WO2006101084A1 - Fibre de carbone, procedes pour la produire (en continu) et utilisation dans des structures catalytiques, electrodes pour piles a combustible a polymere solide et piles a combustible a polymere solide - Google Patents

Fibre de carbone, procedes pour la produire (en continu) et utilisation dans des structures catalytiques, electrodes pour piles a combustible a polymere solide et piles a combustible a polymere solide Download PDF

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Publication number
WO2006101084A1
WO2006101084A1 PCT/JP2006/305571 JP2006305571W WO2006101084A1 WO 2006101084 A1 WO2006101084 A1 WO 2006101084A1 JP 2006305571 W JP2006305571 W JP 2006305571W WO 2006101084 A1 WO2006101084 A1 WO 2006101084A1
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Prior art keywords
carbon fiber
polymer
continuous
fibrillated
catalyst
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PCT/JP2006/305571
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English (en)
Japanese (ja)
Inventor
Yoshinori Iwabuchi
Shinichiro Sugi
Shinichi Toyosawa
Masato Yoshikawa
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Bridgestone Corporation
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Publication date
Priority claimed from JP2005083968A external-priority patent/JP2006265761A/ja
Priority claimed from JP2005094003A external-priority patent/JP2006273645A/ja
Application filed by Bridgestone Corporation filed Critical Bridgestone Corporation
Publication of WO2006101084A1 publication Critical patent/WO2006101084A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • B01J35/58—
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/32—Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Carbon fiber and its (continuous) production method Carbon fiber and its (continuous) production method, catalyst structure using the same, electrode for polymer electrolyte fuel cell, and polymer electrolyte fuel cell
  • the present invention relates to a carbon fiber and a (continuous) production method thereof, a catalyst structure using the carbon fiber, an electrode for a polymer electrolyte fuel cell, and a polymer electrolyte fuel cell. This relates to a (continuous) production method of carbon fiber.
  • carbon fibers include pitch-based carbon fibers by liquid phase carbonization, polyacrylonitrile-based and rayon-based carbon fibers by solid-phase carbonization, vapor-grown carbon fibers by vapor-phase carbonization, and laser methods, Carbon nanotubes by the arc discharge method are known.
  • pitch-based carbon fiber, polyacrylonitrile-based carbon fiber, and rayon-based carbon fiber a spinning process is necessary to obtain a fibrous precursor, and the manufacturing process becomes complicated. It is difficult to obtain finer fibers.
  • vapor-grown carbon fiber there is a problem that a mass production method is not necessarily established because the production equipment is expensive and the yield is not high.
  • the production of carbon nanotubes has the problem that the production equipment is expensive and efficient mass production technology is under investigation, and it is difficult to obtain a fiber diameter exceeding 0.1 / im.
  • Japanese Patent Application Laid-Open No. 5-178603 discloses a carbon that does not require an infusibilization step, can control electric characteristics such as conductivity, has a high residual carbon ratio, and has excellent conductivity.
  • a polyaniline powder is used as a raw material, so that carbon fibers cannot be obtained without going through a spinning process.
  • the pamphlet of International Publication No. 2004/063438 does not require a spinning step and an infusibilization step, has a high residual carbon ratio and is excellent in electrical conductivity, and particularly has a fiber diameter of 30 to several hundred nm.
  • a carbon fiber production method is disclosed in which the carbon fiber can be efficiently obtained, and the electrical properties such as conductivity of the obtained carbon fiber can be controlled. According to the method For example, a compound having an aromatic ring can be electropolymerized to obtain a fibril-like polymer, and the fibril-like polymer can be baked in a non-oxidizing atmosphere to obtain a three-dimensional continuous carbon fiber.
  • the fibrillated polymer is formed by external heating such as a heater in an inert gas (Ar, N, etc.) atmosphere in a firing furnace.
  • an external heating type furnace represented by an electric heater is generally used.
  • an electric heater When heating a fibrillar polymer in a furnace of the type, there is a problem that the heating time of the fibrillar polymer, which is the object to be heated, has to rely on heat conduction, and the firing time becomes difficult because rapid heating is difficult.
  • a temperature difference occurs between the surface and the inside of the fibril polymer that is the object to be heated, making it difficult to heat uniformly. There is also.
  • the input energy is used in addition to the temperature increase of the fibril polymer that is the object to be heated.
  • the fibrillated polymer is continuously fired in the furnace of the above external heating method, for example, there are more problems, for example, the limit of the temperature level due to heat escape, and the arrangement of heat insulating material to prevent heat escape.
  • an object of the present invention is to solve the above-mentioned problems of the conventional technique, and to improve productivity, which can produce carbon fibers having a three-dimensional continuous structure by firing fibrillar polymers in a short time.
  • An object of the present invention is to provide an excellent method for producing carbon fiber and a continuous method for producing carbon fiber.
  • Another object of the present invention is to provide a catalyst structure using the carbon fiber, an electrode for a polymer electrolyte fuel cell using the catalyst structure, and a polymer electrolyte fuel cell provided with the electrode. It is to provide.
  • the inventors of the present invention have made it possible that the fibrillated polymer absorbs the microwave and self-heats by firing the fibrillated polymer by microwave irradiation.
  • the fibrillated polymer can be heated and carbonized with high efficiency, and the fibrillated polymer is continuously carried into and out of the heating chamber, and the microwave irradiation is performed in the chamber to burn the fibrillated polymer. Then, it was found that carbon fiber can be continuously produced by carbonization, and the present invention has been completed.
  • carbon having a three-dimensional continuous structure is obtained by irradiating a fibrillar polymer having a three-dimensional continuous structure with microwaves to heat and carbonize the polymer. It is characterized by producing fibers.
  • the carbon fiber continuous production method of the present invention is a carbon fiber continuous production method using a continuous firing device including a heating chamber, a microwave generation device, and a transport mechanism.
