WO2011070893A1 - Tissu non tisse de fibre de carbone souple - Google Patents

Tissu non tisse de fibre de carbone souple Download PDF

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Publication number
WO2011070893A1
WO2011070893A1 PCT/JP2010/070334 JP2010070334W WO2011070893A1 WO 2011070893 A1 WO2011070893 A1 WO 2011070893A1 JP 2010070334 W JP2010070334 W JP 2010070334W WO 2011070893 A1 WO2011070893 A1 WO 2011070893A1
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Prior art keywords
nonwoven fabric
carbon fiber
fiber nonwoven
flexible carbon
resin
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PCT/JP2010/070334
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English (en)
Japanese (ja)
Inventor
直一 佐々木
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日清紡ホールディングス株式会社
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Application filed by 日清紡ホールディングス株式会社 filed Critical 日清紡ホールディングス株式会社
Priority to JP2011545157A priority Critical patent/JP5672239B2/ja
Priority to CA2782274A priority patent/CA2782274A1/fr
Priority to EP10835815.1A priority patent/EP2511408A4/fr
Priority to US13/513,798 priority patent/US8993199B2/en
Priority to CN201080055628.1A priority patent/CN102652192B/zh
Publication of WO2011070893A1 publication Critical patent/WO2011070893A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28038—Membranes or mats made from fibers or filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • 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
    • 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
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/681—Spun-bonded nonwoven fabric

Definitions

  • the present invention relates to a flexible carbon fiber nonwoven fabric.
  • nonwoven fabrics made of ultrafine carbon fibers have been widely used as impurity removal filters, fuel cell electrode members such as gas diffusion layers and electrode catalysts for fuel cells (see, for example, Patent Documents 1 to 7).
  • these non-woven fabrics are extremely fragile because carbon fibers that are inherently weak to bending are made extremely fine, and have a substantial working strength. For this reason, the ultra-fine carbon fiber nonwoven fabric has a defect that a member cannot be constituted by itself.
  • CNT carbon nanotubes
  • nonpatent literature 1 flexible carbon fiber nanofiber is reported (nonpatent literature 1). This is made by dissolving phenolic resin, high molecular weight polyvinyl butyral using methanol as a solvent, pyridine and sodium carbonate (Na 2 CO 3 ) as electrolytic substances, and electrospinning them to obtain a nanofiber nonwoven fabric. It was obtained by crosslinking with formaldehyde in a solution, baking after neutralization and washing. However, this manufacturing process is not only complicated, but the obtained carbon fiber nanofiber shows a certain degree of flexibility, but it breaks when folded in half, and it can still be said that it is still sufficient in terms of flexibility. There wasn't.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a flexible carbon fiber nonwoven fabric that is strong in bending, flexible, and has good workability, and a simple manufacturing method thereof.
  • the present inventor has mixed at least two kinds of organic components of a polymer substance capable of electrospinning and an organic compound different from that, and a transition metal.
  • the non-woven fabric obtained by electrospinning the resulting composition is further carbonized to find that a flexible carbon fiber non-woven fabric is obtained that is strong enough to bend to the extent that it does not break even when folded in half, and the present invention is completed. I let you.
  • a flexible carbon fiber nonwoven fabric obtained by carbonizing a nonwoven fabric obtained by electrospinning a composition comprising a polymer material capable of electrospinning, an organic compound different from the polymer material, and a transition metal.
  • the polymer substance is a polyacrylonitrile resin, a polyester resin, a polyurethane resin, a polyethylene resin, a polypropylene resin, a polyacrylic resin, a polyether resin, a polyvinylidene chloride resin, a polyvinyl resin, or a polyamide resin.
  • 1 or 2 flexible carbon fiber nonwoven fabrics one or more selected from polyimide resins and polyamideimide resins, 4).
  • Non-woven 5.
