WO2017082276A1 - Feuille poreuse conductrice, pile à combustible à électrolyte polymère, et procédé de fabrication de feuille poreuse conductrice - Google Patents

Feuille poreuse conductrice, pile à combustible à électrolyte polymère, et procédé de fabrication de feuille poreuse conductrice Download PDF

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WO2017082276A1
WO2017082276A1 PCT/JP2016/083179 JP2016083179W WO2017082276A1 WO 2017082276 A1 WO2017082276 A1 WO 2017082276A1 JP 2016083179 W JP2016083179 W JP 2016083179W WO 2017082276 A1 WO2017082276 A1 WO 2017082276A1
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porous sheet
conductive porous
fiber
organic material
carbon
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PCT/JP2016/083179
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English (en)
Japanese (ja)
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達規 伊藤
佳織 針谷
隆 多羅尾
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日本バイリーン株式会社
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Priority to JP2017550347A priority Critical patent/JP6691924B2/ja
Publication of WO2017082276A1 publication Critical patent/WO2017082276A1/fr

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/02—Single bars, rods, wires, or strips
    • 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
    • H01G11/40—Fibres
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M4/88—Processes of manufacture
    • 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
    • H01M4/96—Carbon-based electrodes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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

  • the present invention relates to a conductive porous sheet, a polymer electrolyte fuel cell, and a method for producing a conductive porous sheet.
  • a conductive porous sheet is used as a base material for a gas diffusion electrode for a fuel cell, as an electrode for an electric double layer capacitor, or as an electrode for a lithium ion secondary battery by utilizing its conductivity and porosity.
  • the use of is being considered.
  • a fiber web in which carbon fibers and a papermaking binder are mixed is made, and the fiber web is impregnated with a thermosetting resin such as a phenol resin and cured, and then the temperature is 1000 ° C. or more.
  • a thermosetting resin such as a phenol resin
  • a carbon fiber sheet produced by firing at a temperature is known. This carbon fiber sheet was excellent in electrical conductivity, but had a small surface area because the fibers were bonded using a thermosetting resin such as a phenol resin.
  • a conductive porous body that can solve such problems, the applicant of the present application states that “a conductive material in which fibrous materials having a first conductive material and a second conductive material that connects between the first conductive materials are gathered.
  • This conductive porous body had a large specific surface area, but was inferior in flexibility, such as being broken by a slight bending, and inferior in handling properties.
  • the present invention has been made under such circumstances, and an object thereof is to provide a conductive porous sheet having excellent mechanical properties and conductivity, and a method for producing the same, since it has excellent flexibility and excellent handling properties. To do. Another object of the present invention is to provide a polymer electrolyte fuel cell using the conductive porous sheet.
  • a conductive porous sheet mainly composed of carbon fibers, in which carbon fibers are joined at intersections, and the conductive porous sheet does not break in a three-point bending test [2] The conductive porous sheet according to [1], wherein the carbon fiber is curved, [3] The conductive porous sheet according to [1] or [2], wherein the breaking strength is 0.30 MPa or more, [4] The conductive porous sheet according to any one of [1] to [3], which is used as a substrate for an electrode, [5] A polymer electrolyte fuel cell comprising the conductive porous sheet according to any one of [1] to [4] as a base for a gas diffusion electrode, [6] A step of forming a precursor fiber including a first carbonizable organic material and a second carbonizable organic material made of an organic material different from the first carbonizable organic material, and an intersection of the precursor fibers can be first carbonized.
  • the conductive porous sheet of [1] of the present invention is excellent in handling properties because it has flexibility that does not break even in a three-point bending test. Moreover, since it joins at the intersection of carbon fibers, not only is mechanical strength excellent, but it is excellent also in electroconductivity.
  • the conductive porous sheet of [2] of the present invention is excellent in flexibility because the carbon fiber is curved, and when the conductive porous sheet is bent, the curved portion of the carbon fiber is stretched, Since the intersection where the carbon fibers are joined together is not easily broken simply by stretching the curved portion of the carbon fiber, it is difficult to break when bent.
  • the conductive porous sheet of [3] of the present invention has excellent mechanical strength with a breaking strength of 0.30 MPa or more.
  • the conductive porous sheet of [4] of the present invention is excellent in flexibility, mechanical strength, and conductivity, it can exhibit excellent electrode performance when used as a substrate for electrodes.
  • the polymer electrolyte fuel cell of [5] of the present invention includes the conductive porous sheet as a base material for a gas diffusion electrode.
  • the conductive porous sheet is excellent in electrical conductivity and mechanical strength, and also has excellent flexibility that does not break even when bent, and is difficult to break even when stretched by swelling and shrinking of the solid polymer film. The power generation performance can be demonstrated stably.
  • Electron micrograph on the main surface of the conductive porous sheet of Example 1 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Example 2 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Example 3 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Example 4 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Comparative Example 1 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Comparative Example 2 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Comparative Example 3 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Comparative Example 4 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Comparative Example 5 (2000 times) Electron micrograph on the main surface of the conductive porous sheet of Comparative Example 6 (2000 times) Electron micrograph showing the state of joining at the intersection of carbon fibers (50,000 times) Electron
  • the conductive porous sheet of the present invention is mainly composed of carbon fibers and joined at the intersections of the carbon fibers, it has excellent mechanical strength and conductivity. Moreover, since it has the softness
  • the carbon fiber used in the present invention can be, for example, a PAN-based carbon fiber.
  • the carbon fiber can contain a conductive material. It is preferable to include a conductive material in this manner because it is more excellent in conductivity and mechanical strength.
  • Such conductive materials include, for example, fullerene, carbon nanotube, carbon nanohorn, graphite, graphene, vapor grown carbon fiber, carbon black, metal (for example, gold, platinum, titanium, nickel, aluminum, silver, zinc, iron , Copper, manganese, cobalt, stainless steel, etc.), one type selected from the group of metal oxides of the metal, or two or more types.
  • carbon nanotubes are preferable because they are excellent in electrical conductivity, are easily oriented in the length direction in carbon fibers, and can increase electrical conductivity and mechanical strength. Further, when carbonizing, there is a difference between the shrinkage rate in the portion where the carbon nanotubes are present and the shrinkage rate in the portion where the carbon nanotubes are not present, and the curved carbon fibers tend to be curved. When bent, the curved portion is easy to stretch and is excellent in flexibility, so that it preferably contains carbon nanotubes.
  • a suitable carbon nanotube may be a single-walled carbon nanotube, a multi-walled carbon nanotube, or a coiled one.
  • the size of the suitable conductive material is not particularly limited, but when the conductive material is in the form of particles, the average particle size is preferably 5 nm to 50 ⁇ m so that carbon fibers can be easily formed.
