy Resin Co., Ltd. Epoxy Resin Co., Ltd.
  • DER 438 Down Chemical Co., Ltd.
  • Aldite registered trademark, the same applies hereinafter
  • EPN1138 BASF Corp.
  • Araldite EPN1139
  • BREN-105 BREN-105
  • glycidylamine examples include diglycidylaniline, “Sumiepoxy” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), which is tetraglycidyldiaminodiphenylmethane, and TETRAD (registered trademark, the same applies hereinafter) —tetraglycidyl-m-xylylenediamine— X (manufactured by Mitsubishi Gas Chemical Co., Inc.) can be used, and the resin can be used within a range that does not significantly impair the elongation of the resin.
  • epoxy resins having both glycidyl ether and glycidyl amine structures “Sumiepoxy” ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), which is triglycidyl-m-aminophenol, and “Araldite, which is triglycidyl-p-aminophenol” "MY0510 (manufactured by Ciba-Geigy Corporation) can be mentioned, and it can be used within a range that does not significantly impair the elongation of the resin.
  • glycidyl ester examples include phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and dimer acid diglycidyl ester.
  • triglycidyl isocyanurate can be mentioned as an epoxy resin having a glycidyl group other than these.
  • Examples of the epoxy resin obtained by oxidizing a compound having a plurality of double bonds in the molecule include epoxy resins having an epoxycyclohexane ring. Specific examples thereof include ERL-4206 and ERL-4221 of Union Carbide. , ERL-4234, and the like. Furthermore, epoxidized soybean oil can also be mentioned.
  • epoxy resins it is preferable to include one or more epoxy resins having at least one skeleton selected from biphenyl, naphthalene, fluorene, dicyclopentadiene, and an oxazolidone ring.
  • the mechanical properties are remarkably improved by the synergistic effect with the carbon nanofibers, and the heat resistance of the cured resin can also be improved.
  • Examples of commercially available epoxy resins having a biphenyl skeleton include “Epicoat” YX4000, YX4000H, YL6121 (above, Japan Epoxy Resin Co., Ltd.), NC3000, NC3000H (above, Nippon Kayaku Co., Ltd.). it can.
  • epoxy resins having a naphthalene skeleton include “Epiclon” HP4032, HP4032D, H4032H, EXA4750, EXA4700, EXA4701 (above, manufactured by Dainippon Ink Industries, Ltd.), NC7000L, NC7300L (above, manufactured by Nippon Kayaku Co., Ltd.) ) And the like.
  • epoxy resins having a fluorene skeleton include “Epon (registered trademark, the same shall apply hereinafter)”, HPT resin 1079 (manufactured by Shell), “Ogsol (registered trademark, same shall apply hereinafter)” PG, EG (hereinafter referred to as Nagase ChemteX) And the like).
  • epoxy resins having a dicyclopentadiene skeleton include “Epiclon” HP7200L, HP7200, HP7200H, HP7200HH (above, manufactured by Dainippon Ink & Chemicals, Inc.), XD-1000-L, XD-1000-2L (above , Nippon Kayaku Co., Ltd.), “Tactix (registered trademark, the same applies hereinafter)” 556 (manufactured by Huntsman), and the like.
  • Examples of commercially available epoxy resins having an oxazolidone ring skeleton include “Araldite” AER4152, XAC4151, and the like, manufactured by Asahi Kasei Epoxy Corporation.
  • a curing agent may be used.
  • Curing agents bring about a curing reaction in the presence of thermosetting resins and include not only general curing agents but also initiators, catalysts, curing accelerators, curing aids, and combinations thereof. But you can.
  • the curing agent includes activities such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, m-phenylenediamine, and m-xylylenediamine.
  • Tertiary amines such as phenol and 1-substituted imidazole that do not have active hydrogen, dicyandiamide, tetramethylguanidine, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic acid Carboxy
  • curing agents can be combined with a curing aid as appropriate in order to increase the curing activity.
  • Preferred examples include dicyandiamide, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (3-chloro-4-methylphenyl).
  • DCMU 3-(,4-dichlorophenyl) -1,1-dimethylurea
  • DCMU 3- (3-chloro-4-methylphenyl).
  • urea derivatives such as 1,1-dimethylurea and 2,4-bis (3,3-dimethylureido) toluene
  • tertiary amines on carboxylic anhydrides and novolac resins Examples of combinations as agents are given.