  • a gas diffusion layer for a fuel cell comprising the flexible carbon fiber nonwoven fabric of any one of 1 to 9, 12
  • a flexible carbon fiber characterized in that a non-woven fabric is obtained by electrospinning a composition comprising a polymer material capable of electrospinning, an organic compound different from the polymer material, and a transition metal, and the non-woven fabric is carbonized.
  • a method for producing a nonwoven fabric is provided.
  • the flexible carbon fiber nonwoven fabric which was flexible and was rich in workability can be provided as a result of being able to give the characteristic strong to bending to the ultra-fine carbon fiber which was not able to be achieved by the conventional method. Since the flexible carbon fiber nonwoven fabric of the present invention does not require the conventional reinforcing treatment as described above, the flexible carbon fiber nonwoven fabric can be used for various applications while still being a thin nonwoven fabric. Moreover, since the process using reagents, such as an acid, an alkali, a hardening
  • Such a flexible carbon fiber nonwoven fabric alone is a fuel cell electrode member such as a gas diffusion layer, other electrode materials, a support for a catalyst or hydrogen storage particles, a chemical and heat resistant filter, a heat conductor, It can be suitably used as a heat radiating material, a heat insulating material, a filler, an adsorbent, a sound absorbing material and the like.
  • the carbon fiber which comprises the flexible carbon fiber nonwoven fabric of this invention has many micropores on the surface, it can be used also as a hydrogen storage material.
  • the flexible carbon fiber nonwoven fabric of the present invention is advantageous when filling a high-pressure container for storing hydrogen.
  • the nonwoven fabric of the present invention is rolled to form a high density.
  • it is easy to secure a flow path suitable for taking in and out of hydrogen by using a gap between fibers.
  • FIG. 1 is an electron micrograph of a carbon fiber nonwoven fabric obtained in Example 1.
  • FIG. It is a figure which shows the transmission electron micrograph of the fiber which comprises the carbon fiber nonwoven fabric obtained in Example 1.
  • FIG. It is a figure which shows the electron micrograph of the bending part after the bending test
  • FIG. It is a figure which shows the electron micrograph of the bending part after the bending test
  • FIG. It is a figure which shows the relationship between the hydrogen adsorption amount per 1g and measurement pressure (mmHg) in Example 10 and Comparative Example 6.
  • FIG. It is a figure which shows the relationship between the hydrogen adsorption amount per 1g and measurement pressure (mmHg) in Example 10 and Comparative Example 6.
  • the flexible carbon fiber nonwoven fabric according to the present invention is obtained by carbonizing a nonwoven fabric obtained by electrospinning a composition containing a polymer substance capable of electrospinning, an organic compound different from the polymer substance, and a transition metal.
  • the polymer material that can be electrospun is not particularly limited, and can be appropriately selected from conventionally known polymer materials that can be electrospun. Specific examples include polyacrylonitrile resins, polyester resins, polyurethane resins, polyethylene resins, polypropylene resins, polyacrylic resins, polyether resins, polyvinylidene chloride resins, polyvinyl resins, polyamide resins.
  • Polyimide resins polyamideimide resins, and the like. These may be used alone or in combination of two or more. Among these, in consideration of further increasing the bending strength of the obtained carbon fiber nonwoven fabric, a polymer substance containing a nitrogen atom in its molecule is preferable, and a polyacrylonitrile resin is particularly preferable.
  • the above-described polymer material capable of electrospinning and an organic compound generally used as a carbon precursor are used to develop the carbon fiber nonwoven fabric obtained in order to develop flexibility and toughness that does not break even when bent. It is necessary to use together.
  • the electrospinable polymer serves as a “tie”, so that the electrospinning as a whole can be achieved. It becomes possible, and the development of the graphene sheet in the carbon fiber constituting the ultrafine carbon fiber nonwoven fabric to be obtained can be prevented to obtain a carbon fiber that is strong against bending.