  • a fibrillated polymer having a sheet-like or plate-like three-dimensional continuous structure is carried into the heating chamber of the continuous baking apparatus, and the fibrillated polymer is irradiated with microwaves generated by the microwave generating apparatus.
  • the polymer is calcined and carbonized to produce carbon fibers having a three-dimensional continuous structure.
  • the fibrillated polymer When continuous calcination is performed by irradiating the fibrillated polymer with microwaves using the continuous baking apparatus, the fibrillated polymer absorbs the microwave and self-heats, so that the fibrillated polymer is heated with high efficiency and carbonized. Can be made.
  • the fibrillated polymer is irradiated with microwaves in a vacuum or in an inert gas atmosphere. In this case, disappearance of the fibrillated polymer due to microwave irradiation can be suppressed.
  • the microwave The frequency of is 28GHz (millimeter wave).
  • the fibrillar polymer sufficiently absorbs microwaves (millimeter wave with a frequency of 28 GHz), enables uniform heating without thermal runaway, and also prevents arcing. .
  • the fibrillar polymer is a polymer obtained by electrolytic polymerization of a compound having an aromatic ring. That is, the carbon fiber production method of the present invention includes a step of electropolymerizing a compound having an aromatic ring to produce a fibrillated polymer, and irradiating the fibrillated polymer with microwaves to heat the polymer. And carbonizing to produce a carbon fiber having a three-dimensional continuous structure.
  • the fibrillar polymer strength is more preferably composed of polyaniline, polypyrrole, polythiophene or derivatives thereof.
  • the fibrillated polymer is supported on a conductive substrate. More preferably, the fibrillated polymer is a polymer obtained by electropolymerizing a compound having an aromatic ring on a conductive substrate. That is, the method for producing carbon fiber of the present invention comprises a compound having an aromatic ring. It is preferable to include a step of performing the electrolytic polymerization on a conductive substrate and generating a fibrillated polymer on the conductive substrate.
  • carbon paper is preferred as the conductive substrate.
  • the shape of the conductive substrate is preferably a sheet shape or a plate shape.
  • the fibrillar polymer is a sheet
  • the transport mechanism is a roll-to-roll system transport mechanism.
  • the fibrillar polymer is plate-shaped, and the transport mechanism is composed of a plurality of drive rolls.
  • the heating chamber 1 has a heat insulating material or a vacuum heat insulating layer above and below the passage position of the fibrillated polymer.
  • a heater is provided in the heat insulating material.
  • the temperature can be raised quickly.
  • a microwave absorber layer is further disposed on the surface of the heat insulating material facing the fibrillar polymer. It is also preferable. In this case, it is possible to easily control the heating temperature of the fibril polymer by limiting the amount of microwave absorption of the fibril polymer.
  • the continuous firing apparatus further includes a cooling chamber for cooling the carbon fiber generated by microwave irradiation at the subsequent stage of the heating chamber. It is preferable. Since the carbon fiber that has passed through the heating chamber is at a high temperature, the carbon fiber may be oxidized when exposed to the air atmosphere.
  • the continuous firing apparatus includes a cooling chamber, and the carbon fiber is contained in the cooling chamber. By sufficiently cooling, it is possible to prevent the carbon fibers from being oxidized in an air atmosphere.
  • the continuous firing apparatus further generates a fibrillar polymer by electropolymerizing a compound having an aromatic ring in the previous stage of the heating chamber. It is preferable to provide an electrolytic polymerization tank. Here, the produced polymer 1 is carried into the heating chamber 1 as the fibrillated polymer. Further, when the continuous baking apparatus includes an electrolytic polymerization tank, it is preferable to further include a cleaning apparatus and a drying apparatus for the polymer between the electrolytic polymerization tank and the heating chamber.
  • the carbon fiber of the present invention is characterized by being produced by the above-described method, and has a three-dimensional continuous structure
  • the catalyst structure of the present invention comprises a catalyst supported on the carbon fiber. It is characterized by this.
  • the catalyst structure of the present invention has a catalyst structure comprising a continuous firing device including a heating chamber, a microwave generator, and a transport mechanism, and a catalyst support device disposed at a subsequent stage of the heating chamber of the continuous firing device. It can also be produced continuously by supporting the catalyst on carbon fiber using a continuous body production apparatus.
  • the continuous production apparatus for the catalyst structure further includes a carbon fiber cleaning apparatus and a drying apparatus in which a catalyst is supported downstream of the catalyst supporting apparatus.
  • an electrode for a polymer electrolyte fuel cell according to the present invention includes a gas diffusion layer and a catalyst layer disposed on the gas diffusion layer, and the catalyst structure is used for the catalyst layer. It is characterized by this. Furthermore, the polymer electrolyte fuel cell of the present invention is characterized by comprising the above electrode.
  • a fibrillated polymer is irradiated with microwaves to be heated and carbonized.
  • a carbon fiber having a three-dimensional continuous structure can be produced in a short time.
  • a fibrillated polymer having a sheet-like or plate-like three-dimensional continuous structure is continuously formed by using a continuous baking apparatus having a heating chamber, a microwave generator, and a transport mechanism. Carrying into the heating chamber of the firing device, irradiating the fibrillar polymer with the microwave generated by the microwave generator, firing and carbonizing the polymer, continuous carbon fibers having a three-dimensional continuous structure Can be manufactured automatically.
  • carbon fibers produced by these methods, catalyst structures using the carbon fibers, electrodes for solid polymer fuel cells using the catalyst structures, and solid polymer fuel cells including the electrodes Can be provided.
  • FIG. 1 is a schematic view of an example of a continuous firing apparatus suitable for carrying out the present invention.
  • FIG. 2 is a schematic view showing an example of a continuous baking apparatus suitable for continuous baking of a sheet-like fibril polymer.
  • FIG. 3 is a schematic view showing an example of a continuous firing apparatus suitable for continuous firing of a plate-like fibril polymer.
  • FIG. 4 is a schematic view showing another preferred example of a continuous baking apparatus suitable for carrying out the present invention.