  • the thickness is more preferably 20 nm to 25 ⁇ m, and further preferably 30 nm to 10 ⁇ m.
  • each said lower limit and each upper limit can be arbitrarily combined as desired.
  • This “average particle size” basically represents the number average particle size of the particles obtained from a particle size distribution meter by the dynamic light scattering method. For example, a state called an aggregate or structure such as carbon black was formed.
  • the fiber diameter is preferably 10 nm to 5000 nm, more preferably 10 nm to 1000 nm, still more preferably 10 nm to 500 nm, and more preferably 10 nm to 250 nm. More preferably.
  • each said lower limit and each upper limit can be arbitrarily combined as desired.
  • the fiber length is preferably a fiber length having an aspect ratio of 1000 or less, and more preferably a fiber length of 500 or less so that the fiber length can be easily dispersed in the carbon fiber.
  • the amount of the conductive material is not particularly limited, but the carbon fiber has 1 mass in order to be excellent in conductivity, mechanical strength and flexibility.
  • % Is preferably contained, more preferably 5 mass% or more, and even more preferably 10 mass% or more.
  • flexibility tends to be low, it is preferably contained at 80 mass% or less, more preferably at 50 mass% or less, and even more preferably at 40 mass% or less.
  • each said lower limit and each upper limit can be arbitrarily combined as desired.
  • the carbon fiber of the present invention is preferably curved regardless of whether or not it contains a conductive material.
  • the carbon fiber is curved, even if the carbon fibers are joined at the intersection, when the conductive porous sheet is bent, the curved portion of the carbon fiber is stretched, and the flexibility is excellent. This is because the intersection where the carbon fibers are joined to each other is not easily broken simply by stretching the curved portion of the carbon fiber, so that it is difficult to break when bent.
  • the carbon fiber of the present invention is free of voids inside the fiber, it is suitable because it is excellent in mechanical strength and conductivity. “There is no void inside the fiber” means that the entire cross section of the carbon fiber having a continuous contour and a clear cross sectional shape is accommodated in the cut surface in the thickness direction of the conductive porous sheet. The observation of the carbon fibers in the visual field is carried out at 10 locations, which means that the number of carbon fibers in which no voids are observed is 70% or more.
  • the carbon fiber contains the conductive material as described above, and when the conductive porous sheet is cut in the thickness direction, the gap that is clearly formed by dropping the conductive material is the gap. Not included.
  • the carbon fiber contains a conductive material containing voids.
  • the carbon fiber composed mainly of the conductive porous sheet is “no void inside the fiber”, that is, the carbon fiber joined at the intersection is preferably “no void inside the fiber”, Since carbon fibers that are not bonded have little influence on the mechanical strength and the like of the conductive porous sheet, there may or may not be voids inside the fibers.
  • the average fiber diameter of the carbon fiber of the present invention is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less. If the average fiber diameter exceeds 50 ⁇ m, the number of contact points between the carbon fibers in the conductive porous sheet is small, and the mechanical strength and conductivity of the conductive porous sheet tend to be inferior.
  • the lower limit of the average fiber diameter of the carbon fiber is not particularly limited, but it is realistic that it is 0.1 ⁇ m or more. The lower limit and each upper limit can be arbitrarily combined as desired.
  • the “average fiber diameter” in the present invention means an arithmetic average value of fiber diameters at 40 points of the carbon fiber, and the “fiber diameter” is a width orthogonal to the length direction when the carbon fiber is observed with a micrograph. is there.
  • the carbon fiber is continuous so as to be excellent in conductivity.
  • a continuous carbon fiber is obtained by, for example, spinning a continuous precursor fiber by a spinning solution containing a carbonizable organic material by an electrostatic spinning method or a spunbond method, and then carbonizing the carbonizable organic material. Can be manufactured.
  • the conductive porous sheet of the present invention is mainly composed of carbon fibers, but can be composed of two or more types of carbon fibers.
  • presence or absence of conductive material difference in conductive material (type, shape, size, length, etc.), difference in content of conductive material, presence or absence of voids inside carbon fiber, average fiber diameter, fiber length, etc.
  • It can be composed of two or more types of carbon fibers that differ in at least one point.
  • the conductive porous sheet of the present invention is mainly composed of the above-described carbon fiber, it has excellent conductivity.
  • the “main body” in the present invention means that the carbon fiber occupies 50 mass% or more of the conductive porous sheet. The higher the ratio of the carbon fiber, the better the conductivity. It preferably occupies 70 mass% or more of the porous sheet, more preferably occupies 90 mass% or more, and most preferably consists of 100 mass% carbon fiber.
  • examples of materials that can form conductive porous sheets include fullerenes, carbon nanotubes, carbon nanohorns, graphite, graphene, vapor-grown carbon fibers, carbon black, fine particles such as metals and metal oxides; rayon , Recycled fibers such as polynosic and cupra, semi-synthetic fibers such as acetate fibers, nylon fibers, vinylon fibers, fluorine fibers, polyvinyl chloride fibers, polyester fibers, acrylic fibers, polyethylene fibers, polyolefin fibers or polyurethane fibers, Glass fibers, inorganic fibers such as ceramic fibers, plant fibers such as cotton and hemp, animal fibers such as wool and silk; activated carbon powder (for example, steam activated carbon, alkali-treated activated carbon, acid-treated activated carbon, etc.), inorganic particles (for example, , Manganese dioxide
  • Non-conductive materials such as iron oxide, copper oxide, nickel oxide, cobalt oxide, zinc oxide, titanium-containing
  • the conductive porous sheet of the present invention is excellent in mechanical strength and conductivity because carbon fibers are joined at an intersection.
  • the carbon fibers are bonded to each other with a carbide of an organic material so that the carbon fibers are excellent in adhesion and the conductivity is excellent.
  • an organic fiber containing two or more types of carbonizable organic materials and bonding the organic fibers with one or more types of carbonizable organic materials, followed by carbonization the carbon fibers are bonded at the intersection. It can be a perforated sheet.
  • FIG. 11 is an electron micrograph (50000 times) on the main surface of the conductive porous sheet, but it is confirmed that carbon fibers are bonded to each other because a water-like film can be observed at the intersection of carbon fibers. it can.
  • FIG. 12 is an electron micrograph (50000 times) on the main surface of the conductive porous sheet, but the carbon fibers are not joined to each other because a water-fouling film cannot be observed at the intersection of the carbon fibers. Can be confirmed.
  • the conductive porous sheet of the present invention is mainly composed of carbon fibers, it may have a single-layer structure or a multilayer structure of two or more layers, and the content ratio of carbon fibers gradually increases. It may change.
