WO2007116706A1 - Matériau conducteur utilisant des nanotubes de carbone, son procédé de production, et condensateur électrique à double couche l'utilisant - Google Patents

Matériau conducteur utilisant des nanotubes de carbone, son procédé de production, et condensateur électrique à double couche l'utilisant Download PDF

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Publication number
WO2007116706A1
WO2007116706A1 PCT/JP2007/056298 JP2007056298W WO2007116706A1 WO 2007116706 A1 WO2007116706 A1 WO 2007116706A1 JP 2007056298 W JP2007056298 W JP 2007056298W WO 2007116706 A1 WO2007116706 A1 WO 2007116706A1
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WIPO (PCT)
Prior art keywords
resin composition
epoxy resin
composition layer
conductive material
carbon nanotubes
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PCT/JP2007/056298
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English (en)
Japanese (ja)
Inventor
Hideki Shiozaki
Takaharu Kitamura
Kenji Yoshikawa
Tetsuya Shiraishi
Takeshi Nishihata
Akira Shimomura
Original Assignee
Hitachi Zosen Corporation
Risho Kogyo Co., Ltd.
Research Institute Of Innovative Technology For The Earth
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Application filed by Hitachi Zosen Corporation, Risho Kogyo Co., Ltd., Research Institute Of Innovative Technology For The Earth filed Critical Hitachi Zosen Corporation
Priority to JP2008509757A priority Critical patent/JP5178509B2/ja
Publication of WO2007116706A1 publication Critical patent/WO2007116706A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a conductive material using carbon nanotubes and a method for producing the same.
  • the conductive material according to the present invention can be applied, for example, as a polarizable electrode which is a main component of an electric double layer capacitor capable of storing a large amount of electricity.
  • carbon nanotube means a plurality of brush-like carbon nanotubes.
  • a carbon nanotube is an ultrafine cylinder (a tube having a normal hole diameter of nano (one nano is 1 billionth) meter) in which a graph sheet sheet in which a six-membered ring consisting of carbon atoms is continuously formed is rounded. Material with a very high aspect ratio. Carbon nanotubes have various unique properties such as chemical stability, high strength, and a wide range of electrical properties, and are expected to be applied as new carbon materials for industrial use!
  • the present inventors have previously obtained a carbon nanotube obtained by transferring a carbon nanotube grown on a substrate to a conductive film or a conductive adhesive layer in a direction substantially perpendicular to the surface thereof.
  • a conductive material, a method for producing the same, and an electrode using the same have been proposed (see Patent Document 1 and Patent Document 2).
  • the shape of the energy regeneration system is required to be short, thin, light and thin like other electronic parts and circuits, and a large-capacity electric double layer capacitor with higher efficiency is desired.
  • the electrical capacity charged in the electric double layer capacitor is, of course, better as it is larger, but the electric capacitance of the electric double layer capacitor is larger as the operating voltage is higher, as shown by the following equation [I]. It is advantageous.
  • Thinning of the component parts enables miniaturization and thinning of the electric double layer capacitor, and lowering of resistance of the polarizable electrode may lead to an improvement in the conductivity of the electric double layer capacitor itself and hence to a large capacity. it can.
  • a method of removing a substrate and providing a supported and aligned carbon nanotube film on a second substrate has been proposed (see Patent Document 5).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-30926
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-127737
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-281388
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2005-7861
  • Patent Document 5 Japanese Patent Application Publication No. 2003-500325
  • the conductive carbon nanotube material described in Patent Document 1 is, as shown in FIG. 3, a conductive film (52) made of brush hairy carbon nanotube (51) grown with a catalyst particle on the substrate as a core.
  • the force conductive film (52) which is substantially vertically transferred onto the upper side, is formed by adding the polyethylene layer (54), and therefore, is inferior in heat resistance and strength. Therefore, when the ambient temperature reaches the melting temperature of polyethylene, the carbon nanotubes (51) transferred in a substantially perpendicular manner to the conductive film (52) can not maintain the vertical orientation. In extreme cases, there is a risk of falling off.