  • an organic compound various compounds conventionally used as a carbon precursor material can be used, which are different from the above-described polymer substances. Specific examples thereof include phenolic resins, epoxy resins, melamine resins, urea resins, polycarbodiimides, pitches, celluloses, cellulose derivatives, lignins, and the like. These may be used alone or in combination of two or more. Also good. In addition, when using what does not contain a nitrogen atom as said high molecular substance, it is preferable that the said organic compound contains a nitrogen atom for the same reason as the above-mentioned.
  • a transition metal is essential for the expression of the softness
  • the carbon fiber nonwoven fabric can be provided with flexibility and toughness that are not damaged even when bent.
  • transition metals include, but are not limited to, titanium, cobalt, iron, nickel, copper, zirconia, platinum, and the like, and titanium, iron, and cobalt are particularly preferable. These may be used alone or in combination of two or more.
  • transition metals are preferably used in the form of complexes, salts, hydroxides, sulfides and organic oxides.
  • tetraalkoxytitanium such as tetra-n-butoxytitanium, titanium (III) chloride, titanium chloride ( IV) organic acid salts such as titanium halides and titanium lactate ammonium salts
  • Cobalt halides such as cobalt (II) iodide and cobalt (II) iodate, cobalt (II) acetate, organic acid cobalt such as cobalt (II) octylate, cobalt hydroxide (II), cobalt nitrate (II) Cobalt (III) nitrate; iron (II) chloride, iron (III
  • the blending amount of the polymer substance, the organic compound and the transition metal is not particularly limited as long as the composition can be electrospun. 0.0 to 15 parts by mass, especially 1.5 to 15 parts by mass, 1.0 to 15 parts by mass of organic compound, particularly 1.5 to 15 parts by mass, and 0.1 to 2 parts by mass of transition metal (as the metal content) In particular, those containing 0.1 to 1.5 parts by mass are preferred.
  • the preparation method of the said composition is arbitrary, What is necessary is just to mix said each component by a conventional method. In that case, the blending order of each component is arbitrary.
  • an ultrafine fiber nonwoven fabric is obtained using electrospinning, it is necessary to use a solvent for preparing a dope for electrospinning.
  • a solvent capable of dissolving it can be appropriately selected and used depending on the resin to be used.
  • These solvents may be used alone or in combination of two or more. The mixing order of these solvents is also arbitrary, and they may be mixed together with the above components or added after the preparation.
  • the electrospinning method is a method in which a dope for electrospinning (electrospinning solution) charged in an electric field is spun and the dope is ruptured by the repulsive force of the electric charge to form a very fine fibrous material made of resin. It is. Specifically, when the nozzle for ejecting dope is one electrode, the collector is the other electrode, and a high voltage of several thousand to several tens of thousands of volts is applied to the dope, the dope is ejected from the nozzle, and a high-speed jet is generated in the electric field. And it becomes ultrafine fiber by bending and expansion
  • electrospinning electrospinning solution
  • the obtained ultrafine fiber nonwoven fabric is fired to obtain an ultrafine carbon fiber nonwoven fabric.
  • the ultrafine fiber nonwoven fabric obtained using a polymer capable of being infusibilized may be subjected to curing and infusibilization treatment by oxidizing the fiber surface as in the prior art.
  • the heating temperature is not particularly limited as long as it can be made infusible, but usually the temperature is raised from room temperature to about 300 ° C. over about 2 to 10 hours, and then at the same temperature for 30 minutes to 3 minutes. A method of holding for about an hour is used.
  • the ultrafine fiber nonwoven fabric obtained above is bonded to the fibers by melting them gradually by heating them to the firing temperature of about 800 to 1,500 ° C.
  • the rate of temperature increase is arbitrary, and can be set to about 1 to 10 ° C./min, for example, and does not require strict temperature control.
  • the ultrafine carbon fiber nonwoven fabric of the present invention thus obtained is a flexible carbon fiber nonwoven fabric that is strong against bending so that it does not break even when folded in half. Further, this flexibility is maintained even after removing metal atoms from the obtained carbon fiber nonwoven fabric. From this, it is considered that the transition metal has an action of constructing a structure strong against bending during the carbonization process. Removal of metal atoms can be performed by acid treatment, for example. This acid treatment can be performed by exposing the carbon fiber nonwoven fabric to a mixed acid obtained by mixing or mixing inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid. Therefore, what is necessary is just to remove the metal part by an acid treatment, when using the carbon fiber nonwoven fabric of this invention for the use which a metal part has a bad influence.