  • FIG. 5 is a schematic view showing an example of a continuous production apparatus for a catalyst structure suitable for carrying out the present invention.
  • FIG. 6 is a cross-sectional view of an example of a polymer electrolyte fuel cell of the present invention.
  • the carbon fiber production method of the present invention is characterized in that a fibrillated polymer having a three-dimensional continuous structure is irradiated with microwaves, and the polymer is heated and carbonized to produce a carbon fiber having a three-dimensional continuous structure.
  • the fibrillated polymer absorbs the microwave and self-heats by irradiating the fibrillated polymer with microwaves, whereby the fibrillated polymer is heated and carbonized with high efficiency. Can do.
  • the carbon fiber production method of the present invention does not rely on heat conduction from a heat source, the temperature can be increased in a short time.
  • the microwave heating used in the present invention has the advantages of excellent temperature controllability and high responsiveness. Furthermore, since microwave heating is performed by self-heating of the fibrillar polymer, uniform heating is possible, and this prevents the sample from warping and stress generation due to firing, which was a problem in the conventional method. Monkey.
  • the fibrillar polymer used as a raw material has a three-dimensional continuous structure.
  • the fibril-like polymer can be obtained by polymerizing a compound having an aromatic ring, preferably electrolytic polymerization, more preferably electrolytic oxidation polymerization.
  • examples of the compound having an aromatic ring include a compound having a benzene ring and a compound having an aromatic heterocyclic ring.
  • aniline and aniline derivatives are preferred.
  • pyrrole, thiophene, and derivatives thereof are preferable as the compound having an aromatic heterocyclic ring.
  • These compounds having an aromatic ring may be used singly or as a mixture of two or more.
  • the fibrillated polymer is preferably composed of polyaniline, polypyrrole, polythiophene or their derivatives.
  • the fibrillar polymer has a diameter of 30 nm to several hundreds of nm, preferably 40 nm to 500 nm, and a length of 0.5 ⁇ m to 100 mm, preferably 1 ⁇ m to 10 mm.
  • the fibrillated polymer is produced by electrolytic oxidation polymerization
  • the negative ion of the acid is taken into the fibril polymer synthesized as a dopant to obtain a fibril polymer excellent in conductivity, and the carbon fiber finally obtained by using this fibril polymer is obtained.
  • the electrical conductivity of can be improved.
  • the acid mixed during the polymerization is not particularly limited, and examples thereof include HBF, HSO, HC1, and HCIO.
  • the acid concentration is preferably in the range of 0.1 to 3 mol / L, more preferably in the range of 0.5 to 2.5 mol / L.
  • the working electrode and the counter electrode are immersed in a solution containing a compound having an aromatic ring, and the compound having the aromatic ring is sandwiched between both electrodes. A voltage higher than the oxidation potential is applied, or the compound having the aromatic ring is polymerized. It is only necessary to pass an electric current under such a condition that a sufficient voltage can be secured, and a fibrillated polymer is formed on the working electrode.
  • the working electrode and the counter electrode it is possible to use a plate or a porous material made of a highly conductive material such as stainless steel, platinum or carbon.
  • the concentration of the electrolytic solution of the compound with a 0.1-1000111 eight I 111 2 ranges preferably tool 0.2 ⁇ 100mA N of m 2 range is more preferably tool aromatic ring, 0.05
  • the range of ⁇ 3 mol / L is preferred.
  • the range of 0.25 to 1.5 mol / L is even more preferred.
  • a soluble salt or the like may be appropriately added to the electrolytic solution in order to adjust the pH.
  • the fibrillated polymer obtained on the working electrode as described above can be suitably used in the production method of the present invention by washing with a solvent such as water or an organic solvent and drying.
  • a fibrillar polymer can be obtained.
  • the drying method is not particularly limited, and examples thereof include a method using a fluid bed dryer, a flash dryer, a spray dryer, etc. in addition to air drying and vacuum drying.
  • the fibrillated polymer is irradiated with microwaves.
  • the frequency of the irradiated microwave is usually in the range of 300 MHz to 300 GHz, and 28 GHz (millimeter wave) is particularly preferable.
  • Microwaves with a frequency of 2.45 GHz typified by microwave ovens are widely used.
  • microwaves with a frequency of 2.45 GHz there are the following problems.
  • the fibrillar polymer hardly absorbs 2.45 GHz microwaves.
  • Ii When the fibrillar polymer has a complicated shape, an electric field is concentrated on the protrusions, causing thermal runaway and making uniform heating difficult.
  • the heating temperature of the fibrillated polymer by microwave irradiation is determined from the fibrillated polymer. It is also possible to set the temperature to 2000 ° C or higher by suppressing the heat dissipation of heat with a heat insulating material.
  • a heat insulating material alumina can be preferably used up to about 1800 ° C, and boron nitride (BN) or the like can be suitably used above 1800 ° C.
  • a microwave generator used to generate microwaves it is possible to use a general one that is not particularly limited.
  • microwave irradiation on the fibrillated polymer in a vacuum or in an inert gas atmosphere.
  • disappearance of the polymer due to combustion can be suppressed.
  • microwave irradiation is performed in a vacuum, it is preferable to set the system to 3 ⁇ 10 2 Pa or less.
  • an inert gas atmosphere a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, or the like is used. Can be mentioned.
  • the fibrillated polymer is preferably supported on a conductive substrate.
  • a fibrillated polymer supported on a conductive substrate is heated by microwaves, the conductive substrate efficiently absorbs microwaves and generates heat, so that it conducts from the conductive substrate in addition to the self-heating of the fibril polymer. Heat is applied, so to speak hybrid heating, and more efficient firing is possible.
  • the conductive substrate include carbon paper, carbon non-woven fabric, carbon cloth, carbon net, and mesh-like carbon. Among these, carbon paper is preferred.
  • FIG. 1 is an example of a continuous firing apparatus suitable for the practice of the present invention.