  • the polyethylene-based conductive film and porous film, and the polymer film of Patent Document 5 are inferior in strength, as shown in FIG. 4, the conductive film (52) and the reinforcing layer laminated thereon are shown in FIG. (55) Sometimes a multilayer film (56) is used. However, in this case, the total thickness of the film is inevitably increased.
  • the temperature of the conductive film before transfer is raised to a temperature above the softening temperature, and transferred and held in that state, and then the carbon nanotube is transferred to the conductive film.
  • the temperature of the conductive film before transfer is raised to a temperature above the softening temperature, and transferred and held in that state, and then the carbon nanotube is transferred to the conductive film.
  • carbon nanotubes could not be reliably transferred, and the carbon nanotubes grown on the substrate remained or the polyethylene layer of the conductive film was melted and peeled off. .
  • the conductive carbon nanotube material described in Patent Document 2 is, as shown in FIG. 5, a conductive adhesive in which carbon nanotubes (63) grown with catalyst particles as nuclei are laminated on a substrate (61). Transfer to the agent layer (62).
  • thermoplastic resin such as poly salt resin is preferable, but this conductive material is also the same as that of the patent document 1 in heat resistance and melting temperature or more.
  • the retention of carbon nanotubes at high temperatures Less reliable, power!
  • this conductive material When this conductive material is used as a polarizable electrode of an electric double layer capacitor, the transferred carbon nanotubes are simply bonded on the surface of the adhesive layer. Equally, carbon nanotubes may be desorbed by external factors such as temperature change, which is unreliable.
  • the conductive adhesive layer is inferior in strength, as the conductive material to which carbon nanotubes have been transferred, it is necessary to bond together a support such as a film, sheet or thin plate made of an inorganic or organic synthetic resin. There is no choice but to increase the thickness of the conductive material o
  • the operating voltage when the conductive material according to Patent Document 2 is used as a polarizable electrode for an electric double layer capacitor is that the reaction current is generated in a relatively low voltage region. It can not withstand use in the high voltage range that it has. Therefore, the polarizing electrode for a large capacity electric double layer capacitor is not satisfactory in terms of characteristics.
  • Patent Document 3 includes a step of adhering a single-walled carbon nanotube to a surface of a conductive binder layer patterned on a substrate, a step of curing the conductive binder layer as needed, and a conductive step.
  • a method of manufacturing a field emission type cold cathode is disclosed, which comprises the steps of peeling the substrate leaving only the oriented carbon nanotube portion adhered to the conductive binder layer.
  • a method for transferring oriented carbon nanotubes to a flexible substrate having a reversible adhesive surface, and a method for fixing oriented carbon nanotubes on an electrode are described.
  • Patent Document 4 proposes a functional sheet having a three-layer structure intended to prevent contamination and improve convenience during transfer of oriented carbon nanotubes, as shown in FIG.
  • the two functional sheets (72X73) disposed on both sides of the oriented carbon nanotube film (71) have a carbon nanotube film (71) fixed thereto.
  • Immobilization of the carbon nanotube film (71) is described to mean that the surface of the functional sheet (72 ⁇ 73) and the surface of the oriented carbon nanotube film (71) contact and adhere to each other. For this reason, when the conductive material obtained by Patent Document 4 is used as an electrode, there is a possibility that the orientation of carbon nanotubes may be disturbed or dropped as in the case of the above-mentioned patent documents. The reliability of carbon nanotube retention is inferior and it can not be used in some cases.
  • the object of the present invention is to solve the problems in the above-mentioned patent documents by maintaining thinness and high conductivity, and being excellent in strength and reliability of carbon nanotube retention, and excellent in production efficiency.
  • An object of the present invention is to provide a conductive material using a carbon nanotube and a method for producing the same, which is suitable for production and advantageous in cost. Further, according to the present invention, since the conductive material can be thinner and retain high conductivity, and the operation is secured in a high voltage region, the conductive material can be used as a polarizable electrode. Another object of the present invention is to provide a large capacity electric double layer capacitor used.