  • the compound used as a curing aid is preferably a compound having the ability to cure an epoxy resin alone.
  • thermoplastic resin is not particularly limited, and any thermoplastic resin can be suitably used. Specifically, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl acetate resin, acrylonitrile-butadiene-styrene (ABS) resin, poly (methyl methacrylate) resin, polyamide resin, polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, Polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, polyamideimide resin, polyvinyl alcohol resin and the like can be used.
  • ABS acrylonitrile-butadiene-styrene
  • ABS acrylonitrile-butadiene-styrene
  • poly (methyl methacrylate) resin polyamide resin
  • polycarbonate resin polybutylene terephthalate resin
  • polyethylene terephthalate resin polyethylene terephthalate resin
  • Polyphenylene sulfide resin polyether
  • the double-walled carbon nanotube-containing composite of the present invention is a composite containing 0.001 wt% (wt%) to 10 wt% of double-walled carbon nanotubes with respect to such a resin. Preferably, it is contained at 0.005 wt% or more and 5 wt% or less. Thereby, the resin characteristic of a double-walled carbon nanotube containing composite can be improved suitably.
  • FIG. 1 is a diagram for explaining Raman spectroscopic analysis for a double-walled carbon nanotube-containing composite according to an embodiment of the present invention.
  • the double-walled carbon nanotube-containing composite is subjected to Raman spectroscopic analysis with a predetermined load applied, and a graph showing the relationship between strain and G ′ band shift is obtained.
  • the G ′ band shift with respect to the distortion is acquired by performing the following operation.
  • the composite 1 of the double-walled carbon nanotube and the resin is fixed on the base 10 and stress is applied to the base 10 to distort the composite 1 (see FIG. 1).
  • the stress applied to the base material 10 is a direction in which each surface is pressed from the front surface (upper surface in the figure) and the back surface (lower surface in the figure) in the sheet-like base material 10, and the pressing position on the back surface side is These are applied so as to be located in the center portion from the pressurizing position on the surface side.
  • Due to the distortion of the base material 10, the composite 1 is distorted in an arc shape having a convex surface side.
  • the strain (ratio) at this time is measured with a strain gauge and plotted on the horizontal axis of the graph.
  • the Raman spectroscopic analysis is performed using a laser having a wavelength of 514 nm or 633 nm in a state where the composite 1 is distorted.
  • scattered light from the complex 1 corresponding to the irradiated laser is detected.
  • a G ′ band derived from a double-walled carbon nanotube appears around 2600 cm ⁇ 1 .
  • the G ′ band derived from the inner layer side carbon nanotube is detected in the vicinity of 2590 cm ⁇ 1
  • the G ′ band derived from the outer layer side carbon nanotube is detected in the vicinity of 2630 cm ⁇ 1 .
  • the strain is plotted on the horizontal axis as the pressing rate (Strain (%)), and the G ′ band shift of each of the inner layer and the outer layer is expressed by (G′ ⁇ Band frequency (cm -1 )) is plotted on the vertical axis.
  • the composite containing a double-walled carbon nanotube according to the present invention has a G ′ band shift (plot) with respect to the tensile strain when the graph is prepared in a tensile strain range of 0% to 0.4%.
  • Each of the side carbon nanotubes is located near the approximate straight line.
  • the method of producing the approximate straight line is preferably the least square method.
  • the respective inclinations (cm ⁇ 1 /%) can be obtained. Using this slope value, when the ratio of the slope of the inner carbon nanotube to the slope of the outer carbon nanotube (the slope of the inner layer / the slope of the outer layer) was determined, the composite according to the present invention was 0.5 It is 1.5 or less.
  • the value of the inner layer inclination / outer layer inclination is 0.8 or more and 1.2 or less.
  • the value of the inclination of the inner layer / the inclination of the outer layer is not less than 0.5 and not more than 1.5, indicating that the stress between the inner layer and the outer layer propagates in the double-walled carbon nanotube.
  • the same G ′ band shift occurs, and this inclination becomes nearly parallel. If this inclination exceeds the specified range, it indicates that the force applied to the outer layer is not propagated to the inner layer.