  • the continuous firing apparatus shown in Fig. 1 is a heating chamber 11 and a microwave generator for firing a sheet-like or plate-like fibril-like polymer by microwave irradiation and carbonizing it into carbon fibers in the heating chamber.
  • a transport mechanism 3 for transporting the fibrillated polymer into the heating chamber and transporting the carbon fiber generated by microwave irradiation from the heating chamber.
  • Conveying mechanism 3 of the continuous firing apparatus shown in (A) of Fig. 1 is a conveying mechanism of a roll 'toe' roll system, and roll 3A in which a sheet-like fibril polymer is sprinkled and microwave irradiation A roll 3B on which the generated sheet-like carbon fiber is wound.
  • the continuous baking apparatus shown in FIG. 1A connects the heating chamber 1 and the microwave generator 2 to guide the microwave generated by the microphone mouth wave generator 2 to the heating chamber 11.
  • a sheet-like fibril polymer is supplied from a roll 3A to a heating chamber 11, and is generated by a microwave generator 2 in the heating chamber 11.
  • the irradiated microwave is irradiated to the sheet-like fibril polymer, and the sheet-like fibril polymer is carbonized to form a sheet-like carbon fiber, and the sheet-like carbon fiber is scraped off by the roll 3B, and the roll tow 'The ability to continuously produce sheet-like carbon fibers in a roll system is possible.
  • the sheet-like fibrillated polymer may be stacked on a sheet-like substrate, where carbon paper or the like is preferred as the sheet-like substrate.
  • the transport mechanism 3 of the continuous firing apparatus shown in FIG. 1B is composed of a plurality of drive rolls 3C, and the plate-like fibrillar polymer is transported by the drive rolls 3C.
  • the continuous firing apparatus shown in FIG. 1B also includes a waveguide 4A, an introduction line 4B, and an exhaust line 4C, as in the apparatus shown in FIG.
  • a plate-like fibril polymer is supplied to the heating chamber 11 by the drive roll 3C, and the microwave generator 2 is provided in the heating chamber 11.
  • the microwaves generated in the plate are irradiated to the plate-like fibrillar polymer, and the plate-like fibrils are irradiated.
  • the brittle polymer is carbonized to form plate-like carbon fibers, and the plate-like carbon fibers are continuously carried out of the heating chamber 11 by the drive roller 3C, thereby continuously forming the plate-like carbon fibers.
  • the plate-like fibrillated polymer may be stacked on a plate-like substrate, and examples of the plate-like substrate include a glass substrate.
  • the fibrillated polymer When continuous firing is performed by irradiating the fibrillated polymer with microwaves using the continuous firing apparatus, the fibrillated polymer absorbs the microwave and self-heats, so that the fibrillated polymer can be obtained with high efficiency. It can be heated and carbonized. In addition, since it does not rely on heat conduction from the heat source, the temperature can be raised in a short time, and it is possible to realize a short time and energy saving process. Furthermore, in microwave heating, since heating is performed by self-heating of the fibrillar polymer, uniform heating is possible. Furthermore, the fibrillated polymer absorbs microwaves as the temperature rises and the carbonization progresses and can be heated well. Furthermore, microwave heating is also characterized by excellent temperature controllability and high responsiveness.
  • the frequency of the microphone mouth wave to be irradiated is usually in the range of 300 MHz to 300 GHz, and 28 GHz (millimeter wave) is particularly preferable.
  • a microwave with a frequency of 2.45 GHz typified by a microwave oven is widely used.
  • a microwave with a frequency of 2.45 GHz is used, there are the following problems.
  • the fibrillar polymer hardly absorbs 2.45 GHz microwaves.
  • Fibrils When the polymer has a complicated shape, the electric field concentrates on the protrusions, causing thermal runaway and uniform heating is difficult.
  • the heating chamber 11 of the continuous baking apparatus transmits microwaves above and below the passing position of the fibrillated polymer in order to avoid a temperature drop due to heat dissipation from the fibrillated polymer that is a sampnore. It is preferable to have a heat insulating material 5.
  • alumina is preferably used up to about 1800 ° C, and boron nitride (BN) or the like can be suitably used at 1800 ° C or higher.
  • BN boron nitride
  • the plate-like fibrillar polymer is made of carbon fiber by placing the heat insulating material 5 on the top, as shown in FIG.
  • the heat insulating material 5 By disposing the heat insulating material 5 below the driving roll 3C on which the plate-like fibril polymer is placed, the temperature drop due to heat radiation from the fibril polymer is suppressed, and the heating temperature of the fibril polymer due to microwave irradiation is reduced. Can be raised easily.
  • the heating chamber 11 of the continuous baking apparatus has a vacuum heat insulating layer 6 above and below the passing position of the fibrillated polymer.
  • a vacuum heat insulating layer made of quartz or the like that transmits microwaves can be used.
  • a sheet-like fibril polymer is made into a sheet-like carbon fiber by a roll-to-roll method, as shown in Fig. 2 (B), above and below the passing position of the sheet-like fibril polymer.
  • the plate-like fibrillar polymer is made of carbon fiber by arranging the vacuum heat insulating layer 6 on the top, as shown in FIG.
  • the vacuum heat insulating layer 6 By disposing the vacuum heat insulating layer 6 below the driving roll 3C on which the plate-like fibril-like polymer is placed, the temperature drop due to heat radiation from the fibril-like polymer is suppressed, and the fibril-like polymer caused by microwave irradiation is suppressed.
  • the heating temperature can be easily raised.
  • the heating chamber 1 may have both the heat insulating material 5 and the vacuum heat insulating layer 6.
  • the heater 7 is embedded in the heat insulating material 5.
  • the fibrillar polymer which is a sampnore, absorbs microwaves, and even if it is rapidly heated, the surrounding heat insulating material 5 may be deprived of heat.
  • the heater 7 by embedding the heater 7 in the heat insulating material 5, the temperature can be raised quickly, and the power S can be stabilized more quickly.