  • a carbon nanotube grown by using catalyst particles on a substrate as a core is transferred to an epoxy resin composition layer and pierced in a direction substantially perpendicular to the surface thereof. It is an object of the present invention to provide a conductive material using a carbon nanotube, which is characterized in that the resin composition layer is penetrated.
  • the carbon nanotubes in the present invention are transferred to the epoxy resin composition layer, pierced substantially perpendicularly to the surface, and kept penetrating the resin composition layer.
  • the carbon nanotube is reliably held in the resin composition layer by penetrating the epoxy resin composition layer, and the reliability of carbon nanotube retention is greatly improved as compared with the prior art.
  • Carbon nanotubes substantially vertically oriented on a substrate can be produced by a known method.
  • a solution containing a complex of a metal such as nickel, complex, or iron is applied by spraying or brushing on at least one surface of a silicon substrate, and then heated to form a film, or particles of the above metal or its compound
  • a film is formed by striking the substrate with a cluster gun.
  • the film is heated, preferably in an inert gas atmosphere, preferably at 700 to 800 ° C., preferably for 1 to 30 minutes, to form catalyst particles from the film.
  • the obtained particulate form is preferably subjected to a general chemical vapor deposition method (CVD method) using an acetylene gas to obtain a diameter of 10 to 38 nm, a length of 1 to 300 ⁇ m, and a distance between carbon nanotubes 10 to 10: LOOOnm carbon nanotubes are raised on a substrate in a multi-layer structure.
  • CVD method general chemical vapor deposition method
  • the carbon nanotubes preferably have a multi-layered structure, and their outer diameter is preferably 10 to 30 nm!
  • An electric double layer capacitor configured by using such a carbon nanotube as a polarizable electrode exhibits good charge and discharge characteristics.
  • the epoxy resin yarn or composite layer to which a carbon nanotube is to be transferred is further a) a multifunctional epoxy resin having three or more epoxy groups in its molecule, b) a phenoxy resin, c) a synthetic rubber It is preferable to include at least one of or derivatives thereof and d) polyamide resin or derivatives thereof.
  • the epoxy resin composition can obtain appropriate elasticity by containing at least one of the components a) to d), carbon nanotubes are immediately transferred to the epoxy resin composition layer, and It is held in a state of penetrating the epoxy resin composition layer.
  • the epoxy resin composition layer preferably further contains a conductive filler.
  • a conductive filler By the addition of the conductive filler, the electrical bondability between the carbon nanotubes is improved, whereby the conductivity can be improved and the internal resistance of the obtained conductive material can be reduced.
  • the present invention also provides a method of producing a conductive material using carbon nanotubes.
  • carbon nanotubes which are grown with the catalyst particles on the substrate as a core, are transferred to the epoxy resin composition layer, pierced in a direction substantially perpendicular to the surface thereof, It is a method for producing a conductive material using a carbon nanotube, characterized in that before the transfer, the epoxy resin composition layer is heated to 50 ° C. or more and 200 ° C. or less before transfer.
  • the epoxy resin composition layer is preferably in the B-stage state (semi-cured state) at the stage before the heating.
  • the epoxy resin composition layer by containing at least one of the components a) to d), has a proper elasticity for the carbon nanotube to be transferred, and the carbon nanotube is The resin composition layer can be easily penetrated.
  • the present invention provides an electric double layer capacitor characterized by using the above-mentioned conductive material as a polarizable electrode. By using the above-mentioned conductive material for the polarizable electrode, a large capacity electric double layer capacitor can be realized by securing low resistance and high operating voltage.
  • a large capacity electric double layer capacitor in which a further higher operating voltage is secured by using the above-mentioned conductive material as a polarizable electrode and using an ionic liquid as an electrolytic solution Can be realized.