  • the outer layer of the double-walled carbon nanotube exhibits affinity with the resin, and the externally applied force propagates stress between the resin, the outer layer, and the inner layer, thereby demonstrating the high mechanical strength of the very high-quality carbon nanotube of the inner layer itself. Therefore, it exhibits a very high mechanical strength as a composite.
  • the absolute value of the inclination derived from the outer layer is preferably 10 cm ⁇ 1 /% to 50 cm ⁇ 1 /%, and preferably 15 cm ⁇ 1 /% to 30 cm ⁇ 1. /% Or less is more preferable.
  • the inclination within the specified range means that in the double-walled carbon nanotube-containing composite, the stress propagates between the matrix resin and the outer layer of the double-walled carbon nanotube, and the elastic modulus of the double-walled carbon nanotube is high. Indicates.
  • the method for producing a double-walled carbon nanotube preferably used in the present invention is produced, for example, as follows.
  • a fluidized bed made of powdered catalyst with iron supported on magnesia is formed on the entire horizontal cross-sectional direction of the reactor, and methane is circulated in the vertical direction in the reactor. Is obtained by contacting the catalyst at 500 to 1200 ° C. with the catalyst to produce carbon nanotubes, and then purifying the obtained carbon nanotubes.
  • magnesia which is a carrier
  • magnesia a commercially available product may be used, or a synthesized product may be used.
  • magnesium metal is heated in air, magnesium hydroxide is heated to 850 ° C. or higher, or magnesium carbonate 3MgCO 3 .Mg (OH) 2 .3H 2 O is heated to 950 ° C. or higher. There are ways to do it.
  • magnesia light magnesia is preferable.
  • Light magnesia is magnesia having a low bulk density, specifically 0.20 g / mL or less, preferably 0.05 to 0.16 (g / mL). It is preferable from the point.
  • Bulk density is the mass of powder per unit bulk volume. The bulk density measurement method is shown below. The bulk density of the powder may be affected by the temperature and humidity at the time of measurement. The bulk density referred to here is a value measured at a temperature of 20 ⁇ 10 ° C. and a humidity of 60 ⁇ 10%. For the measurement, a 50 mL graduated cylinder is used as a measurement container, and the powder is added so as to occupy a predetermined volume while tapping the bottom of the graduated cylinder.
  • the iron carried on the carrier is not always in a zero-valent state. Although it can be estimated that the metal is in a zero-valent state during the reaction, it may be a compound containing iron or an iron species.
  • organic salts or inorganic salts such as iron formate, iron acetate, iron trifluoroacetate, iron iron citrate, iron nitrate, iron sulfate, and iron halide, complex salts such as ethylenediaminetetraacetic acid complex and acetylacetonate complex, etc. Used.
  • Iron is preferably fine particles. The particle diameter of the fine particles is preferably 0.5 to 10 nm. When iron is a fine particle, a carbon nanotube with a small outer diameter is likely to be generated.
  • the method for producing the carbon nanotube production catalyst is not particularly limited.
  • magnesia is impregnated in a non-aqueous solution (for example, a methanol solution) or an aqueous solution in which a metal salt of iron is dissolved, sufficiently dispersed and mixed, and then dried. Thereafter, it may be heated at a high temperature (100 ° C. to 600 ° C.) in the atmosphere or in an inert gas such as nitrogen, argon or helium or in vacuum (impregnation method).
  • a carrier such as magnesia is impregnated in an aqueous solution in which an iron metal salt is dissolved, sufficiently dispersed and mixed, and reacted under heat and pressure (100 ° C.
  • a catalyst for carbon nanotube production by a hydrothermal method is prepared by mixing and stirring an iron compound and an Mg compound in water, heating the mixture, and hydrothermal reaction by pressurization to obtain a catalyst precursor. Obtained by heating the body at a specific temperature.
  • the iron compound and the Mg compound are each hydrolyzed to become a composite hydroxide via dehydration polycondensation. This becomes a catalyst precursor in a state where iron is highly dispersed in Mg hydroxide.
  • Mg compound nitrate, nitrite, sulfate, ammonium sulfate, carbonate, acetate, citrate, oxide and hydroxide are preferable, and oxide is more preferable.
  • the amount of the iron compound and the Mg compound used may be mixed in two layers so that the amount of the iron component in the iron compound is 0.1 wt% or more and 1 wt% or less with respect to the MgO equivalent amount of the Mg compound. It is preferable in terms of easy production of the contained relatively thin carbon nanotube, and more preferably in the range of 0.2 wt% or more and 0.6 wt% or less.