  • the fiber diameter is preferably 0.1 to 15 ⁇ m, preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 1 ⁇ m, and measured by a bubble point method.
  • the pore diameter of the carbon fiber is preferably 5 ⁇ m or less, the surface pore diameter is preferably 0.4 to 50 nm, and the surface micropore (2 nm or less) area is preferably 27 to 2,700 m 2 / g.
  • the BET specific surface area is preferably 30 to 3,000 m 2 / g.
  • the basis weight is preferably 0.3 to 100 g / m 2
  • the thickness is preferably 5 to 500 ⁇ m
  • the bulk density is preferably 0.06 to 0.3 g / cm 3 .
  • the bending resistance of the nonwoven fabric measured by the B method (slide method) described in JIS L 1096 is preferably 0.0005 to 50 mN ⁇ cm.
  • the nonwoven fabric measured by the A method (fragile type method) described in JIS L 1096 is preferable.
  • the gas permeability is preferably 0.5 to 300 ml / sec / cm 2 .
  • the ratio Id between the peak intensity Id near 1,355 cm ⁇ 1 and the peak intensity Ig near 1,580 cm ⁇ 1 which indicates the degree of graphitization measured by Raman spectroscopy.
  • / Ig is preferably in the range of 0.7 to 1.3. This range means that the carbon fiber nonwoven fabric is more excellent in flexibility because the crystal structure of graphite is disordered and close to amorphous amorphous carbon.
  • the fiber diameter and the thickness of the nonwoven fabric were measured by the following methods.
  • Example 1 (1) Production of electrospinning solution Polyacrylonitrile (manufactured by Mitsubishi Chemical Corporation, Valex) (hereinafter referred to as PAN): 2.7 Phenolic resin (manufactured by Gunei Chemical Industry Co., Ltd., PSK-2320) (hereinafter Ph): 3.0 Titanium (IV) butoxide (manufactured by Aldrich): 3.5 Dimethylformamide (Wako Pure Chemical Industries, Ltd., special grade): 90.8
  • the electrospinning solution was prepared by mixing and dissolving at a mass ratio of (2) Electrospinning The electrospinning solution obtained above was set in an electrospinning apparatus (manufactured by Fuence, ESP-2300), needle outlet diameter 0.5 mm, applied voltage 17 kV, extrusion pressure 7 kPa, relative humidity Electrospinning was performed at 50% (25 ° C.) to obtain an ultrafine fiber nonwoven fabric in which long fibers having a fiber diameter of about 600 nm were laminated.
  • Example 2 (1) Synthesis of polyacrylonitrile-polymethacrylic acid copolymer 30.93 g of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), 4.07 g of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 300 mL of pure water. A solution in which 100 mg of potassium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 50 mL of pure water was charged into a flask and deaerated (oxygen) by bubbling nitrogen gas and then heated to 70 ° C. Was added with stirring.
  • PAN-MAA polyacrylonitrile-polymethacrylic acid copolymer
  • PAN-MAA polyacrylonitrile-polymethacrylic acid copolymer
  • the electrospinning solution was prepared by mixing and dissolving at a mass ratio of (3)
  • Electrospinning Electrospinning was performed under the same conditions as in Example 1 to obtain an ultrafine fiber nonwoven fabric in which long fibers having a fiber diameter of about 200 nm were laminated.
  • Example 3 (1) Preparation of electrospinning solution PAN: 15 Ph: 15 Titanium tetrachloride (IV) (manufactured by Aldrich): 4.0 Dimethylformamide (Wako Pure Chemical Industries, Ltd., special grade): 66
  • the electrospinning solution was prepared by mixing and dissolving at a mass ratio of
  • Electrospinning Electrospinning was performed under the same conditions as in Example 1 to obtain an ultrafine fiber nonwoven fabric in which long fibers having a fiber diameter of about 15 ⁇ m were laminated.