  • a multilayer structure having two or more layers made of carbon fibers having different fiber diameters may be used.
  • the carbon fiber abundance ratio may be different on the main surface of the conductive porous sheet.
  • the main surface of the conductive porous sheet it has a region mainly composed of carbon fibers having a small fiber diameter and a region mainly composed of carbon fibers having a large fiber diameter, and either region is dotted, linear, and / Or can have a curved shape (such as a circle).
  • the abundance ratio of the carbon fibers may gradually change on the main surface of the conductive porous sheet.
  • the form of the conductive porous sheet of the present invention is not particularly limited, and may be, for example, a nonwoven fabric form in which fibers are randomly oriented, or a woven or knitted form in which fibers are regularly oriented.
  • the non-woven fabric is suitable because it has many intersections between carbon fibers, is excellent in electrical conductivity, has fine voids, and has a high porosity, and preferably comprises only a non-woven fabric.
  • the conductive porous sheet of the present invention is mainly composed of the above-described carbon fiber, but has flexibility that does not break in the three-point bending test and has excellent handling properties.
  • the “three-point bending test” in the present invention is performed by the following procedure using a load-displacement measuring unit (manufactured by Imada Co., Ltd., FSA-1KE-5N + GA-10N). (1) The conductive porous sheet is cut and five test pieces (flow direction test pieces) of 50 mm (flow direction at the time of manufacturing the conductive porous sheet) ⁇ 10 mm [width direction (direction perpendicular to the flow direction)] are obtained.
  • test pieces width direction test pieces
  • 50 mm [width direction] ⁇ 10 mm flow direction during production of the conductive porous sheet
  • the fulcrum is arranged so that the distance between the metal rod-shaped fulcrums having a rounded end of 2 ⁇ 0.2 mm is 16 mm.
  • a test piece is arranged so as to straddle between fulcrums.
  • a bar-shaped metal pressure wedge having a roundness with a tip of 5 ⁇ 0.1 mm is set at a speed of 1 mm / min.
  • the test piece is pushed from above the test piece to the fulcrum until the distance between the initial position of the upper surface or the lower surface of the test piece and the broken position becomes 4 mm.
  • the indentation length and the stress are measured sequentially, and when the stress drops abruptly, the indentation length at this time is defined as the bending deflection (mm).
  • mm bending deflection
  • the bending deflection amount is measured for each of the five flow direction test pieces and the five width direction test pieces, and among the five flow direction test pieces, the bending deflection amount indicating the maximum value and the minimum value are indicated. Three of the three flow direction test pieces excluding the bending deflection, and three of the five width direction test pieces, excluding the bending deflection showing the maximum value and the bending deflection showing the minimum value. The arithmetic average value of three test pieces in the width direction is calculated. As a result, a value larger than the arithmetic average value of the bending deflection is adopted as the “bending deflection”. (6) When the amount of bending deflection is more than 4 mm, it is determined that the conductive porous sheet of the test piece is “not broken”.
  • the basis weight of the conductive porous sheet of the present invention is not particularly limited, but the basis weight is preferably 0.5 to 500 g / m 2 so as to be excellent in mechanical strength and conductivity. / M 2 is more preferred, 5 to 300 g / m 2 is still more preferred, and 5 to 200 g / m 2 is even more preferred.
  • the thickness is not particularly limited, but is preferably 1 to 2000 ⁇ m, more preferably 3 to 1000 ⁇ m, still more preferably 5 to 500 ⁇ m, and further preferably 10 to 300 ⁇ m. In addition, each lower limit and each upper limit in the said fabric weight and thickness can be combined arbitrarily as desired.
  • the “weight per unit” in the present invention is a value obtained by measuring the mass of a sample obtained by cutting a conductive porous sheet into a 10 cm square and converting it to a mass of 1 m 2
  • “thickness” is a thickness gauge. This is a value measured using Mitutoyo Corporation (code No. 547-401: measuring force 3.5 N or less).
  • Conductive porous sheet of the invention are excellent in electrical conductivity, the degree is preferably an electric resistance of 20 m [Omega ⁇ cm 2 or less, more preferably at 15m ⁇ ⁇ cm 2 or less, 10 m [Omega ⁇ cm 2 less more preferably in the range, further preferably at 8m ⁇ ⁇ cm 2 or less, and even more preferably 6m ⁇ ⁇ cm 2 or less.
  • the conductive porous sheet of the present invention has excellent mechanical strength, but the degree of breakage is preferably 0.30 MPa or more, more preferably 0.40 MPa or more, and 0.50 MPa. More preferably, it is more preferably 0.60 MPa or more.
  • This breaking strength is a quotient obtained by dividing the breaking load by the cross-sectional area of the conductive porous sheet.
  • the breaking load is a value measured under the following conditions.
  • the cross-sectional area is the width of the conductive porous sheet (test piece) at the time of measurement. And the value obtained from the product of thickness.
  • the breaking load is measured for 10 flow direction test pieces and 10 width direction test pieces, and the arithmetic average value of 20 test pieces is taken as the breaking load.
  • Test piece 50 test pieces (flow direction test piece) of 50 mm (flow direction during manufacture of the test piece) ⁇ 5 mm [width direction (direction orthogonal to the flow direction)], 50 mm [width direction] ⁇ 5 mm (test piece) 10 test pieces (width direction test piece) in the manufacturing direction)
  • Product name Small tensile tester (model: TSM-41-cre, manufactured by Search Inc.) Spacing between chucks: 20 mm
  • Tensile speed 20 mm / min.
  • the conductive porous sheet of the present invention is mainly composed of carbon fibers, but the specific apparent Young's modulus is preferably 100 [MPa / (g / cm 3 )] or more.
  • the high specific Young's modulus means that the rigidity is high, and because it is a highly conductive conductive porous sheet, it has excellent dimensional stability, is easy to handle by itself, and is wound into a roll shape. There is an advantage that it can be stored and transported. For example, when such a conductive porous sheet having a high apparent Young's modulus is used as a base material for an electrode of a polymer electrolyte fuel cell, swelling and shrinkage of the polymer electrolyte membrane can be suppressed. Cracks due to swelling and shrinkage of the molecular film can be prevented.
  • this specific apparent Young's modulus is a value obtained by dividing the apparent Young's modulus, which is an index of rigidity of the conductive porous sheet, by the apparent density of the conductive porous sheet. .
  • the apparent Young's modulus is the same, when the apparent density is high and low, the lower apparent density is the same apparent Young's modulus even though the amount of carbon fiber is small.