  • the water and Mg compound are preferably mixed at a molar ratio of 4: 1 to 100: 1, more preferably 9: 1 to 50: 1, and further preferably 9: 1 to 30: 1.
  • the iron compound and Mg compound may be mixed and stirred in water after mixing, concentrating and drying in advance, and the hydrothermal reaction may be carried out. However, in order to simplify the process, the iron compound and Mg compound are directly combined.
  • it is preferably subjected to a hydrothermal reaction.
  • the hydrothermal reaction is carried out under heating and pressure, but it is preferable to generate a self-generated pressure by heating the mixed water containing the suspension in a pressure vessel such as an autoclave in the range of 100 ° C to 250 ° C.
  • the heating temperature is more preferably in the range of 100 ° C to 200 ° C. It is also possible to apply pressure by adding an inert gas.
  • the heating time at the time of hydrothermal reaction is closely related to the heating temperature, usually 30 minutes to 10 hours, and the higher the temperature, the shorter the hydrothermal reaction. Is short. For example, when it is performed at 250 ° C., 30 minutes to 2 hours are preferable, and when it is performed at 100 ° C., 2 hours to 10 hours are preferable.
  • the catalyst precursor is a slurry suspension.
  • the recovery method is not particularly limited, but the catalyst precursor can be easily recovered preferably by filtration or centrifugation. More preferably, filtration is performed, and either suction filtration or natural filtration may be performed.
  • the catalyst precursor subjected to solid-liquid separation is a composite hydroxide of iron and Mg, and when heated, becomes a composite oxide of iron and Mg.
  • the heat treatment is performed in the atmosphere or in an inert gas such as nitrogen, argon, helium, etc., and is preferably heated in the range of 400 ° C. to 1000 ° C., more preferably in the range of 400 ° C. to 700 ° C.
  • the heating time is preferably in the range of 1 to 5 hours. Since the catalyst precursor before heating is mainly composed of Mg hydroxide, it has a flaky primary structure.
  • the reaction system is not particularly limited, but the reaction is preferably carried out using a vertical fluidized bed reactor.
  • the vertical fluidized bed reactor is a reactor installed so that methane as a raw material (carbon source) flows in a vertical direction (hereinafter sometimes referred to as “longitudinal direction”). Methane flows in the direction from one end of the reactor toward the other end and passes through the catalyst layer.
  • a reactor having a tube shape can be preferably used.
  • the vertical direction includes a direction having a slight inclination angle with respect to the vertical direction (for example, 90 ° ⁇ 15 °, preferably 90 ° ⁇ 10 ° with respect to the horizontal plane).
  • the methane supply section and the discharge section do not necessarily have to be end portions of the reactor, and methane may flow in the above-described direction and pass through the catalyst layer in the flow process.
  • FIG. 2 is a schematic diagram showing a configuration example of a carbon nanotube production apparatus for producing a carbon nanotube of a double-walled carbon nanotube-containing composite according to the present embodiment.
  • a synthesis apparatus 100 shown in FIG. 2 is provided on the outer periphery of a reaction tube 101 that synthesizes carbon nanotubes using a carbon source such as methane, and generates heat when energized.
  • a carrier gas supply for supplying a carrier gas as a mobile phase connected to a linear velocity control unit 104 for controlling the linear velocity of the carbon source from the source supply unit 104a and a side pipe 103a branched at the center of the introduction pipe 103
  • Catalyst holding unit having a linear velocity control unit 105 that controls the linear velocity of the carrier gas from the unit 105a and a quartz sintered plate 106a that is provided at the end of the introduction tube 103 on the reaction tube 101 side and that holds the catalyst.
  • Comprising 106 a recovery unit 107 for recovering the carbon nanotubes produced in the reaction tube 101, a thermometer 108 for measuring the temperature of the catalyst retaining section 106, a.
  • the recovery unit 107 is provided with a gas exhaust pipe 107 a that exhausts the carrier gas and the like that has passed through the reaction tube 101 and the recovery unit 107.
  • the catalyst is in a state of being present in the entire horizontal cross-sectional direction of the reactor in the vertical fluidized bed reactor, and a fluidized bed is formed during the reaction. By doing in this way, a catalyst and methane can be made to contact effectively.