  • Example 4 (1) Preparation of electrospinning solution PAN: 1.5 Ph: 1.5 Cobalt (II) chloride (manufactured by Aldrich): 0.4 Dimethylformamide (Wako Pure Chemical Industries, Ltd., special grade): 96.6
  • the electrospinning solution was prepared by mixing and dissolving at a mass ratio of
  • Electrospinning Electrospinning was performed under the same conditions as in Example 1 to obtain an ultrafine fiber nonwoven fabric in which long fibers having a fiber diameter of about 500 nm were laminated.
  • the fiber diameter was about 400 nm.
  • the thickness of the nonwoven fabric was 20 ⁇ m.
  • Example 5 (1) Preparation of electrospinning solution PAN: 1.5 Ph: 1.5 Iron (III) chloride (manufactured by Aldrich): 0.5 Dimethylformamide (Wako Pure Chemical Industries, Ltd., special grade): 96.5
  • the electrospinning solution was prepared by mixing and dissolving at a mass ratio of
  • Electrospinning Electrospinning was performed under the same conditions as in Example 1 to obtain an ultrafine fiber nonwoven fabric in which long fibers having a fiber diameter of about 500 nm were laminated.
  • the fiber diameter was about 400 nm.
  • the thickness of the nonwoven fabric was 20 ⁇ m.
  • the ultrafine carbon fiber nonwoven fabrics obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to bending inspection, bending inspection after concentrated hydrochloric acid treatment (for Examples 1 to 5), specific surface area measurement, and Raman analysis. The method was used. The results are shown in Table 2.
  • (1) Bending inspection Each ultrafine carbon fiber nonwoven fabric (sample size: 10 cm ⁇ 10 cm) obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was folded in two, and sandwiched between two stainless steel plates, 98 kPa ( By applying a load of 1 kgf / cm 2 ), it was observed whether or not the nonwoven fabric broke.
  • FIG. 4 shows an electron micrograph of the folded portion of the ultrafine carbon fiber nonwoven fabric obtained in Example 1, and FIG.
  • Example 6 (1) Preparation of electrospinning solution PAN-MAA prepared in Example 2: 1.5 Ph: 1.5 Titanium tetrachloride (2.7): 2.7 Dimethylformamide (Wako Pure Chemical Industries, Ltd., special grade): 94.3 The electrospinning solution was prepared by mixing and dissolving at a mass ratio of (2) Electrospinning Electrospinning was performed under the same conditions as in Example 1 to obtain an ultrafine fiber nonwoven fabric in which long fibers having a fiber diameter of about 300 nm and a thickness of about 6 ⁇ m were laminated. (3) Curing / Firing (Carbonization) Continuous Treatment Under the following conditions, the ultrafine fiber nonwoven fabric after electrospinning was heat-treated to obtain an ultrafine carbon fiber nonwoven fabric.
  • Example 7 An ultrafine carbon fiber nonwoven fabric was prepared under the same conditions as in Example 6 except that the thickness of the nonwoven fabric was changed to 110 ⁇ m during electrospinning. Next, curing and baking were performed under the same conditions as in Example 6 to obtain an ultrafine carbon fiber nonwoven fabric having a fiber diameter of about 200 nm and a thickness of about 100 ⁇ m.
  • Example 8 An ultrafine carbon fiber nonwoven fabric was produced under the same conditions as in Example 6 except that the thickness of the nonwoven fabric was changed to 550 ⁇ m during electrospinning. Next, curing and baking were performed under the same conditions as in Example 6 to obtain an ultrafine carbon fiber nonwoven fabric having a fiber diameter of about 200 nm and a thickness of about 500 ⁇ m.