  • the rigidity of each carbon fiber is so high that it is expressed by the specific apparent Young's modulus, which is the apparent Young's modulus of the conductive porous sheet divided by the apparent density. ing. The higher the specific Young's modulus is, the higher the rigidity of each carbon fiber is.
  • each said lower limit and upper limit can be arbitrarily combined as desired.
  • This “specific apparent Young's modulus” is a value obtained by the following procedure.
  • the apparent density (g / cm 3 ) is calculated by dividing the basis weight (g / cm 2 ) of the conductive porous sheet to be evaluated by the thickness (cm).
  • 10 directional test specimens obtained by cutting the conductive porous sheet into a rectangular shape of 50 mm in the flow direction during the production of the conductive porous sheet and 5 mm in the width direction (direction perpendicular to the flow direction); And 10 horizontal direction test pieces cut into a rectangular shape of 50 mm in the width direction and 5 mm in the flow direction are respectively collected.
  • the apparent Young's modulus is obtained by dividing the tensile stress by the strain at the maximum point (dimensionalless) [elongation length of test piece (mm) ⁇ initial test piece length (mm)].
  • the arithmetic average value of the apparent Young's modulus of the 20 test pieces is calculated and set as the “average apparent Young's modulus”.
  • the “average apparent Young's modulus” is calculated by dividing the average apparent Young's modulus by the apparent density.
  • the conductive porous sheet of the present invention when used as a base material for a gas diffusion electrode of a polymer electrolyte fuel cell and a gas diffusion layer is formed, when the surface smoothness is low, the conductive porous sheet and The conductive porous sheet may pierce other materials that abut (in the case of polymer electrolyte fuel cells, the solid polymer membrane), possibly damaging other materials, and other materials (solid polymer membranes)
  • a gap is formed between the solid polymer membrane and / or the separator and the conductive porous sheet, resulting in poor adhesion and sufficient performance (in the case of a polymer electrolyte fuel cell). , Power generation performance) tends to be difficult to demonstrate.
  • the surface of the conductive porous sheet is smooth so that other materials are not easily damaged and sufficient performance is easily exhibited.
  • the “average arithmetic average surface roughness” on the main surface of the conductive porous sheet is preferably 0.01 ⁇ m to 20 ⁇ m, more preferably 0.1 ⁇ m to 10 ⁇ m, and more preferably 0.1 ⁇ m to 5 ⁇ m. It is more preferable that the thickness is 0.1 to 4 ⁇ m.
  • each said lower limit and each upper limit can be arbitrarily combined as desired.
  • This “average arithmetic average surface roughness” is a laser microscope (OLS4100, manufactured by Olympus) that can prepare a sample by cutting a conductive porous sheet into 5 cm square and measure roughness (three-dimensional) parameters in accordance with ISO25178. Is used to mean the value obtained by further averaging the values of each arithmetic average surface roughness (Sa) after measuring the arithmetic average surface roughness (Sa) for each of five evaluation regions (260 ⁇ m ⁇ 260 ⁇ m) in the sample. To do.
  • OLS4100 laser microscope
  • the conductive porous sheet of the present invention preferably has a porosity of 50% or more so that the voids can be effectively utilized.
  • a porous porous conductive sheet is used as, for example, an electrode substrate of a polymer electrolyte fuel cell, a fuel cell having excellent drainage and gas diffusibility and high power generation performance can be produced.
  • the shape stability of the conductive porous sheet tends to be extremely lowered, and therefore it is preferably 99% or less.
  • each said lower limit and upper limit can be arbitrarily combined as desired.
  • the porosity P (unit:%) is a value obtained from the following formula.
  • P 100- (Fr1 + Fr2 + .. + Frn)
  • Frn indicates the filling rate (unit:%) of component n constituting the conductive porous sheet, and is a value obtained from the following formula.
  • Frn [M ⁇ Prn / (T ⁇ SGn)] ⁇ 100
  • M is the mass per unit (unit: g / cm 2 ) of the conductive porous sheet
  • T is the thickness (cm) of the conductive porous sheet
  • Prn is the component n (for example, carbon fiber) in the conductive porous sheet.
  • SGn means the specific gravity (unit: g / cm 3 ) of component n.
  • the conductive porous sheet of the present invention is not only excellent in mechanical strength and conductivity, but is flexible and excellent in handling properties, and therefore can be suitably used as an electrode substrate.
  • an electrode substrate For example, when used as an electrode of a lithium ion secondary battery or an electric double layer capacitor, a secondary battery or capacitor having a large capacity can be produced.
  • a base material for a gas diffusion electrode of a polymer electrolyte fuel cell a polymer electrolyte fuel cell capable of exhibiting excellent power generation performance can be produced.
  • the conductive porous sheet of the present invention when the conductive porous sheet of the present invention is provided as the base material for the gas diffusion electrode of the solid polymer fuel cell, the conductive porous sheet of the present invention is porous. If nothing is filled, the drainage property in the thickness direction and the surface direction of the gas diffusion electrode substrate (conductive porous sheet) is excellent, and the diffusibility of the supplied gas is excellent.
  • fluororesin examples include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene.
  • PTFE polytetrafluoroethylene
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • PVDF polyvinyl fluoride
  • PVF polyvinyl fluoride
  • PFA perfluoroalkoxy fluororesin
  • Ethylene / hexafluoropropylene copolymer FEP
  • Ethylene / hexafluoropropylene copolymer ETFE
  • ETFE ethylene / tetrafluoroethylene copolymer
  • ECTFE ethylene / chlorotrifluoroethylene copolymer
  • vinylidene fluoride / tetrafluoroethylene / hexafluoro Examples thereof include a propylene copolymer and a copolymer of various monomers constituting the resin.
  • examples of carbon include carbon fiber, fullerene, carbon nanotube, carbon nanohorn, graphite, graphene, vapor growth carbon fiber, and carbon black.
  • the polymer electrolyte fuel cell of the present invention can be exactly the same as a conventional polymer electrolyte fuel cell except that the above-mentioned conductive porous sheet is provided as a base material for a gas diffusion electrode. That is, a cell in which a bonded body of a gas diffusion electrode having a catalyst supported on the surface of a gas diffusion electrode substrate (conductive porous sheet) as described above and a solid polymer film is sandwiched between a pair of bipolar plates. It has a structure in which a plurality of units are stacked.
  • Such a conductive porous sheet of the present invention includes, for example, a step of forming a precursor fiber including a first carbonizable organic material and a second carbonizable organic material made of an organic material different from the first carbonizable organic material.
  • a conductive porous sheet that does not break in the three-point bending test can be manufactured by the process of carbonizing the carbon fiber while it is bonded at the intersection to form a curved carbon fiber. According to this manufacturing method, after joining the intersections of the precursor fibers, carbonized while being joined at the intersections to form a curved carbon fiber, the conductivity, excellent in flexibility, mechanical strength, and conductivity A perforated sheet can be produced.