  • the operating voltage of the electric double layer capacitor is determined by a potential window derived from the reaction current measured by cyclic voltammetry.
  • the potential window is a range of voltage range without generation of reaction current, and the range is large! /, The higher the operating voltage is secured, the large capacity can be realized.
  • the generation of the reaction current means that the electricity once charged in the electric double layer capacitor is lost to the outside, that is, it is difficult to operate the electric double layer capacitor in the voltage region where the reaction current is generated. Do.
  • the conductive material according to the present invention has a structure in which the carbon nanotube penetrates the epoxy resin composition layer, so that strength and carbon nanotube retention can be achieved.
  • the high reliability, thin, high conductivity operating voltage is ensured, the operation is ensured in the high voltage region, the production efficiency is excellent, it is suitable for mass production, and the cost is also favorable.
  • the carbon nanotube penetrates through the epoxy resin yarn or compound layer, when the epoxy resin composition layer is formed on the substrate, it is in direct contact with the substrate surface. Ru. Therefore, when using a conductive material obtained by raising a carbon nanotube in a laminate composed of an epoxy resin composition layer and its base material as a collecting electrode, the high conductivity of the carbon nanotube is the electrode itself. It is possible to express a synergetic effect on the conductivity of the electrode and to form a low resistance electrode.
  • the epoxy resin composition layer further contains at least one kind of specific components a) to d).
  • the epoxy resin composition layer has a suitable elasticity, so carbon nanotubes Immediately after being transferred to the resin composition layer, the epoxy resin composition layer is kept penetrating.
  • the epoxy resin composition layer further includes a conductive filler, whereby the effects according to the inventions of claims 1 and 2 can be improved.
  • a conductive filler By improving the electrical connectivity between carbon nanotubes, it is possible to improve the conductivity and reduce the internal resistance as a conductive material.
  • the resin composition layer is suitably flexible for transfer.
  • the transferred carbon nanotubes can be kept penetrating through the resin composition layer.
  • Catalyst particles are formed on a substrate, and carbon nanotubes are grown from a source gas in a high temperature atmosphere using the catalyst particles as nuclei.
  • the substrate may be a silicon substrate which preferably supports catalyst particles, as long as it supports catalyst particles.
  • the catalyst particles may be metal particles such as nickel, cobalt, iron and the like.
  • a solution of a compound such as these metals or complexes thereof is applied to a substrate by spraying or brushing to form a film.
  • the thickness of the film is preferably 1 to: LOO nm.
  • the coating is preferably heated in an inert gas atmosphere, preferably at 700-800 ° C., preferably for 1-30 minutes, to form catalyst particles.
  • aliphatic hydrocarbons such as acetylene, methane and ethylene can be used, and acetylene gas is particularly preferable.
  • acetylene carbon nanotubes with a multilayer structure of 12 to 60 nm in thickness are formed in a brush shape on the substrate with the catalyst particles as the core by the CVD method.
  • the formation temperature of carbon nanotubes is preferably 650 to 800. It is C.
  • the epoxy resin used in the present invention may have two or more glycidyl groups in the molecule.
  • Examples of the epoxy resin S include diglycidinoleate tenore type, diglycydolic ester type, glididylamine type, linear aliphatic epoxide type, alicyclic epoxide type and the like. These may be used alone or in combination of two or more.
  • the epoxy resin may be one modified by a known method.
  • the epoxy resin may be liquid, semi-solid, solid, or loose at room temperature, but the epoxy resin composition may be used alone or as a mixture of organic solvents to facilitate handling. It is preferable to contain a reactive diluent.
  • a reactive diluent various ones such as monofunctional, bifunctional, polyfunctional and the like can be suitably used.
  • the organic solvent methanol, acetone, methyl ethyl ketone, toluene, methyl sequestrub, dimethylformamide and the like can be appropriately used.
  • the epoxy resin composition contains a curing agent.