  • a sheet-like fibril polymer is made into a sheet-like carbon fiber by the roll 'toe' roll method, as shown in Fig.
  • a microwave absorber layer 8 is further disposed on the surface of the heat insulating material 5 facing the fibrillated polymer.
  • the microwave absorption rate of the fibrillated polymer is limited, the heating temperature can be easily controlled, and thermal runaway can be prevented.
  • the microwave absorber layer a carbon thin film, a SiC thin film, or the like can be used. For example, when a sheet-like fibril polymer is made into a sheet-like carbon fiber by the roll 'toe' roll method, as shown in Fig. 2 (D), above and below the passage position of the sheet-like fibril polymer.
  • the heat insulating material 5 having the microwave absorber layer 8 disposed on the surface facing the fibril polymer is disposed, and when the plate-like fibril polymer is made of carbon fiber, the carbon fiber shown in FIG. As shown in (D), the microwave absorber layer is placed on the surface facing the fibril-like polymer above the passing position of the plate-like fibril-like polymer and below the driving roll 3C on which the plate-like fibril-like polymer is placed.
  • the firing temperature is not particularly limited and can be appropriately set according to the purpose, and can be controlled by adjusting the microwave power.
  • the fibrillated polymer is continuously baked using the continuous baking apparatus, it is preferable to perform microwave irradiation on the fibrillated polymer in the heating chamber 11 under a vacuum or an inert gas atmosphere.
  • the introduction line 4B can be used for introducing the inert gas
  • the exhaust line 4C can be used for exhausting the inert gas.
  • the heating chamber 1 may be depressurized by connecting a vacuum pump or the like to the exhaust line 4C.
  • microwave irradiation is performed in a vacuum, it is preferable to maintain the heating chamber 1 at 3 ⁇ 10 2 Pa or lower.
  • the inert gas atmosphere a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, or the like is used. Can be mentioned.
  • the rolls 3A and 3B can be made into a normal air atmosphere.
  • the heating chamber 1 is evacuated by a large-capacity vacuum exhaust pump, so that only the heating chamber 1 is evacuated, and in the case of a roll-to-roll system, roll 3A,
  • the part 3B may be a normal air atmosphere, and air, tow, and air may be used.
  • the rolls 3A and 3B may also be installed in a vacuum or in an inert gas atmosphere as in the heating chamber 11.
  • the continuous baking apparatus further includes a cooling chamber 9 for cooling the carbon fiber generated by the microwave irradiation at the subsequent stage of the heating chamber 11.
  • a cooling chamber 9 for cooling the carbon fiber generated by the microwave irradiation at the subsequent stage of the heating chamber 11.
  • the cooling chamber By blowing the inert gas cold air in the cooling chamber 9, the carbon fiber can be sufficiently cooled and the carbon fiber can be prevented from being oxidized in the air atmosphere.
  • the cooling chamber By filling the carbon fiber with a cooling drum or the like while filling it with a vacuum or an inert gas, it is possible to sufficiently cool the carbon fiber and prevent the carbon fiber from being oxidized in the atmosphere.
  • the inert gas to be circulated through the cooling chamber 9 the same inert gas as that of the heating chamber 1 can be used.
  • the cooling chamber 9 is evacuated, the degree of vacuum is the same as that of the heating chamber 11. Similar levels can be achieved.
  • FIG. 4 (A) For example, when a sheet-like fibril polymer is made into a sheet-like carbon fiber by a roll 'toe' roll method, as shown in FIG. 4 (A), the sheet-like fibril polymer is fired.
  • a cooling chamber 9 that cools the sheet-like carbon fiber that has been heated to a high temperature after the heating chamber 1 is provided, and an inert gas is circulated through the cooling chamber 9.
  • a cooling chamber 9 is provided after the heating chamber 11 and the generated carbon fiber is sufficiently cooled by flowing an inert gas through the cooling chamber 9. be able to.
  • the cooling chamber 9 shown in FIG. 4A is similar to the heating chamber 1 in that the introduction line 10A for introducing a gas such as an inert gas into the cooling chamber 9 and the cooling chamber 9 And an exhaust line 10B for exhausting gas from.
  • a roll 3B for scraping the sheet-like carbon fiber may be disposed in the cooling chamber 9.
  • a cooling chamber is provided after the heating chamber 1 and the cooling chamber 1 is filled with vacuum or an inert gas, and the carbon fiber is supplied to the cooling plate. By making it contact, the produced
  • the cooling chamber 9 shown in FIG. 4B includes an exhaust line 10B for exhausting gas from the cooling chamber 9.
  • the conveyance of the sheet-like or plate-like fibril polymer may be continuous conveyance at a constant speed, or may be stopped and fired after conveyance for a certain length, and then conveyed again. It may be a process of repeating the transfer and firing (stop).
  • a load lock chamber (not shown) is provided before and after the heating chamber 1 to perform preliminary exhaust and gas replacement. And the heating chamber 11 may be kept under desired conditions.
  • the fibrillated polymer includes a polymer obtained by electrolytic polymerization of a compound having an aromatic ring, and the polymer is usually It is fibrillar and has a three-dimensional continuous structure.
  • the diameter and length of the fibril-like polymer having a three-dimensional continuous structure are as described above, and the compound having an aromatic ring as a raw material is also as described above.
  • the fibrillated polymer is preferably supported on a sheet-like or plate-like conductive substrate.
  • a fibrillar polymer supported on a sheet-like or plate-like conductive substrate is heated by microwaves, the conductive substrate efficiently absorbs microwaves and generates heat. The heat conducted from the substrate is applied, so to speak, hybrid heating, enabling more efficient firing.
  • the conductive substrate include force-bon paper, carbon non-woven fabric, carbon cloth, carbon net, mesh-like force, and the like, and among these, carbon paper is preferable. It is also preferable to electropolymerize a compound having an aromatic ring on a conductive substrate to produce a polymer on the conductive substrate, and to supply the polymer 'conductive substrate composite as a sample to a continuous baking apparatus.