  • a quartz sintered plate 106a which is a table for placing the catalyst, is installed in the reaction tube 101, and the catalyst layer formed thereon exists over the entire horizontal cross-sectional direction of the reaction tube 101. .
  • the fluidized bed type is preferable because continuous synthesis is possible by continuously supplying a catalyst and continuously removing the catalyst and carbon nanotubes after the reaction, and carbon nanotubes can be obtained efficiently.
  • the carbon nanotube synthesis reaction is performed uniformly, the catalyst coating by impurities such as amorphous carbon is suppressed, and the catalyst activity is expected to continue for a long time. .
  • a horizontal reactor In contrast to a vertical reactor, a horizontal reactor has a laterally (horizontal) reactor in which a catalyst placed on a quartz plate is placed, and methane passes over the catalyst. It refers to a reaction device in a mode of contacting and reacting. In this case, carbon nanotubes are generated on the catalyst surface, but methane does not reach the inside of the catalyst, so that the yield tends to be lower than that of the vertical reactor. In contrast, in the vertical reactor, the raw material methane can be brought into contact with the entire catalyst, so that a large amount of carbon nanotubes can be efficiently synthesized.
  • the reactor is preferably heat resistant and is preferably made of a heat resistant material such as quartz or alumina.
  • Methane is distributed at a linear speed of 8 cm / sec or higher.
  • the carbon nanotube synthesis reaction in order to increase the decomposition efficiency of methane and increase the yield, it was usual to circulate methane at a low linear velocity.
  • the aggregate of the catalyst is larger than the conventional one. is doing. Therefore, when flowing at a low linear velocity and at a heating temperature, the catalyst layer does not flow, and a problem of so-called short path occurs in which methane passes only through the most easily passing portion of the catalyst layer. Therefore, the linear velocity is preferably 8 cm / sec or more and 10 cm / sec or less.
  • the synthesized double-walled carbon nanotubes are usually removed from the catalyst and subjected to complex formation through purification, oxidation treatment or the like, if necessary.
  • the inner layer side with respect to the slope of the straight line derived from the outer layer side carbon nanotubes Since the ratio of the slope of the straight line derived from the carbon nanotube is 0.5 or more and 1.5 or less, the double-walled carbon nanotube has high mechanical strength and high affinity between the double-walled carbon nanotube and the resin. A complex can be obtained.
  • the autoclave container was allowed to cool, the slurry-like cloudy substance was taken out from the container, and excess water was separated by suction filtration.
  • the moisture content in the filtered product at this time was 2.16.
  • the filtered product was dried by heating in a dryer at 120 ° C. to evaporate water.
  • a catalyst having a particle size in the range of 0.85 mm to 2.36 mm was recovered by using a sieve while refining the obtained solid content in a mortar.
  • the obtained catalyst contained 27.5% of a catalyst having a particle size in the range of 2.0 mm to 2.36 mm.
  • These granular catalysts were introduced into an electric furnace and heated at 600 ° C. for 3 hours in the atmosphere.
  • the iron content in the catalyst was 0.40 wt%.
  • Carbon nanotubes were synthesized using the synthesis apparatus 100 shown in FIG.
  • a cylindrical quartz tube having an inner diameter of 75 mm and a length in the central axis direction of 1100 mm was used.
  • three electric furnaces 102 having an annular shape surrounding the circumference of the reaction tube 101 were arranged so that the reaction tube 101 could be maintained at an arbitrary temperature.
  • the prepared solid catalyst 132 g is taken and introduced onto the quartz sintered plate 106 a at the center of the reaction tube 101 installed in the vertical direction to form a catalyst layer on the catalyst holding unit 106. It was. While the catalyst layer is heated until the temperature in the reaction tube 101 reaches about 860 ° C., 21.6 L of nitrogen gas is controlled from the bottom of the reaction tube 101 toward the top of the reaction tube 101 under the control of the linear velocity control unit 105. / Min, and allowed to pass through the catalyst layer. Thereafter, while supplying nitrogen gas, under the control of the linear velocity control unit 104, methane gas was introduced at 1.0 L / min for 46 minutes, vented so as to pass through the catalyst layer, and reacted.
  • the linear velocity (v) of the gas containing methane at this time was 8.55 cm / sec.