  • first, a first carbonizable organic material and a second carbonizable organic material made of an organic material different from the first carbonizable organic material are prepared.
  • the first carbonizable organic material and the second carbonizable organic material are not particularly limited.
  • thermosetting resins such as resins, thermosetting polyimide resins, thermosetting polyimide resins, thermosetting polyamide resins; polystyrene resins, polyester resins, polyolefin resins, polyimide resins, polyamide resins, polyamideimide resins, polyvinyl acetate resins, Thermoplastic resins such as vinyl chloride resin, fluororesin, polyacrylonitrile resin, acrylic resin, polyether resin, polyvinyl alcohol, polyvinyl pyrrolidone, pitch, polyamino acid resin, polybenzimidazole resin; cellulose (polysaccharide), tar; Mention may be made of a copolymer of a monomer of the resin component (e.g., acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylon
  • thermosetting resin is included as the first carbonizable organic material or the second carbonizable organic material.
  • the thermosetting resin is included, as described later, the intersection of the precursor fibers containing the first carbonizable organic material and the second carbonizable organic material is joined by the thermosetting resin, and at the time of carbonization, This is because it is easy to maintain the joined state.
  • a phenol resin and / or an epoxy resin are suitable because they are excellent in conductivity after carbonization in addition to the above-described action.
  • a carbonizable organic material having a carbonization process or a carbonization rate different from that of the thermosetting resin is preferable to use.
  • the first or second carbonizable organic material having a different carbonization process not only the spinnability is improved, but also the chemical change mechanism (optimum temperature, time, decomposition, etc.) in the carbonization process is different. This is because differences in shrinkage rate, fluidity, and the like cause bending during carbonization to easily form a curved carbon fiber.
  • thermosetting resin such as a phenol resin and / or an epoxy resin
  • polyacrylonitrile resin As the first carbonizable organic material or the second carbonizable organic material, a thermosetting resin such as a phenol resin and / or an epoxy resin, and as the second carbonizable organic material or the first carbonizable organic material, a polyacrylonitrile resin.
  • a thermoplastic resin such as pitch
  • polyacrylonitrile resin is suitable as the first carbonizable organic material or the second carbonizable organic material because it has a high carbonization rate and easily forms carbon fibers having no voids inside the fibers.
  • the conductive material can be a conductive material as described above, and is preferably a carbon nanotube.
  • the conductive material when carbonizing, there is a difference between the shrinkage rate in the portion where the carbon nanotubes are present and the shrinkage rate in the portion where the carbon nanotubes are not present, which tends to be a curved carbon fiber. Even if it is bent, the curved portion is easy to stretch, so it has excellent flexibility.
  • silicone such as polydimethylsiloxane and metal alkoxide (methoxide such as silicon, aluminum, titanium, zirconium, boron, tin, and zinc) are used.
  • metal alkoxide methoxide such as silicon, aluminum, titanium, zirconium, boron, tin, and zinc
  • ethoxide, a propoxide, a butoxide, etc. can be used in combination with a polymer obtained by polymerizing a known inorganic compound.
  • a spinning solution containing the first carbonizable organic material and the second carbonizable organic material as described above is prepared to form the precursor fiber.
  • a spinning solution including a conductive material is prepared.
  • a spinning solution containing silicone and an inorganic polymer is prepared.
  • the solvent constituting the spinning solution is not particularly limited as long as the first carbonizable organic material and the second carbonizable organic material can be dissolved.
  • Examples thereof include carbon, methylene chloride, chloroform, trichloroethane, ethylene carbonate, diethyl carbonate, propylene carbonate, water, and the like.
  • These solvents can be a single solvent or a mixed solvent.
  • a poor solvent can be added as long as there is no problem in spinnability
  • the solid content concentration in the spinning solution is not particularly limited, but is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. This is because when the content is less than 1 mass%, the productivity is extremely lowered, and when the content exceeds 50 mass%, the spinning tends to become unstable.
  • each said lower limit and each upper limit can be arbitrarily combined as desired.
  • the solid content mass ratio of the 1st carbonizable organic material and the 2nd carbonizable organic material in a spinning liquid changes with combinations of the 1st carbonizable organic material and the 2nd carbonizable organic material, it does not specifically limit
  • the first carbonizable organic material is made of an organic material having a high carbonization rate such as polyacrylonitrile resin and the second carbonizable organic material is made of a thermosetting resin such as an epoxy resin
  • the first carbonizable organic material and the first carbonizable organic material are superior in electrical conductivity due to the first carbonizable organic material, and excellent in mechanical strength, electrical conductivity, and flexibility due to bending by the second carbonizable organic material.
  • the solid content ratio with the carbonizable organic material is preferably 40 to 90:60 to 10, more preferably 50 to 80:50 to 20, and 50 to 70:50 to 30. And even more preferred.
  • each said lower limit and each upper limit can be arbitrarily combined as desired.
  • the first carbonizable organic material and the second carbonizable organic material are selected so as to have excellent conductivity. It is preferable to include a conductive material having a mass of 1 to 90, and more preferable to include a conductive material having a mass of 5 to 50 with respect to a total mass of 100 solids of the carbonizable organic material. More preferably, a conductive material having a mass of ⁇ 40 is included. In addition, each said lower limit and each upper limit can be arbitrarily combined as desired.
  • a spinning fiber containing the first carbonizable organic material and the second carbonizable organic material as described above is spun to form a precursor fiber.
  • a method of forming this precursor fiber for example, a dry spinning method, an electrostatic spinning method, and a gas parallel to a spinning solution discharged from a liquid discharging unit as disclosed in JP-A-2009-287138 is used. And a method of producing a fiber by applying a shearing force in a straight line to the spinning solution.
  • the electrospinning method or the spinning method disclosed in Japanese Patent Application Laid-Open No. 2009-287138 is preferable because a precursor fiber having a small average fiber diameter of 3 ⁇ m or less can be easily spun.
  • the dry spinning method or the electrostatic spinning method is preferable because continuous precursor fibers can be spun.
  • the electrospinning method is suitable because a precursor fiber having a continuous fiber length can be spun in addition to a small fiber diameter.
  • seat shape can be formed by collecting the precursor fiber spun by the above methods directly with a collection body.
  • the “precursor fiber” in the present invention means a fiber in a state where neither the first carbonizable organic material nor the second carbonizable organic material is carbonized, and the first carbonizable organic material and the second carbonized carbon. Since all of the possible organic materials are carbonized to form carbon fiber, it is expressed as a precursor fiber in the sense of a fiber that is a source of carbon fiber.