  • the continuous baking apparatus further includes an electrolytic polymerization tank 12 for generating a polymer by electrolytic polymerization of a compound having an aromatic ring at the front stage of the heating chamber 11. It is preferable that the fibrillated polymer can be carried into the heating chamber 11.
  • an acid it is preferable to mix an acid together with a raw material compound having an aromatic ring, in the same manner as in the carbon fiber production method.
  • the kind of acid mixed in the polymerization and the concentration of the acid are as described above.
  • the working electrode and the counter electrode are immersed in a solution containing a compound having an aromatic ring, and the oxidation potential of the compound having the aromatic ring between both electrodes
  • the above voltage may be applied, or a current having a condition sufficient to secure a voltage sufficient to polymerize the compound having an aromatic ring may be applied, and a polymer is formed on the working electrode.
  • the working electrode and the counter electrode it is possible to use a plate or a porous material having a good conductive material force such as stainless steel, platinum, and carbon.
  • a polymer can be continuously produced on the sheet-like substrate to produce a sheet-like polymer substrate composite.
  • the current density in the electropolymerization and the concentration of the compound having an aromatic ring in the electrolytic solution are as described above.
  • the electrolytic solution contains a soluble salt or the like in order to adjust the pH. It may be added appropriately.
  • the continuous baking apparatus includes an electrolytic polymerization tank 12, as shown in Fig. 5, a polymer washing apparatus and a drying apparatus 13A are further provided between the electrolytic polymerization tank 12 and the heating chamber 11. In this case, it is possible to prevent the residue and moisture derived from electrolytic polymerization from adhering to the polymer.
  • a cleaning device a general device can be used.
  • the drying device include a vacuum dryer, a fluidized bed dryer, an air flow dryer, and a spray dryer.
  • the carbon fiber produced by the method of the present invention has a fibril-like and three-dimensional continuous structure, and preferably has a diameter of 30 nm to several hundreds of nm, more preferably 40 nm to 500 nm, Length force 0 ⁇ 5 ⁇ ⁇ ! ⁇ 100m is preferred ⁇ ⁇ ⁇ ! Is further preferably les, it is further preferable device is preferably a surface resistance 10 6 ⁇ 10- 2 ⁇ tool 10 4 ⁇ 10- 2 ⁇ it is ⁇ 10 mm.
  • the carbon fiber has a residual carbon ratio of 95 to 30%, preferably 90 to 40%.
  • the remaining charcoal rate is expressed by the following formula:
  • Residual carbon ratio (mass of carbon fiber after firing) ⁇ (mass of polymer before firing) X 100 force, etc.
  • the carbon fiber obtained as described above has higher conductivity than granular carbon because the entire carbon has a three-dimensional continuous structure.
  • the catalyst structure of the present invention is formed by supporting a metal, preferably a noble metal, on the carbon fiber having the three-dimensional continuous structure described above.
  • the catalyst structure is a catalyst layer of a polymer electrolyte fuel cell.
  • it can be used as a catalyst for various chemical reactions such as hydrogenation reactions.
  • Pt is particularly preferable as the noble metal supported on the carbon fiber.
  • Pt is preferably used alone, or is preferably used as an alloy with other metals such as Ru.
  • the metal supported on the carbon fiber is preferably in the form of fine particles, and the particle diameter of the fine particles is preferably in the range of 0.5 to 100 nm, more preferably in the range of 1 to 50 nm.
  • the metal loading is preferably in the range of 0.05 to 5 g with respect to the carbon fiber lg.
  • the method for supporting the metal on the carbon fiber is not particularly limited, and examples thereof include an impregnation method, an electro plating method (electrolytic reduction method), an electroless plating method, and a sputtering method.
  • the catalyst structure includes a continuous firing device including a heating chamber, a microwave generator, and a transport mechanism, and a catalyst support device disposed at a subsequent stage of the heating chamber of the continuous firing device. It can also be produced continuously by supporting the catalyst on carbon fiber using a continuous body production apparatus.
  • FIG. 5 shows an example of a continuous production apparatus for a catalyst structure suitable for carrying out the present invention.
  • the continuous production apparatus for the catalyst structure includes the above-mentioned continuous calcining apparatus and a catalyst supporting unit for supporting the catalyst on the carbon fiber in the chambers 1 and 9 of the continuous calcining apparatus, preferably in the subsequent stage of the cooling chamber 9. And a device (14).
  • the continuous production apparatus for the catalyst structure preferably includes a cleaning device and a drying device 13B for the carbon fiber (that is, the catalyst structure) on which the catalyst is supported after the catalyst supporting device 14. In this case, it is possible to prevent the residue derived from catalyst loading and water from adhering to the catalyst structure.
  • the fibrous polymer produced in the electrolytic polymerization tank 12 is supplied to the heating chamber 11 through the cleaning device and the drying device 13A, and the heating chamber 1 Microwave irradiation at 1 makes carbon fiber.
  • the produced carbon fiber is sent to the cooling chamber 9 and cooled in the cooling chamber 9, and then the catalyst supporting device. 14, the catalyst is supported on the carbon fiber by the catalyst supporting device 14, and the catalyst structure is manufactured. Thereafter, the produced catalyst structure is washed and dried by the washing device and the drying device 13B, and the sheet-like catalyst structure is scraped off on the roll 3B.
  • An electrode for a polymer electrolyte fuel cell of the present invention comprises a gas diffusion layer and a catalyst layer disposed on the gas diffusion layer, wherein the catalyst structure described above is used for the catalyst layer. To do.
  • the catalyst layer It is preferable to impregnate the catalyst layer with a polymer electrolyte.
  • a polymer electrolyte an ion conductive polymer can be used, and as the ion conductive polymer, a sulfonic acid can be used. And polymers having an ion exchange group such as carboxylic acid, phosphonic acid, and phosphonous acid, and the polymer may or may not contain fluorine.