  • Example 9 An ultrafine carbon fiber nonwoven fabric was produced under the same conditions as in Example 6 except that the thickness of the nonwoven fabric was 500 ⁇ m during electrospinning. Next, curing and firing were performed under the same conditions as in Example 6 to obtain a carbon fiber nonwoven fabric having a fiber diameter of about 200 nm and a thickness of about 450 ⁇ m. Subsequently, this nonwoven fabric was pressed and the thickness was compressed to 300 ⁇ m.
  • Carbonization treatment Carbonization treatment was performed under the same conditions as in Example 1 except that the holding temperature was 1,500 ° C.
  • the ultrafine carbon fiber nonwoven fabric after the treatment was observed with an electron microscope, and it was confirmed that the fibers were not melted and joined.
  • the fiber diameter was about 200 nm.
  • the thickness of the nonwoven fabric was about 100 ⁇ m.
  • the non-woven fabric after firing was very brittle, and it was impossible to carry out measurement of maximum pore diameter, bending resistance and gas permeation by the bubble point method described later.
  • the treated nonwoven fabric was observed with an electron microscope, and it was confirmed that there was no change in the fiber shape and the fibers were not melted and joined.
  • the ultrafine carbon fiber nonwoven fabric after the treatment was observed with an electron microscope, and it was confirmed that the fibers were not melted and joined.
  • the fiber diameter was about 200 nm.
  • the thickness of the nonwoven fabric was about 100 ⁇ m.
  • the non-woven fabric after firing was very brittle, and it was impossible to measure the maximum pore diameter, the bending resistance, and the gas permeation by the bubble point method.
  • Example 10 Hydrogen adsorption measurement of ultrafine carbon fiber nonwoven fabric 150 mg of the ultrafine carbon fiber nonwoven fabric crushed in Example 1 was subjected to hydrogen adsorption isothermal at 77K using a specific surface area measuring device (Bellsorb Max, manufactured by Bell). The curve was measured. From the hydrogen adsorption volume (cm 3 / g ⁇ STP, STP: 101.325 kPa, gas volume converted to 0 ° C. (273 K)) obtained by the measurement, the hydrogen adsorption amount per 1 g was obtained, and the measurement pressure (mmHg) and Was plotted on a graph. The results are shown in FIG.
  • the hydrogen adsorption amount at a pressure of 760 mmHg was about 3.6 wt% / g for the activated carbon
  • the ultrafine carbon fiber nonwoven fabric was about 4.0 wt% / g.
  • the value was as high as g.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

L'invention concerne un tissu non tissé de fibre de carbone souple qui résiste à la flexion, qui est souple, et qui présente une excellente aptitude au traitement. Ledit tissu non tissé de fibre de carbone souple est obtenu par carbonisation d'un tissu non tissé que l'on obtient par électro-filage d'une composition contenant: une matière polymère que l'on peut électrofiler, par exemple des résines de polyacrylonitrile; un composé organique, différent de ladite matière polymère, par exemple des résines phénoliques; et un métal de transition
PCT/JP2010/070334 2009-12-09 2010-11-16 Tissu non tisse de fibre de carbone souple WO2011070893A1 (fr)

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JP2011545157A JP5672239B2 (ja) 2009-12-09 2010-11-16 フレキシブル炭素繊維不織布
CA2782274A CA2782274A1 (fr) 2009-12-09 2010-11-16 Tissu non tisse de fibre de carbone souple
EP10835815.1A EP2511408A4 (fr) 2009-12-09 2010-11-16 Tissu non tisse de fibre de carbone souple
US13/513,798 US8993199B2 (en) 2009-12-09 2010-11-16 Flexible carbon fiber nonwoven fabric
CN201080055628.1A CN102652192B (zh) 2009-12-09 2010-11-16 柔性碳纤维非织造布

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CN113600033B (zh) * 2021-07-30 2022-09-02 南通大学 一种酚醛基超亲水碳纳米纤维网膜的制备方法

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JPWO2011070893A1 (ja) 2013-04-22
US8993199B2 (en) 2015-03-31
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