  • a sheet in which precursor fibers are gathered is formed.
  • the sheet in which the precursor fibers are gathered can be formed, for example, by collecting the spun precursor fibers directly by a collecting body, or winding the spun precursor fibers as continuous fibers and then cutting them to a desired fiber length. After forming into short fibers, it can be formed by a dry method such as a card method, an air array method, or a wet method, and can be formed by weaving or knitting by a conventional method using continuous precursor fibers. You can also.
  • the method of collecting the spun precursor fiber directly with a collector is preferable because it can be a precursor fiber having a continuous fiber length and is excellent in productivity.
  • thermosetting resin is included as the first carbonizable organic material or the second carbonizable organic material
  • thermosetting resin is In order to cure, the thermosetting resin can be bonded by performing a heat treatment at a temperature at which the thermosetting resin is thermally cured. Since the heat curing conditions such as the heat treatment temperature and time vary depending on the thermosetting resin, they are appropriately adjusted according to the thermosetting resin.
  • a solvent capable of dissolving the first carbonizable organic material or the second carbonizable organic material was applied to the sheet in which the precursor fibers were assembled, and the first carbonizable organic material or the second carbonizable organic material was dissolved. Later, bonding can be performed by drying and removing the solvent. Since the plasticizing joining conditions such as the type of solvent, the solvent application amount, the solvent temperature, the drying temperature, and the drying time vary depending on the first carbonizable organic material or the second carbonizable organic material, It adjusts suitably according to the organic material which can be carbonized.
  • the precursor fiber sheet mainly composed of the precursor fibers can be formed by the above-described method.
  • the precursor fibers include materials other than the precursor fibers
  • the precursor fibers are aggregated when the precursor fibers are spun.
  • the material other than the precursor fiber can be applied when forming the sheet or after forming the sheet in which the precursor fibers are aggregated.
  • a precursor fiber sheet in which carbon nanotubes are mixed can be formed by spraying carbon nanotubes on the flow of spun precursor fibers.
  • the precursor fiber constituting the precursor fiber sheet is carbonized while being joined at the intersection, and a conductive porous sheet that is not broken by a three-point bending test is manufactured as a curved carbon fiber.
  • the conductive porous sheet having excellent flexibility, mechanical strength, and conductivity Can be manufactured. That is, the precursor fiber contains the first carbonizable organic material and the second carbonizable organic material, and has different shrinkage rates when carbonized, and thus becomes a curved carbon fiber.
  • This carbonization is not particularly limited as long as the first carbonizable organic material and the second carbonizable organic resin can be carbonized.
  • the maximum temperature is 800 to 3000 ° C. in an inert gas atmosphere such as nitrogen, helium, and argon. It can be performed by heating.
  • the rate of temperature rise is preferably 5 to 100,000 ° C./min, and more preferably 5 to 1000 ° C./min.
  • the holding time at the maximum temperature is preferably within 3 hours, more preferably 1 to 120 minutes. In each of these parameters, the lower limit and the upper limit can be arbitrarily combined as desired.
  • the polyacrylonitrile resin is included as the first carbonizable organic material or the second carbonizable organic material constituting the precursor fiber.
  • an infusibilization step may be performed before the carbonization treatment. This infusibilization can be performed by heating at a temperature of 200 to 300 ° C. for 10 to 120 minutes in an oxidizing atmosphere. The infusible heating can be carried out twice or more under different conditions of temperature or time.
  • the conductive porous sheet of the present invention preferably has a large porosity of 50% or more.
  • the conductive porous sheet having such a high porosity is a carbon fiber having an average fiber diameter of 0.1 ⁇ m to 50 ⁇ m.
  • the porosity is easily satisfied.
  • Precursor fibers which are the basis of carbon fibers having such an average fiber diameter are easy to produce by, for example, the electrostatic spinning method or the spinning method disclosed in JP-A-2009-287138.
  • the binder fills the gaps between the precursor fibers or covers the periphery of the intersections of the precursor fibers more than necessary, and the porosity tends to be low. Therefore, when the first carbonizable organic material or the second carbonizable organic material constituting the precursor fiber is bonded without using a binder, the porosity is easily satisfied.
  • the conductive porous sheet of the present invention can impart or improve physical properties suitable for each application by various post-processing.
  • a conductive porous sheet of the present invention is used as a base material for a gas diffusion electrode of a polymer electrolyte fuel cell, in order to increase the water repellency of the conductive porous sheet and to enhance drainage and gas diffusion properties, A conductive porous sheet is immersed in a fluorine-based dispersion such as a tetrafluoroethylene dispersion to give a fluorine-based resin, and then sintered at a temperature of 300 to 350 ° C.
  • carbon fibers without voids inside are easy to manufacture by using an organic material having a high carbonization rate for both the first carbonizable organic material and the second carbonizable organic material. That is, since there are few organic materials which lose
  • the first carbonizable organic material or the second carbonizable organic material having a high carbonization rate include polyacrylonitrile, epoxy resin, and phenol resin.
  • a rigid conductive porous sheet having a specific apparent Young's modulus of 100 MPa / (g / cm 3 ) or more is easy to manufacture by forming carbon fibers from a rigid material. That is, the first carbonizable organic material and / or the second carbonizable organic material can be easily manufactured by using a thermosetting resin, particularly an epoxy resin or a phenol resin.
  • the average arithmetic average surface roughness on the main surface is 0.01 ⁇ m to 20 ⁇ m (preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and more preferably 0.1 to 4 ⁇ m.
  • the conductive porous sheet is, for example, a carbon fiber having an average fiber diameter of 20 ⁇ m or less, a non-woven fabric in the form of the conductive porous sheet, and / or a static porous sheet. It is easy to produce by directly producing by an electrospinning method and a method as disclosed in JP-A-2009-287138.
  • each said minimum and each upper limit in the said average arithmetic average surface roughness can be arbitrarily combined as desired.
  • EP a second carbonizable organic material
  • a dispersion was prepared by mixing with the solution.
  • EP carbonizable organic material
  • a second spinning solution having a solid content mass ratio of CNT: PAN: EP of 10:60:30 and a solid content concentration of 25 mass% was prepared.
  • CNT carbon nanotubes synthesized by CVD (trade name: VGCF-H (manufactured by Showa Denko KK), fiber diameter: 150 nm, aspect ratio: 40, multi-walled carbon nanotubes] are used as the conductive material.
  • DMF was further added to dilute to obtain a dispersion solution in which the carbon nanotubes were dispersed.
  • a sixth spinning solution having a solid content of 20 mass% at 30:30 was prepared.