  • the ion conductive polymer is preferably a perfluorocarbon sulfonic acid polymer such as Nafion (registered trademark).
  • the amount of the polymer electrolyte impregnated is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass of carbon fibers in the catalyst layer.
  • the thickness of the catalyst layer is not particularly limited, but is preferably in the range of 0.1 to 100 ⁇ .
  • the amount of metal supported on the catalyst layer is determined by the loading rate and the thickness of the catalyst layer, and is preferably in the range of 0.001 to 0.8 mg ⁇ m 2 .
  • the gas diffusion layer is a layer for supplying hydrogen gas or an oxidant gas such as oxygen or air to the catalyst layer to exchange generated electrons, and has a function as a gas diffusion layer. It functions as a current collector.
  • the material used for the gas diffusion layer is particularly preferably carbon paper, which is preferably the conductive substrate described above.
  • a compound having an aromatic ring is electropolymerized on a conductive substrate to form a fibril polymer, and the fibril polymer is irradiated with a micro mouth wave to form a carbon having a three-dimensional continuous structure on the conductive substrate.
  • An electrode for a polymer electrolyte fuel cell can be produced by producing fibers and further supporting a metal, preferably a noble metal such as Pt, on the carbon fiber portion.
  • the polymer electrolyte fuel cell of the present invention comprises the above electrode for a polymer electrolyte fuel cell.
  • the illustrated polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) 21 and separators 22 positioned on both sides thereof.
  • the membrane electrode assembly (MEA) 21 includes a solid polymer electrolyte membrane 23, and a fuel electrode 24A and an air electrode 24B located on both sides thereof.
  • a reaction represented by 2H ⁇ 4H ++ 4e— occurs, and the generated H + is solid.
  • the polymer electrolyte membrane 23 reaches the air electrode 24B, and the generated e- is taken out to become an electric current.
  • At least one of the fuel electrode 24A and the air electrode 24B is the above-described polymer electrolyte fuel cell electrode of the present invention.
  • the fuel electrode 24A and the air electrode 24B include a catalyst layer 25 and a gas diffusion layer 26, respectively, and are arranged so that the catalyst layer 25 is in contact with the solid polymer electrolyte membrane 23.
  • the polymer electrolyte fuel cell of the present invention is characterized in that the electrode for a polymer electrolyte fuel cell described above is used for at least one of the fuel electrode 24A and the air electrode 24B. Since the electrode has high electronic conductivity, it is possible to effectively extract electric energy without increasing the internal resistance of the fuel cell.
  • an ion conductive polymer can be used, and the ion conductive polymer is exemplified as a high molecular electrolyte that can be impregnated in the catalyst layer. Can be used. Further, as the separator 22, a normal separator having a surface (not shown) formed with a flow path of fuel, air, generated water and the like can be used.
  • the obtained fired product was taken out and observed with SEM, and it was confirmed that the carbon fiber strength S having a diameter of 40 to 100 nm was obtained on carbon paper.
  • the residual carbon ratio of this carbon fiber was measured and found to be 43.7%.
  • the sample was warped due to the shrinkage and carbonization process in the heating process of polyaniline.
  • a three-dimensional continuous structure of polyaniline was produced on carbon paper in a continuous electrolytic polymerization tank, and a long roll of polyaniline / carbon paper structure was produced.
  • a carbon paper as a working electrode in an acidic aqueous solution containing a Anirinmonoma 0.5 mol / L and HBF 1.0 mol / L, using a platinum plate as the counter electrode, N 15mA at room temperature m 2
  • the carbon paper transport speed was adjusted so that electropolymerization could be performed at a constant current of 3 minutes, and polyaniline was electrodeposited on the working electrode (on the carbon paper), then washed with ion-exchanged water and dried.
  • the obtained long roll sample with a width of 30 cm The gyrotron oscillator was set in a continuous firing device connected by a waveguide, and nitrogen gas was introduced into the heating chamber to replace the gas.
  • the microwave power was adjusted so that the maximum temperature force was 50 ° C, and the sheet-like long roll sample was conveyed at a speed of 0.25 m / min and scraped off.
  • a long carbon fiber sheet could be obtained by this firing.
  • carbon fibers having a diameter of 40 to 20 Onm were obtained on carbon paper in the same manner as in the conventional firing method that was not continuous, and the carbon fibers Was confirmed to have a three-dimensional continuous structure.
  • the carbon residue rate of this carbon fiber was measured and found to be 40.5%. It was confirmed that the carbon residue rate was the same as that of sampnore fired by batch processing using a conventional furnace, and carbonization was possible even during continuous firing.

Abstract

L’invention concerne des procédés de production (en continu) de fibre de carbone qui permettent de produire en un court laps de temps de la fibre de carbone ayant une structure tridimensionnelle continue ; sont plus spécifiquement décrits un procédé (A) de production de fibre de carbone, caractérisé en ce que l’on chauffe par irradiation aux micro-ondes un polymère fibrillaire ayant une structure tridimensionnelle continue, de manière à carboniser le polymère et à ainsi obtenir de la fibre de carbone ayant une structure tridimensionnelle continue ; et un procédé (B) permettant de produire en continu de la fibre de carbone, au moyen d’un appareil de cuisson en continu équipé d’une enceinte de chauffage (1), d’un générateur de micro-ondes (2) et d’un convoyeur (3), caractérisé en ce que l’on convoie un polymère fibrillaire de type feuille ou plaque ayant une structure tridimensionnelle continue dans l’enceinte de chauffage (1), on irradie le polymère au moyen de micro-ondes générées par le générateur (2) afin de cuire et carboniser le polymère et ainsi obtenir de la fibre de carbone ayant une structure tridimensionnelle continue.