  • curing agents include polyamines such as aliphatic, alicyclic and aromatic; polyamidoamines; modified polyamines; hexahydrophthalic anhydride; Acids, acid anhydrides such as trimellitic anhydride; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole and derivatives thereof; dicyandiamide or derivatives thereof; organic acid dihydrazides such as sebacic acid dihydrazide; 3- (3 Urea derivatives such as 4-dichlorophenyl) -1,1 dimethylurea; mention may be made of boron fluoride-monoethylamine complex, phenol resin, amino acid, polyisosocyanate complex, diaminodiphenyl sulfone and the like.
  • any curing agent can be used as long as it cures by crosslinking reaction with the epoxy resin to be used, and is not particularly limited.
  • the curing agent may be used alone or in combination of two or more. It is also possible to blend other thermosetting resin and thermoplastic resin with the epoxy resin composition. Moreover, in order to impart the necessary characteristics, it is preferable to add organic and inorganic additives and fillers.
  • the epoxy resin yarn composite layer further comprises: a) a polyfunctional epoxy resin having three or more epoxy groups in its molecule, b) a phenoxy resin, c) a synthetic rubber or a derivative thereof, and d It is preferable to include at least one kind of polyamide resin or its derivative.
  • polyfunctional epoxy resins having three or more epoxy groups in the molecule phenol nopolac type epoxy resins, creosoyl novolac type epoxy resins, triglycidyl-P-amitraglycidyldiaminodiphenylmethane And polyfunctional epoxy resins such as tetraglycidyl-1, 3-bisaminomethylcyclohexane.
  • polyfunctional epoxy resins it is possible to use phenol novolac type epoxy resin or cresol novolac type epoxy resin, heat resistance of the epoxy resin composition layer and transferability of carbon nanotube, etc. Force is also preferred.
  • the polyfunctional epoxy resin When the polyfunctional epoxy resin is added to the epoxy resin composition, it is preferable to add 5 to 50 parts by weight to 100 parts by weight of the resin composition. If the addition amount is less than 5 parts by weight or more than 50 parts by weight, transfer of carbon nanotubes in the form of penetrating the same resin composition layer becomes difficult.
  • Fukinoxy resin is generally a linear epoxy resin having a molecular weight of 30000 or more, and has thermoplastic resin-like properties.
  • any of those having a basic structure of bisphenol A type and bisphenol F type can be used.
  • those which are flame-retardant-modified with bromine, phosphorus or the like or modified with other functional groups can also be used.
  • "Fuenotot" from Toto Kasei Co., Ltd. can be mentioned.
  • By adding 5 to 45 parts by weight of phenoxy resin to 100 parts by weight of the same resin composition appropriate rigidity and flexibility are imparted, so carbon in the form of penetrating the epoxy resin composition layer. It is possible to transfer nanotubes. When the addition amount is less than 5 parts by weight and more than 50 parts by weight, transfer of carbon nanotubes in the form of penetrating the same resin composition layer can not be performed.
  • Synthetic rubbers are styrene butadiene rubber, polyisoprene rubber, acrylonitrile butadiene It may be rubber, epichlorohydrin rubber or the like.
  • the derivative of the synthetic rubber may be a derivative derived from hydrogenation of synthetic rubber, modification of carboxyl group and the like.
  • Medium-to-high-tolyl type and high-tolyl type acrylonitrile butadiene rubber and carboxylated acrylonitrile butadiene rubber are preferable because the epoxy resin yarn composite layer can obtain appropriate flexibility and rigidity in transferring carbon nanotubes. .
  • "Nipo 1" manufactured by Nippon Zeon Co., Ltd. and the like can be mentioned.
  • the epoxy resin composition layer is imparted with flexibility and rigidity, so that carbon nanotube transfer in a form penetrating the resin composition layer. Is possible.
  • the addition amount of the synthetic rubber or its derivative is 5 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin composition.
  • the addition amount is 5 parts by weight or less, it becomes difficult to transfer the carbon nanotube to the same resin composition, and when it becomes 50 parts by weight or more, the transferred carbon nano tube is retained in the same resin composition layer. It becomes difficult.