  • CNT carbon nanotubes synthesized by CVD (trade name: VGCF-H (manufactured by Showa Denko KK), fiber diameter: 150 nm, aspect ratio: 40, multi-walled carbon nanotubes] are used as the conductive material.
  • DMF was further added to dilute to obtain a dispersion solution in which the carbon nanotubes were dispersed.
  • a seventh spinning solution having a solid content concentration of 25 mass% was prepared at 60:30.
  • Example 1 The first spinning solution is formed by spinning the precursor continuous fiber under the following conditions by the electrostatic spinning method, and is directly accumulated on the stainless drum as the counter electrode, and is composed of only the precursor continuous fiber, and the intersection of the fibers is joined. A non-woven fabric precursor fiber assembly sheet was formed.
  • Electrode Metal nozzle (inner diameter: 0.33 mm) and stainless steel drum Discharge amount: 5 g / hour Distance between nozzle tip and stainless steel drum: 10 cm Applied voltage: 10 kV Temperature / humidity: 25 ° C / 30% RH
  • the precursor fiber assembly sheet was heat-treated for 1 hour with a hot air dryer at a temperature of 150 ° C. to cure the epoxy resin, thereby obtaining a precursor fiber sheet in which the intersections of the fibers were joined.
  • the precursor fiber sheet is oxidized in air at a temperature of 220 ° C. for 30 minutes and at a temperature of 260 ° C. for 1 hour to infusibilize the PAN constituting the precursor continuous fiber, so that the infusible precursor fiber A sheet was used.
  • the infusibilized precursor fiber sheet is subjected to carbonization firing treatment (temperature increase rate: 10 ° C./min) at a temperature of 1300 ° C. for 1 hour in a nitrogen gas atmosphere using a vacuum substitution type electric furnace to obtain a precursor continuous fiber.
  • PAN and EP constituting carbon are made into carbon continuous fibers, and are composed of continuous carbon fibers, and have a non-woven structure and are bonded to each other at the intersection of continuous carbon fibers (unit weight: 6.5 g / m 2 , thickness: 65 ⁇ m, fiber diameter: 1.1 ⁇ m, porosity: 91%).
  • the electron micrograph (2000 times) in the main surface of this electroconductive porous sheet was image
  • Example 2 A conductive perforated sheet composed of continuous carbon fibers and having a non-woven structure and joined at the intersection of continuous carbon fibers (except for the use of the second spinning liquid as the spinning liquid).
  • the basis weight was 10 g / m 2 , the thickness was 84 ⁇ m, the fiber diameter was 0.7 ⁇ m, and the porosity was 94%.
  • the electron micrograph (2000 times) in the main surface of this electroconductive porous sheet was image
  • Example 3 Similar to Example 2, except that the PAN constituting the precursor continuous fiber was not infusible without performing the oxidation treatment, the carbon continuous fibers having a single-layer structure having only a non-woven fabric structure.
  • a conductive porous sheet (weight per unit area: 10 g / m 2 , thickness: 84 ⁇ m, fiber diameter: 0.7 ⁇ m, porosity: 94%) was produced.
  • the electron micrograph (2000 times) in the main surface of this electroconductive porous sheet was image
  • the carbon continuous fiber was in the state where the inside of the fiber had no voids, and the mass ratio of CNT in the carbon continuous fiber was 12 mass%.
  • Example 4 A conductive perforated sheet composed of continuous carbon fibers and having a non-woven structure joined at the intersection of continuous carbon fibers (except for the use of the third spinning liquid as the spinning liquid)
  • the basis weight was 5.6 g / m 2 , the thickness was 34 ⁇ m, the fiber diameter was 0.8 ⁇ m, and the porosity was 91%.
  • the electron micrograph (2000 times) in the main surface of this electroconductive porous sheet was image
  • Example 1 In the same manner as in Example 1 except that the fourth spinning solution is used as the spinning solution and spinning is performed under the following electrostatic spinning conditions, the nonwoven fabric is formed of only PAN precursor continuous fibers and the intersections of the fibers are not joined. A precursor fiber assembly sheet was formed.
  • Electrode Metal nozzle (inner diameter: 0.33 mm) and stainless steel drum Discharge amount: 1 g / hour Distance between nozzle tip and stainless steel drum: 8 cm Applied voltage: 10 kV Temperature / humidity: 25 ° C / 30% RH
  • the precursor fiber assembly sheet is subjected to an oxidation treatment in air at a temperature of 220 ° C. for 30 minutes and at a temperature of 260 ° C. for 1 hour to infusibilize the PAN constituting the precursor continuous fiber, and then a vacuum replacement type Using an electric furnace, carbonization firing treatment (temperature increase rate: 10 ° C./min) for 1 hour at a temperature of 1300 ° C.
  • PAN constituting the precursor continuous fiber is carbonized to be a carbon continuous fiber
  • Conductive porous sheet consisting of continuous carbon fibers only and having a non-woven structure, in which intersections of continuous carbon fibers are not joined (weight: 5 g / m 2 , thickness: 20 ⁇ m, fiber diameter: 0.3 ⁇ m, Porosity: 86%) was produced.
  • the carbon continuous fiber was linear.
  • the carbon continuous fiber was in a state of being fully filled without voids inside the fiber.
  • Comparative Example 2 Before carrying out the oxidation treatment, the precursor fiber assembly sheet is immersed in a mixed solution of DMF / water adjusted to a concentration of 7 mass%, squeezed between a pair of rolls, and then placed in an oven set at a temperature of 80 ° C. for 10 minutes. Subsequently, only the carbon continuous fiber was obtained in the same manner as in Comparative Example 1 except that the mixed solvent was removed by heat treatment in an oven set at a temperature of 160 ° C., and the intersection of the PAN precursor continuous fibers was adhered.
  • a conductive porous sheet having a single-layer structure having a nonwoven fabric structure and joined at the intersections of carbon continuous fibers (weight: 5 g / m 2 , thickness: 18 ⁇ m, fiber diameter: 0.3 ⁇ m, porosity: 85%) was made.
  • carbon continuous fiber was linear.
  • the carbon continuous fiber was in a state of being fully filled without voids inside the fiber.
  • Example 3 A single-layered carbon continuous fiber having a non-woven structure consisting of carbon continuous fibers in the same manner as in Example 1, except that the fifth spinning liquid was used as the spinning liquid and spinning was performed under the following electrostatic spinning conditions.
  • the electroconductive porous sheet (weight per unit: 8 g / m 2 , thickness: 62 ⁇ m, fiber diameter: 0.6 ⁇ m, porosity: 93%) in which the crossing points are not joined was prepared.
  • the carbon continuous fiber was in a state of being fully filled without voids inside the fiber.