  • the introduction of methane gas was stopped, and the inside of the reaction tube 101 was cooled to room temperature while supplying nitrogen gas at 21.6 L / min.
  • the heating was stopped and the mixture was allowed to stand at room temperature, and after reaching room temperature, the catalyst and carbon nanotubes were taken out from the reactor.
  • Concentrated nitric acid (first grade Assay 60% manufactured by Kishida Chemical Co., Ltd.) about 0.3 times the weight was added to the dry weight of the obtained carbon nanotubes in the wet state. Thereafter, the mixture was heated to reflux with stirring in an oil bath heated to about 140 ° C. for 24 hours. After heating to reflux, the mixture was allowed to cool to room temperature, a nitric acid solution containing carbon nanotubes was diluted 3 times with ion-exchanged water, and an omnipore membrane filter (Millipore, filter type: 1.0 ⁇ m JA) was installed. Suction filtration was performed using a filter (liquid phase oxidation treatment). After washing with ion-exchanged water until the suspension of the filtered material became neutral, carbon nanotubes (first wet cake) were obtained in a wet state containing water.
  • the obtained first wet cake was added to 0.3 L of a 28% aqueous ammonia solution (special grade, manufactured by Kishida Chemical Co., Ltd.) and stirred at room temperature for 1 hour. Thereafter, the solution was subjected to suction filtration (ammonia treatment) using a filter having an inner diameter of 90 mm provided with an omnipore membrane filter (manufactured by Millipore, filter type: 1.0 ⁇ m JA). Thereafter, the membrane was washed with ion-exchanged water until the wet cake on the membrane filter became near neutral, and carbon nanotubes (second wet cake) were obtained in a wet state containing water.
  • a 28% aqueous ammonia solution special grade, manufactured by Kishida Chemical Co., Ltd.
  • the obtained 2nd wet cake was added in 0.3 L of 60% nitric acid aqueous solution (Kishida Chemical Co., Ltd. grade 1 Assay 60%). After stirring at room temperature for 24 hours, suction filtration was performed using a filter having an inner diameter of 90 mm equipped with an Omnipore membrane filter (filter type: 1.0 ⁇ m JA) manufactured by Millipore (nitric acid dope). Thereafter, the membrane was washed with ion-exchanged water until the wet cake on the membrane filter became near neutral. Wet carbon nanotubes (third wet cake) containing water obtained by this washing treatment were stored.
  • the obtained wet carbon nanotubes (third wet cake) were used in a dried form by appropriately evaporating water with a 120 ° C. drier.
  • purification treatment was performed as follows. First, a 6N aqueous hydrochloric acid solution was added to the calcined carbon nanotube aggregate, and the mixture was stirred in a water bath at 80 ° C. for 2 hours. The recovered material obtained by filtration using a filter having a pore diameter of 1 ⁇ m was added to a 6N aqueous hydrochloric acid solution, and stirred in a water bath at 80 ° C. for 60 minutes. This was filtered using a filter having a pore diameter of 1 ⁇ m, washed with water several times, and then the filtrate was dried in an oven at 120 ° C. overnight to remove magnesia and metal, thereby purifying the carbon nanotubes.
  • Raman spectroscopy measurement was performed on the double-walled carbon nanotubes obtained as described above.
  • a powder sample was placed on a Raman spectrometer (INF-300 manufactured by Horiba Joban Yvon), and measurement was performed using a laser wavelength of 633 nm.
  • the analysis was performed at three different locations, and an arithmetic average was taken.
  • the G / D ratio was 52, and it was a high-quality double-walled carbon nanotube with a high degree of graphitization.
  • XPS analysis of double-walled carbon nanotubes obtained by purification step 1 XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy) measurement was performed on the double-walled carbon nanotubes produced as described above. XPS measurement was performed under the following conditions. Excitation X-ray: Monochromatic Al K 1, 2 wire X-ray diameter: 1000 ⁇ m Photoelectron escape angle: 90 ° (inclination of detector with respect to sample surface)
  • the nanotube composite was prepared using a two-component mixed epoxy composed of an epoxy resin (Araldite (registered trademark) LY 5052) and a curing agent (Araldite (registered trademark) HY 5052).
  • the carbon nanotubes were dispersed in the curing agent using an ultrasonic probe (Ultrasonic Processor CPX 750 manufactured by Cole-Parmer, amplitude 35%, output 750 W).