  • a vulcanizing agent suitable for improving the strength, adhesion and the like of the rubber itself such as phenol resin and its derivative may be used in combination. It is preferable to add 5 to 20 parts by weight of phenol resin and its derivative to 100 parts by weight of synthetic rubber or its derivative.
  • the polyamide resin may have a basic structure such as 6-nylon or 6,6-nylon, or the like, or may be a copolymer thereof.
  • CM4000 and CM8000 which are made of East Rene clay copolymer nylon "AMIRAN”.
  • elastomers or synthetic resins having a polyamide group in the molecular structure of “Kayaflex” manufactured by Nippon Kayaku Co., Ltd. can also be used.
  • Polyamide resin or its derivative is powdery fine particles, liquid at room temperature
  • the addition amount of the polyamide resin or its derivative is 100 parts by weight of the epoxy resin composition. Preferably, it is 5 to 60 parts by weight. When the addition amount is 5 parts by weight or less, the flexibility of the resin composition layer is insufficient, and when it is more than 60 parts by weight, the transferred carbon nano tube is retained in the same resin composition layer. It will be difficult to do.
  • a conductive filler in the epoxy resin composition.
  • the conductive filler include carbon nanotube pieces, carbon nanohorn pieces, carbon nanocoil pieces, conductive carbon fibers, graphite, carbon-based conductive pieces such as carbon black, and carbon-based conductive powders.
  • an electroconductive material in an electric double layer capacitor it is possible to achieve a reduction in resistance of the electrode itself without affecting the electrolyte solution and the like.
  • an epoxy resin yarn is coated with a coater, a doctor blade or the like on the surface of an inorganic material such as metal foil or a base material made of heat resistant film, and the epoxy resin yarn is formed.
  • an inorganic material such as metal foil or a base material made of heat resistant film
  • the epoxy resin yarn is formed.
  • metal foils copper foils, stainless steel foils, aluminum foils are preferred, such as availability and economy.
  • the heat resistant film is preferably a polyethylene terephthalate film.
  • the thickness of the epoxy resin composition layer is preferably 0.1 to: LOOO ⁇ m, and more preferably 10 to 200 ⁇ m. If the thickness of the resin composition layer is less than 0.1 ⁇ m, carbon nanotubes can not be reliably held, and if it is more than 1000 m, it becomes extremely difficult to form the resin composition layer. Poor productivity.
  • the step of transferring the carbon nanotubes to the epoxy resin composition layer is carried out at the stage where the solvent is evaporated and the resin composition is dried after the epoxy resin composition is applied to the surface of the substrate. It will be.
  • an epoxy resin composition is coated on a base material having a suitable releasability such as a metal foil or a heat resistant film, and after drying, a laminate comprising the resin composition and the base material is dried.
  • a base material having a suitable releasability such as a metal foil or a heat resistant film
  • a laminate comprising the resin composition and the base material is dried.
  • the carbon nanotube grown on the substrate is planted in the same resin composition layer by pressing the tip from the tip onto the epoxy resin composition layer. After that, carbon nanotubes The carbon nanotube force is also peeled off leaving only the substrate left in the resin composition layer.
  • the transfer of the carbon nanotube to the substrate strength epoxy resin composition layer is completed to obtain the conductive material using the brush-like carbon nanotube.
  • the brush-like carbon nanotube penetrates the epoxy resin composition layer and is surely transferred to the epoxy resin composition layer.
  • the epoxy resin composition layer at the time of transfer is preferably 50 ° C. or more and 200 ° C. or less, and more preferably 60 to 160 ° C. This heating is preferably done in the far infrared or electromagnetic induction mode.
  • the heating time may be, for example, 1 to 20 minutes, preferably 3 to LO minutes.
  • the same resin fiber layer or a composite layer is in a B-stage state at the stage before the above heating.
  • carbon nanotubes can be more reliably penetrated by the resin composition layer.
