WO2022215809A1 - Procédé de fabrication d'une fibre de carbone revêtue d'un catalyseur métallique, et fibre de carbone pour la production d'une électrode fabriquée par ce procédé - Google Patents

Procédé de fabrication d'une fibre de carbone revêtue d'un catalyseur métallique, et fibre de carbone pour la production d'une électrode fabriquée par ce procédé Download PDF

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WO2022215809A1
WO2022215809A1 PCT/KR2021/009270 KR2021009270W WO2022215809A1 WO 2022215809 A1 WO2022215809 A1 WO 2022215809A1 KR 2021009270 W KR2021009270 W KR 2021009270W WO 2022215809 A1 WO2022215809 A1 WO 2022215809A1
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metal catalyst
carbon fiber
coated
precursor
heat treatment
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PCT/KR2021/009270
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Korean (ko)
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채한기
백종범
김석진
이가현
이정은
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울산과학기술원
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01D5/04—Dry spinning methods
    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
    • 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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
    • 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
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • 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
    • 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

Definitions

  • the present invention relates to a method for manufacturing a carbon fiber coated with a metal catalyst and a carbon fiber for manufacturing an electrode prepared thereby, specifically, a metal catalyst in the form of a metal ion or a ligand bound to a metal ion on the surface of the polymer carbon fiber. It relates to a method for producing a carbon fiber having a uniform morphology and excellent mechanical and electrochemical properties by coating the carbon fiber, and to a carbon fiber for manufacturing an electrode produced thereby.
  • An electrochemical reaction can be said to be a process of converting electrical energy into chemical energy using electrical energy.
  • a chemical reaction (oxidation/reduction reaction) occurs through the movement of electrons between substances, and as it begins to be used as a means of converting and storing energy, with the revival of eco-friendly energy, carbon such as fuel cells, green hydrogen (hydrolyzed hydrogen) production, carbon dioxide reduction, etc. Attempts to reduce energy are being studied a lot, and commercialization is actually taking place.
  • a metal catalyst was used to lower the energy of an electrochemical reaction, and platinum was used as the metal.
  • the platinum catalyst has a low overvoltage (meaning the generation of additional applied voltage or dissipated energy than the theoretical reaction voltage) and high efficiency with a fast reaction rate.
  • the surface area decreases dramatically as the size of a single nano-particle increases due to the gradual agglomeration over time, against the high degree of dispersibility, resulting in a significant deterioration in performance.
  • the inventors of the present invention have previously studied a method for producing a carbon fiber supported with a metal catalyst. More specifically, in order to support the metal catalyst on the carbon fiber, the metal catalyst is first mixed with the polymer carbon to prepare a spinning solution, and then morphologically uniform and excellent in the form of a fiber through direct dry/wet spinning or wet spinning. It was confirmed that the chemical properties were shown. However, it was confirmed that these carbon fibers have a structure in which relatively many catalysts are wasted because they cannot be used for catalytic reactions as metal particles are evenly spread therein.
  • the inventors of the present invention prepare a carbon fiber on which a metal catalyst is supported, but the metal catalyst is coated so that it is distributed only on the outer surface of the carbon fiber, and the inside of the carbon fiber is formed of polymer carbon to increase mechanical properties.
  • the invention related to a method for manufacturing carbon fibers and carbon fibers for manufacturing electrodes produced thereby has been completed.
  • Patent Document 1 Korean Patent Laid-Open No. 10-2009-0041135
  • the present invention is morphologically uniform and excellent mechanical properties and electrochemical properties by coating a metal catalyst in the form of a metal ion or a ligand bound to a metal ion on the surface of a polymer carbon fiber.
  • An object of the present invention is to provide a method for producing a carbon fiber having
  • the method for producing a carbon fiber coated with a metal catalyst comprises the steps of: preparing a precursor fiber including a carbon fiber precursor and an organic solvent; impregnating the precursor fiber in a coating solution containing a metal catalyst in the form of a metal ion or a ligand bound to a metal ion; coating the metal catalyst by heating and stretching the precursor fiber impregnated in the coating solution; and heat-treating the precursor fiber coated with the metal catalyst under an inert gas atmosphere.
  • the carbon fiber precursor may have a molar mass of 100,000 to 750,000 g/mole.
  • the carbon fiber precursor is polyacrylonitrile (PAN), petroleum / coal-based hydrocarbon residue pitch (Pitch), cellulose (Cellulose), polyamic acid (Polyamic acid), polyimide (polyimide, PI) , polybenzimidazole (polybenzimidazole, PBI) and polyvinyl alcohol (Polyvinyl alcohol, PVA) selected from the group consisting of single or two or more types may be combined.