PCT/JP2006/305571 2005-03-23 2006-03-20 Fibre de carbone, procedes pour la produire (en continu) et utilisation dans des structures catalytiques, electrodes pour piles a combustible a polymere solide et piles a combustible a polymere solide WO2006101084A1 (fr)

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JP2005-083968 2005-03-23
JP2005083968A JP2006265761A (ja) 2005-03-23 2005-03-23 炭素繊維及びその製造方法、並びにそれを用いた触媒構造体、固体高分子型燃料電池用電極及び固体高分子型燃料電池
JP2005-094003 2005-03-29
JP2005094003A JP2006273645A (ja) 2005-03-29 2005-03-29 有機物の連続焼成装置及び連続焼成方法、炭素材料並びにそれを用いた触媒構造体、固体高分子型燃料電池用電極及び固体高分子型燃料電池

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JP2009001469A (ja) * 2007-06-25 2009-01-08 Ihi Corp 黒鉛高純度化装置とその方法
JP2009001468A (ja) * 2007-06-25 2009-01-08 Ihi Corp 高機能化炭素繊維の製造装置および方法
WO2011014105A1 (fr) * 2009-07-28 2011-02-03 Soboleva Marina Vladimirovna Procédé de stabilisation de fibres contenant du carbone et procédé de fabrication de fibres à base de carbone
JP2013002767A (ja) * 2011-06-20 2013-01-07 Micro Denshi Kk マイクロ波を応用した加熱装置
WO2014131245A1 (fr) * 2013-03-01 2014-09-04 Abb Technology Ltd Matériau composite d'isolation électrique et dsipositif électrique comprenant un tel matériau
CN104937682A (zh) * 2013-03-01 2015-09-23 Abb技术有限公司 电绝缘复合物材料及包含其的电学装置
CN108085788A (zh) * 2017-11-28 2018-05-29 昆明理工大学 一种微波加热制备预氧丝的装置
JP2018142461A (ja) * 2017-02-28 2018-09-13 株式会社日立国際電気 マイクロ波加熱処理装置
EP3367751A4 (fr) * 2016-12-26 2018-10-24 Hiroji Oishibashi Dispositif chauffant à micro-ondes
CN110257959A (zh) * 2019-06-28 2019-09-20 中国科学院合肥物质科学研究院 一种可以连续加工的碳纤维微波石墨化设备
CN111869321A (zh) * 2018-01-18 2020-10-30 微波化学有限公司 微波处理装置以及碳纤维的制造方法
CN112575412A (zh) * 2020-12-17 2021-03-30 太仓旭云特种纤维科技有限公司 聚丙烯晴短纤维连续碳化方法
EP3828324A4 (fr) * 2018-07-23 2021-09-01 Lg Chem, Ltd. Appareil de carbonisation de fibres de carbone utilisant des micro-ondes

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WO2004063438A1 (fr) * 2003-01-15 2004-07-29 Bridgestone Corporation Procede de production de fibre de carbone, structure de catalyseur et corps de joint d'electrode a membrane pour pile a combustible de type polymere solide

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WO2004063438A1 (fr) * 2003-01-15 2004-07-29 Bridgestone Corporation Procede de production de fibre de carbone, structure de catalyseur et corps de joint d'electrode a membrane pour pile a combustible de type polymere solide

Cited By (18)

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Publication number Priority date Publication date Assignee Title
JP2009001469A (ja) * 2007-06-25 2009-01-08 Ihi Corp 黒鉛高純度化装置とその方法
JP2009001468A (ja) * 2007-06-25 2009-01-08 Ihi Corp 高機能化炭素繊維の製造装置および方法
WO2011014105A1 (fr) * 2009-07-28 2011-02-03 Soboleva Marina Vladimirovna Procédé de stabilisation de fibres contenant du carbone et procédé de fabrication de fibres à base de carbone
JP2013500406A (ja) * 2009-07-28 2013-01-07 マリーナ ウラジーミロヴナ ソボレヴァ， 炭素含有繊維を安定させるための方法、及び炭素繊維を生成するための方法
JP2013002767A (ja) * 2011-06-20 2013-01-07 Micro Denshi Kk マイクロ波を応用した加熱装置
WO2014131245A1 (fr) * 2013-03-01 2014-09-04 Abb Technology Ltd Matériau composite d'isolation électrique et dsipositif électrique comprenant un tel matériau
CN104937682A (zh) * 2013-03-01 2015-09-23 Abb技术有限公司 电绝缘复合物材料及包含其的电学装置
EP3367751A4 (fr) * 2016-12-26 2018-10-24 Hiroji Oishibashi Dispositif chauffant à micro-ondes
JP2018142461A (ja) * 2017-02-28 2018-09-13 株式会社日立国際電気 マイクロ波加熱処理装置
CN108085788A (zh) * 2017-11-28 2018-05-29 昆明理工大学 一种微波加热制备预氧丝的装置
CN111869321A (zh) * 2018-01-18 2020-10-30 微波化学有限公司 微波处理装置以及碳纤维的制造方法
EP3745817A4 (fr) * 2018-01-18 2021-12-15 Microwave Chemical Co., Ltd. Dispositif de traitement par micro-ondes et procédé de production de fibre de carbone
CN111869321B (zh) * 2018-01-18 2023-02-17 微波化学有限公司 微波处理装置以及碳纤维的制造方法
EP3828324A4 (fr) * 2018-07-23 2021-09-01 Lg Chem, Ltd. Appareil de carbonisation de fibres de carbone utilisant des micro-ondes
US11459673B2 (en) 2018-07-23 2022-10-04 Lg Chem, Ltd. Carbon fiber carbonization apparatus using microwave
CN110257959A (zh) * 2019-06-28 2019-09-20 中国科学院合肥物质科学研究院 一种可以连续加工的碳纤维微波石墨化设备
CN110257959B (zh) * 2019-06-28 2024-03-26 中国科学院合肥物质科学研究院 一种可以连续加工的碳纤维微波石墨化设备
CN112575412A (zh) * 2020-12-17 2021-03-30 太仓旭云特种纤维科技有限公司 聚丙烯晴短纤维连续碳化方法

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