  • Electrode Metal nozzle (inner diameter: 0.33 mm) and stainless steel drum Discharge amount: 1 g / hour Distance between nozzle tip and stainless steel drum: 8 cm Applied voltage: 10 kV Temperature / humidity: 25 ° C / 40% RH
  • Comparative Example 4 Similar to Comparative Example 3, except that no oxidation treatment was performed and the PAN constituting the precursor continuous fiber was not infusible, the carbon continuous fibers having a single-layer structure having only a non-woven fabric structure.
  • the electroconductive porous sheet (weight per unit: 8 g / m 2 , thickness: 62 ⁇ m, fiber diameter: 0.6 ⁇ m, porosity: 93%) in which the crossing points are not joined was prepared.
  • the carbon continuous fiber was linear as shown in FIG.
  • the sixth spinning solution is obtained by spinning the precursor continuous fiber by the electrospinning method under the following conditions, and directly accumulating on the stainless drum as the counter electrode, and only the precursor continuous fiber is joined. A non-woven fabric precursor fiber assembly sheet was formed.
  • Electrode Metal nozzle (inner diameter: 0.33 mm) and stainless steel drum Discharge amount: 4 g / hour Distance between nozzle tip and stainless steel drum: 14 cm Applied voltage: 10 kV Temperature / humidity: 25 ° C / 30% RH
  • the precursor fiber assembly sheet was heat-treated with a hot air dryer at a temperature of 150 ° C. for 1 hour to cure the epoxy resin and obtain a precursor fiber sheet in which the intersections of the fibers were joined.
  • carbonization baking treatment temperature increase rate: 10 ° C./min
  • a conductive porous sheet having a single layer structure joined at the intersection of carbon continuous fibrous materials (weight per unit: 20 g / m 2 , thickness: 40 ⁇ m, average fiber diameter: 1.3 ⁇ m, porosity: 73%) is produced. did.
  • CNT orientated in the length direction of the continuous carbon fiber was disperse
  • CNTs are composed of carbon continuous fibers in a porous and continuous state in which the CNTs are partially connected by EP carbide and THV carbide, and the intersections of the carbon continuous fibers are between EP carbide and THV. It was in a bonded state with carbides.
  • the seventh spinning solution is obtained by spinning the precursor continuous fiber under the following conditions by the electrospinning method, and is directly accumulated on the stainless drum as the counter electrode, and is composed only of the precursor continuous fiber. A non-woven fabric precursor fiber assembly sheet was formed.
  • Electrode Metal nozzle (inner diameter: 0.33 mm) and stainless steel drum Discharge amount: 4 g / hour Distance between nozzle tip and stainless steel drum: 14 cm Applied voltage: 17 kV Temperature / humidity: 25 ° C / 35% RH
  • the precursor fiber assembly sheet was heat-treated with a hot air dryer at a temperature of 150 ° C. for 1 hour to cure the epoxy resin and obtain a precursor fiber sheet in which the intersections of the fibers were joined.
  • the precursor fiber sheet is subjected to an oxidation treatment in air at a temperature of 220 ° C. for 30 minutes and at a temperature of 260 ° C. for 1 hour, so that the PAN constituting the precursor continuous fiber is infusible and a part of EP is obtained.
  • a fluidized infusible precursor fiber sheet was obtained.
  • the infusibilized precursor fiber sheet is subjected to carbonization baking treatment (temperature increase rate: 10 ° C./min) for 1 hour at a temperature of 800 ° C. in a nitrogen atmosphere using a tubular furnace, thereby forming a precursor continuous fiber PAN.
  • carbonization baking treatment temperature increase rate: 10 ° C./min
  • bonded to each other at the intersection of carbon continuous fibrous materials having a non-woven structure 5 g / m 2 , thickness: 15 ⁇ m, average fiber diameter: 0.8 ⁇ m, porosity: 82%).
  • the conductive porous sheets of Comparative Examples 3 to 4 had relatively high electrical resistance and low mechanical strength. This was considered because the intersection of carbon fibers was not joined.
  • the conductive porous sheet of the present invention is excellent in flexibility, and excellent in mechanical strength and conductivity, despite being composed of rigid carbon fibers. It was a thing. The excellent flexibility is because the carbon fibers are curved between the intersections where the carbon fibers are joined, so that the stress for bending can be dispersed, and the mechanical strength and conductivity are excellent. It was thought that this was because the intersections of the carbon fibers were joined.
  • the conductive porous sheet of the present invention is excellent in mechanical strength, conductivity, and flexibility, and can be suitably used as an electrode substrate.
  • it is useful as an electrode of a lithium ion secondary battery or an electric double layer capacitor, and as a base material for a gas diffusion electrode of a polymer electrolyte fuel cell.

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Abstract

La présente invention a pour but de pourvoir à une feuille poreuse conductrice qui présente une excellente maniabilité en conséquence de son excellente flexibilité, et qui présente également une excellente résistance mécanique et une excellente conductivité. La présente invention a également pour but de pourvoir à un procédé de fabrication de la feuille poreuse conductrice. La présente invention a en outre pour but de pourvoir à une pile à combustible à électrolyte polymère qui utilise la feuille poreuse conductrice. Cette feuille poreuse conductrice comprend principalement des fibres de carbone qui sont jointes aux intersections. La feuille poreuse conductrice ne se casse pas dans un essai de flexion en trois points. La pile à combustible à polymère solide est pourvue de la feuille poreuse conductrice à titre de substrat d'électrode à diffusion de gaz. La feuille poreuse conductrice peut être fabriquée sous la forme de fibres de carbone courbes par jonction des intersections de fibres précurseurs, qui comprennent un premier matériau organique carbonisable et un second matériau organique carbonisable qui est différent du premier matériau organique carbonisable, à l'aide du premier matériau organique carbonisable ou du second matériau organique carbonisable, puis carbonisation du produit ainsi obtenu.
PCT/JP2016/083179 2015-11-09 2016-11-09 Feuille poreuse conductrice, pile à combustible à électrolyte polymère, et procédé de fabrication de feuille poreuse conductrice WO2017082276A1 (fr)

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CN114976048A (zh) * 2022-05-12 2022-08-30 上海碳际实业集团有限公司 一种燃料电池气体扩散层专用碳纤维纸的连续化生产工艺
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CN114976048A (zh) * 2022-05-12 2022-08-30 上海碳际实业集团有限公司 一种燃料电池气体扩散层专用碳纤维纸的连续化生产工艺
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CN116377606A (zh) * 2023-04-25 2023-07-04 武汉纺织大学 一种螺旋形抗菌纳米纤维及其制备方法和应用
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