  • PAN polyacrylonitrile
  • Pitch petroleum / coal-based hydrocarbon residue pitch
  • cellulose Cellulose
  • polyamic acid Polyamic acid
  • polyimide polyimide, PI
  • polybenzimidazole polybenzimidazole
  • PVA polyvinyl alcohol
  • the organic solvent may be at least one selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), and methanol.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethylsulfoxide
  • NMP N-Methyl-2-pyrrolidone
  • the step of preparing the precursor fiber may be performed by dry-jet wet spinning or wet spinning.
  • the metal catalyst is a metal chloride (X a Cl b ), metal acetyl acetonate (X a (acac) b ) and a ferrician compound (X a CN b ), X a Cl b (NH 3 ) c
  • the group consisting of It may be at least one selected from
  • X is one selected from the group consisting of aluminum, chromium, iron, zinc, rhodium, gold, silver, indium, tin, tungsten, osmium, antimony, iridium, rhenium, copper, cobalt, nickel, ruthenium and palladium may be more than one species.
  • the metal catalyst may be coordinated with at least one selected from the group consisting of phenanthroline, oleate, diethyl triamine and ethylenediaminetetraacetic acid (EDTA). .
  • the metal catalyst may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the carbon fiber precursor.
  • the coating of the metal catalyst may be heated and elongated within the range of 50 to 300 °C.
  • the inert gas may be at least one gas selected from the group consisting of helium, nitrogen, argon, neon, and krypton.
  • the precursor fiber may be carbonized by heat treatment within the range of 200 to 3000 °C.
  • the precursor fiber may be carbonized by heat treatment within the range of 1200 to 1800 °C.
  • the precursor fiber may be carbonized by heat treatment by applying a tension of 0.1 to 10.0 MPa per fiber.
  • the present invention further discloses a carbon fiber coated with a metal catalyst prepared by the method for producing a carbon fiber coated with a metal catalyst according to the present invention.
  • the method for producing a carbon fiber coated with a metal catalyst of the present invention is prepared by coating a metal catalyst in the form of a metal ion or in a form in which a ligand is bound to a metal ion on the surface of the polymer carbon fiber. There is an effect of producing a carbon fiber exhibiting uniform and excellent mechanical and electrochemical properties.
  • the carbon fiber coated with the metal catalyst prepared according to the method for producing the carbon fiber coated with the metal catalyst of the present invention can not only increase the area with a small amount of energy, but also the metal catalyst and the carbon fiber are integrated to stably use the metal catalyst. Since it exhibits stable electrochemical properties even in water for a long period of time by supporting it, it has the effect of being used as a water electrolytic electrode.
  • FIG. 1 is a flowchart illustrating each step of the method for producing a carbon fiber coated with a metal catalyst of the present invention.
  • Figure 2 shows a series of steps of the method for producing a carbon fiber coated with a metal catalyst of the present invention.
  • FIG. 3 is a schematic view showing the manufacturing process of the dry-wet spinning and wet spinning of the present invention.
  • FIG. 4 is a view showing the structure of a cross-section of a carbon fiber according to an embodiment and a comparative example of the present invention.
  • FIG. 5 is a view showing a TEM image of the carbon fiber according to an embodiment and a comparative example of the present invention taken.
  • FIG. 6 is a view illustrating an SEM image of carbon fibers according to an embodiment and a comparative example of the present invention.
  • FIG. 7 is a graph showing the measurement results of X-ray diffraction analysis (X-Ray Diffraction, XRD) for each heat treatment temperature of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention.
  • HER hydrogen evolution reaction
  • FIG. 9 is a graph showing the mass activity conversion results of carbon fibers according to an embodiment of the present invention and a comparative example at the same heat treatment temperature.
  • FIG 10 is a graph showing the measurement results of X-ray diffraction analysis (X-Ray Diffraction, XRD) according to the tension during the manufacture of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention.
  • FIG 11 is a graph showing the change in the diameter of the carbon fiber according to the tension during the manufacture of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention, the amount of the remaining metal catalyst derived by thermogravimetric analysis (TGA), and the hydrogen generation test result. is shown graphically.
  • the inventors of the present invention prepare a carbon fiber supported with a metal catalyst in the form of a metal ion or in a form in which a ligand is bound to a metal ion (a form of a metal precursor bound to a ligand), but the metal catalyst is coated so that it is distributed only on the outer surface of the carbon fiber and the carbon fiber was formed with polymer carbon to complete the present invention, and the degree of metal elution, electrochemical properties, and stability of the electrode were confirmed for the carbon fiber of the present invention prepared accordingly.
  • the present invention is to overcome the problems of energy economy and stability of the existing electrode by utilizing an electrochemical reaction. By supporting and radiating an organic precursor metal including nitrogen, the dispersion of the metal catalyst is increased, and the aggregation phenomenon of the catalyst is reduced. It was confirmed that it has an effect of preventing separation from the support.
  • the present inventors have devised the following invention as a result of research in order to solve the above-mentioned problems.