  • Ultrasonic Processor CPX 750 manufactured by Cole-Parmer, amplitude 35%, output 750 W.
  • the carbon nanotube-epoxy composite was cast on an epoxy cured material having the same composition and not containing carbon nanotubes, and allowed to stand at room temperature for 7 days to be cured.
  • the carbon nanotube concentration of the composite was about 0.01 wt%.
  • the carbon nanotube-epoxy composite was mechanically strained by 4-point bending with the epoxy material supporting it (see FIG. 1).
  • the distortion to the composite film was given to be equivalent to the surface distortion of the epoxy material, and the distortion was measured with a strain gauge.
  • Raman spectra from carbon nanotubes were collected at different strain levels in the 0-0.4% tensile strain range.
  • FIG. 3 is a graph showing the relationship between strain and G ′ band shift in carbon nanotubes of a double-walled carbon nanotube-containing composite according to an example of the present invention. Raman spectroscopic analysis was performed using a laser wavelength of 633 nm. As shown in FIG. 3, G ′ 1 band shift and G ′ 2 band shift, which are G ′ band shifts divided into two peaks, are plotted against the added distortion.
  • the inclination corresponding to G ′ 1 indicating the outer layer side carbon nanotube was ⁇ 18.2 cm ⁇ 1 /%
  • the inclination corresponding to G ′ 2 indicating the inner layer side carbon nanotube was ⁇ 17.0 cm ⁇ 1 /%.
  • the inclination of the straight line derived from the inner layer side carbon nanotubes (inclination of the inner layer / inclination of the outer layer) with respect to the inclination of the straight line derived from the outer layer side carbon nanotubes was 0.93. This not only indicates that the stress transmission between the inner-layer side carbon nanotubes and the outer-layer side carbon nanotubes when strain is applied to the composite is large, and bears almost the same stress. In contrast, the stress transmission between the matrix epoxy resin and the outer-layer side carbon nanotubes is large.
  • FIG. 4 is a graph showing the relationship between strain and G ′ band shift in the carbon nanotubes of the double-walled carbon nanotube-containing composite according to this example.
  • Raman spectroscopic analysis was performed using a laser wavelength of 633 nm.
  • G ′ 1 band shift and G ′ 2 band shift which are G ′ band shifts divided into two peaks, are plotted against the added distortion.
  • the slope corresponding to G ′ 2 indicating the inner layer side carbon nanotube was ⁇ 23.0 cm ⁇ 1 /%
  • the slope corresponding to G ′ 1 indicating the outer layer side carbon nanotube was ⁇ 29.0 cm ⁇ 1 /%.
  • FIG. 5 is a graph showing the relationship between strain and G ′ band shift in the carbon nanotubes of the double-walled carbon nanotube-containing composite according to this example.
  • G ′ 1 band shift and G ′ 2 band shift which are G ′ band shifts divided into two peaks, are plotted against the added distortion.
  • the slope corresponding to G ′ 2 indicating the inner layer side carbon nanotube was ⁇ 19.0 cm ⁇ 1 /%
  • the slope corresponding to G ′ 1 indicating the outer layer side carbon nanotube was ⁇ 26.0 cm ⁇ 1 /%.
  • FIG. 6 is a graph showing the relationship between strain and G ′ band shift in the carbon nanotubes of the double-walled carbon nanotube-containing composite according to this example. As shown in FIG. 6, G ′ 1 band shift and G ′ 2 band shift, which are G ′ band shifts divided into two peaks, are plotted against the added distortion.
  • the slope corresponding to G ′ 2 indicating the inner-layer side carbon nanotube was ⁇ 20.0 cm ⁇ 1 /%
  • the slope corresponding to G ′ 1 indicating the outer-layer side carbon nanotube was ⁇ 24.0 cm ⁇ 1 /%.
  • FIG. 7 is a graph showing the relationship between strain and G ′ band shift in the carbon nanotubes of the double-walled carbon nanotube-containing composite according to this example.
  • G ′ 1 band shift and G ′ 2 band shift which are G ′ band shifts divided into two peaks, were plotted against the added distortion.
  • the slope corresponding to G ′ 2 indicating the inner layer side carbon nanotube was ⁇ 18.0 cm ⁇ 1 /%
  • the slope corresponding to G ′ 1 indicating the outer layer side carbon nanotube was ⁇ 24.0 cm ⁇ 1 /%.