  • the epoxy resin composition layer is cured by heating or the like as required. Thereby, the carbon nanotube can be reliably fixed in the state of penetrating the same resin composition layer.
  • the carbon nanotube is pierced substantially perpendicularly to the surface of the epoxy resin composition layer, and penetrates to reach the opposite surface.
  • the carbon nanotubes of one electrode and the carbon nanotubes of the other electrode are in a noncontact manner facing each other. Together, impregnating carbon nanotubes with electrolyte solution And place them all in a container.
  • a base material (1) which also functions as a polyethylene terephthalate film, bisphenol A type solid epoxy resin ("AER-6051” manufactured by Asahi Kasei Corp.), dicyandiamide as a curing agent, polyfunctional epoxy resin
  • AER-6051 bisphenol A type solid epoxy resin
  • dicyandiamide as a curing agent
  • polyfunctional epoxy resin An epoxy resin composition that also contains phenol novolak-modified epoxy resin (Dei Nippon Ink Chemical Co., Ltd., “Epiclone N-770”, and methyl ethyl ketone which is an organic solvent for dilution) to a thickness of 10 ⁇ m with a doctor blade
  • the organic solvent was evaporated by coating and heating at 150 ° C. for 3 minutes to form a B-stage epoxy resin composition layer (2).
  • the substrate with carbon nanotubes (5) and the epoxy resin composition layer (2) are heated to 130 ° C with far infrared rays, and the substrate with carbon nanotubes is formed on the surface of the resin composition layer (2) (5 ) Was pressed from the tip of the carbon nanotube, and the tip portion was inserted into the epoxy resin composition layer (2) to penetrate the composition layer (2) as shown in FIG. Id.
  • the tip of the carbon nanotube is in contact with the substrate (1).
  • the silicon substrate (3) was mechanically peeled from the carbon nanotubes (4) so as to leave the carbon nanotubes (4) in the epoxy resin composition layer (2).
  • the transfer of the carbon nanotubes to the substrate strength epoxy resin composition layer was completed.
  • the carbon nanotube (4) does not remain in the silicon substrate (3), and the silicon substrate (3) is not
  • the carbon nanotube transfer to the propoxy resin composition layer (2) could be carried out without any problem.
  • the obtained carbon nanotube-embedded epoxy resin composition layer coated substrate (1) was heated in an oven at a temperature of 150 ° C. to cure the epoxy resin composition layer (2).
  • the base material (1) is mechanically peeled off from the epoxy resin cured material layer (6), and as shown in Fig. If, the carbon nanotube (4) is planted in the epoxy resin cured material layer (6) A conductive material (7) was obtained.
  • the carbon nanotube (4) pierces the surface of the cured epoxy resin layer (6) substantially perpendicularly, and penetrates the cured resin layer (6) to reach the opposite surface. It was confirmed that he would be angry.
  • Example 2 In the second to fifth steps, the same operations as the corresponding steps in Example 1 were performed.
  • the carbon nanotube (4) was pierced substantially perpendicularly to the epoxy resin fiber layer (2), and it was confirmed that the carbon nanotube (4) penetrated the resin composition layer (2). Similar to Example 1, the carbon nanotube was transferred to the silicon substrate, and the transfer of the carbon nanotube to the epoxy resin composition layer (2) could be performed without any problem.
  • the aluminum foil (8) was mechanically peeled off from the epoxy resin cured product layer to obtain a conductive material in which carbon nanotubes were embedded in the epoxy resin cured product layer. It was confirmed that the carbon nanotube (4) was pierced substantially perpendicularly to the surface of the cured epoxy resin layer, and penetrated to reach the opposite surface.
  • Example 1 The conductive material obtained in Example 1 and Example 2 was used as a polarizable electrode, and an electrolytic solution was prepared by using an ionic liquid such as tetrafluoroboric acid N, N-jetyl-N-methyl-N- (2- An electrical double layer capacitor was prepared using methoxyethyl ammonium salt (having a potential window of up to 5.5 V).
  • an ionic liquid such as tetrafluoroboric acid N, N-jetyl-N-methyl-N- (2-
  • An electrical double layer capacitor was prepared using methoxyethyl ammonium salt (having a potential window of up to 5.5 V).
  • a voltage was applied between the positive electrode and the negative electrode of the electric double layer capacitor, and the reaction current was measured by cyclic voltammetry. As a result, no reaction current is observed in the potential window region up to 3.5 V, and it is high as an electric double layer capacitor! It was found that operation in the voltage range was possible.
  • a conductive adhesive containing a thermoplastic resin (polychloride resin) as a binder is coated to a thickness of 10 ⁇ m on a polyethylene terephthalate film base material so as to have a thickness of 10 ⁇ m, and the organic solvent is evaporated to coat it.
  • the working layer was dried to form a conductive adhesive layer.
  • Example 2 The same operation as in the second step of Example 1 was performed to produce a carbon nanotube-attached substrate.
  • the above-mentioned carbon nanotube-attached substrate was pressed against the above-mentioned conductive adhesive layer at normal temperature by the tip force of the carbon nanotube to insert the tip into the conductive adhesive. After that, it took 10 minutes for the conductive adhesive layer to fully cure.
  • the silicon substrate was then mechanically peeled away from the carbon nanotubes, leaving carbon nanotubes in the conductive adhesive layer.
  • transfer of the carbon nanotubes to the substrate resin layer was completed.
  • part of the carbon nanotubes remained on the substrate, and the transfer did not proceed well.
  • the conductive material according to the present invention can be applied, for example, as a polarizable electrode which is a main component of an electric double layer capacitor capable of storing a large amount of electricity.
  • FIG. La is a cross sectional view schematically showing a first step of the first embodiment.
  • Figure lb is a cross sectional view schematically showing a second step of the first embodiment.
  • FIG. 1c is a cross sectional view schematically showing a third step of the first embodiment.
  • Figure Id is a cross sectional view schematically showing a third step of the first embodiment.
  • Figure le is a cross-sectional view schematically showing a fourth step of the first embodiment.
  • Figure If is a cross sectional view schematically showing a sixth step of the first embodiment.
  • FIG. 2 is a cross sectional view schematically showing a first step of the second embodiment.
  • FIG. 3 is a cross-sectional view of the carbon nanotube conductive material described in Patent Document 1.
  • FIG. 4 is a cross-sectional view of a carbon nanotube conductive material described in Patent Document 1.
  • FIG. 5 is a cross-sectional view of the carbon nanotube conductive material described in Patent Document 2.
  • FIG. 6 is a cross-sectional view of a carbon nanotube conductive material described in Patent Document 4. Explanation of sign

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Abstract

La présente invention concerne un matériau conducteur utilisant des nanotubes de carbone qui est de type plus mince, conserve une conductivité élevée, présente une solidité et une fiabilité de rétention des nanotubes de carbone excellentes, présente une efficacité de production et une adaptation à la production en série excellentes, et dont le coût est avantageux ; et un procédé de production du matériau conducteur. Le matériau conducteur utilisant des nanotubes de carbone est obtenu en transférant des nanotubes de carbone (4) ayant poussé sur un substrat (3) en noyaux à partir de particules de catalyseur vers une couche de composition de résine époxy de sorte que les nanotubes de carbone percent la couche de composition de résine dans une direction sensiblement perpendiculaire à ses surfaces et s'étendent vers sa surface opposée.
PCT/JP2007/056298 2006-03-27 2007-03-27 Matériau conducteur utilisant des nanotubes de carbone, son procédé de production, et condensateur électrique à double couche l'utilisant WO2007116706A1 (fr)

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JP2018131344A (ja) * 2017-02-13 2018-08-23 日立造船株式会社 カーボンナノチューブ複合材の製造方法、カーボンナノチューブ複合材および異方性カーボンナノチューブ複合材
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