  • Double-walled carbon nanotubes were produced from commercially available arc discharge single-walled carbon nanotubes (Nanocarblab). First, single-walled carbon nanotubes were supplied after being purified through nitric acid treatment, heat treatment in air, and heat treatment at 1000 ° C. in argon. In order to minimize the fragmentation (shortening) effect of the single-walled carbon nanotube and to facilitate the subsequent dispersion step in the polymer, the drying step was performed by freeze drying.
  • the material resulting from this treatment was a powder containing about 70% single-walled carbon nanotubes and about 30% multi-walled carbon shell (for details see S.Cui, et.al., Advanced Materials, 21 ( 2009) See 3591 Supporting Information).
  • the single-walled carbon nanotubes (SWNTs) were mixed with a commercially available fullerene (manufactured by ALFA AESAR, 98% C 60 + 2% C 70 , purity> 98%) and then introduced into a quartz ampoule. In order to facilitate water dispersibility, nitrogen replacement and evacuation were repeated while maintaining the inside of the ampoule at 200 ° C., and finally, sealing was performed in a vacuum state.
  • Ampoule was placed in a heat treatment furnace maintained at about 500 ° C., for 24 hours so that the (SWNTs containing C 60) peapods material. The yield of peapod material was about 75%. The other components remained as single-walled carbon nanotubes.
  • the quartz ampoule was opened, placed in a heat treatment furnace and processed in vacuum up to 1300 ° C. By this treatment, fullerenes were combined to form single-walled carbon nanotubes, and single-walled carbon nanotubes, that is, double-walled carbon nanotubes were synthesized in the single-walled carbon nanotubes. Excess fullerene that was not introduced into the single-walled carbon nanotubes was removed by sublimation in the heat treatment temperature rising process.
  • FIG. 8 is a graph showing the relationship between strain and G ′ band shift in the carbon nanotube of the double-walled carbon nanotube-containing composite according to this example (Comparative Example 1).
  • G ′ 1 band shift and G ′ 2 band shift which are G ′ band shifts divided into two peaks, are plotted against the added distortion.
  • the inclination according to G ′ 1 indicating the outer layer side carbon nanotube was ⁇ 11 cm ⁇ 1 /%
  • the inclination according to G ′ 2 indicating the inner layer side carbon nanotube was ⁇ 0.7 cm ⁇ 1 /%.
  • the double-walled carbon nanotube-containing composite of the present invention can be suitably used to obtain a double-walled carbon nanotube-containing composite having high affinity between the double-walled carbon nanotube and the resin and high mechanical strength.

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Abstract

L'invention concerne un complexe contenant des nanotubes de carbone à double paroi, qui comprend : des nanotubes de carbone à double paroi chacun composés d'un nanotube de carbone de côté de couche interne et d'un nanotube de carbone de côté de couche externe ; et une résine. Dans un graphique illustrant la relation entre la contrainte et le déplacement de bande G' du complexe contenant des nanotubes de carbone à double paroi, qui est un graphique produit par réalisation d'une analyse de spectroscopie Raman du complexe contenant des nanotubes de carbone à double paroi tout en appliquant une charge au complexe contenant des nanotubes de carbone à double paroi, le rapport de la pente d'une droite issue du nanotube de carbone de côté de couche interne à la pente d'une droite issue du nanotube de carbone de côté de couche externe est 0,5 à 1,5, bornes incluses.
PCT/JP2013/080607 2012-11-28 2013-11-12 Complexe contenant des nanotubes de carbone à double paroi WO2014084042A1 (fr)

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CN111244457A (zh) * 2020-01-17 2020-06-05 新奥石墨烯技术有限公司 双层石墨烯管及其制备方法和应用
JP2022090729A (ja) * 2020-12-08 2022-06-20 国立研究開発法人物質・材料研究機構 空気電池正極用のカーボンナノチューブ膜及びその製造方法、並びにカーボンナノチューブ膜を正極に用いた空気電池
JP7486747B2 (ja) 2020-12-08 2024-05-20 国立研究開発法人物質・材料研究機構 空気電池正極用のカーボンナノチューブ膜及びその製造方法、並びにカーボンナノチューブ膜を正極に用いた空気電池

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