  • the present specification includes the steps of preparing a precursor fiber comprising a carbon fiber precursor and an organic solvent; impregnating the precursor fiber in a coating solution containing a metal catalyst in the form of a metal ion or a ligand bound to a metal ion; coating the metal catalyst by heating and stretching the precursor fiber impregnated in the coating solution; and heat-treating the precursor fiber coated with the metal catalyst under an inert gas atmosphere.
  • the method for producing a carbon fiber coated with a metal catalyst of the present invention comprises the steps of preparing a precursor fiber including a carbon fiber precursor and an organic solvent; impregnating the precursor fiber in a coating solution containing a metal catalyst in the form of a metal ion or a ligand bound to a metal ion; coating the metal catalyst by heating and stretching the precursor fiber impregnated in the coating solution; and heat-treating the precursor fiber coated with the metal catalyst under an inert gas atmosphere.
  • Figure 2 shows a series of steps of the method for producing a carbon fiber coated with a metal catalyst of the present invention.
  • the precursor fiber including the carbon fiber precursor and the organic solvent is impregnated in the coating solution containing the metal catalyst by moving through a roller or guide roller in the form of a filament, and the precursor fiber impregnated in the coating solution is a roller
  • the metal catalyst is coated on the outer surface of the precursor fiber while being heated and drawn through a heating roller, and then finally moved through a roller or a guide roller to be heat-treated under an inert gas atmosphere.
  • the present invention may include the step of preparing a precursor fiber including a carbon fiber precursor and an organic solvent.
  • the carbon fiber precursor of the present invention preferably has a molar mass of 100,000 to 750,000 g/mole.
  • the molar mass of the carbon fiber precursor is less than 100,000 g/mole, there is a problem in that mechanical properties are relatively deteriorated when the carbon fiber is manufactured. There is a problem in that it is difficult to prepare a uniform spinning solution due to the aggregation phenomenon of the precursor polymer.
  • the carbon fiber precursor of the present invention it is preferable to use a fiber-like material in which the mass content of carbon element after the carbonization process can have 90% or more.
  • the carbon fiber precursor is polyacrylonitrile (PAN), petroleum / coal-based hydrocarbon residue pitch (Pitch), cellulose (Cellulose), polyamic acid (Polyamic acid), polyimide (polyimide, PI) ), polybenzimidazole (PBI) and polyvinyl alcohol (Polyvinyl alcohol, PVA) may be an organic polymer selected from the group consisting of alone or two or more complexes, but if it can be used in the art However, the present invention is not limited thereto.
  • the organic solvent of the present invention may be at least one selected from the group consisting of DMF (Dimethylformamide), DMAc (Dimethylacetamide), DMSO (Dimethylsulfoxide), NMP (N-Methyl-2-Pyrrolidone), and methanol. It is not
  • a spinning solution is prepared by dissolving the carbon fiber precursor in an organic solvent within a temperature range of 25 to 100 ° C. -jet wet spinning) or wet spinning (Wet spinning) may be performed.
  • the spinning solution may contain 5 to 40% by weight of solids based on the total weight of the spinning solution. For example, when the solid content is less than 5% by weight, there is a limit to the fiber-forming ability of the spinning solution, and on the contrary, when it exceeds 40% by weight, there is a limit to the preparation of a uniform spinning solution, so it is preferable to prepare a spinning solution within the above range.
  • the viscosity of the spinning solution is 50 to 1,000 Pa ⁇ s.
  • the viscosity is less than 50 Pa ⁇ s, there is a limit to the fiber-forming ability of the spinning solution, and conversely, if it exceeds 1,000 Pa ⁇ s, there is a limit to a uniform and stable spinning process.
  • carbon fibers having excellent mechanical properties and easy processing even after heat treatment, high catalytic activity and excellent performance can be obtained by manufacturing fibers through dry or wet spinning.
  • FIG. 3 is a schematic view showing the manufacturing process of the dry-wet spinning and wet spinning of the present invention. More specifically, Figure 3a shows the manufacturing process of the wet spinning of the present invention, Figure 3b is a schematic diagram showing the manufacturing process of the wet spinning of the present invention. Referring to FIG. 3 , it can be seen that in wet spinning and wet spinning, the process of passing through the primary and secondary coagulation baths through rollers or guide rollers is performed.
  • a solvent in which an organic solvent and water are mixed is used in a volume ratio of 3:7 to 1:9, and the temperature can be adjusted within the range of -50 to 100 °C, 2
  • the secondary coagulation bath 2nd coagulation bath
  • water it is preferable to use water as a solvent and to wash the organic solvent from the fibers as much as possible by setting the temperature high. If necessary, the number of baths can be increased to adjust the degree of removing the residual solvent inside the fiber.
  • Dry-wet spinning or wet spinning may be prepared in the form of fibers by discharging at a temperature of -50 to 100° C. in the primary coagulation bath at a rate of 1 to 10 m per minute, but this can be adjusted as needed by those skilled in the art.
  • a step of stabilizing the precursor fiber through heat treatment may be additionally performed.
  • a stabilization process for cyclization it is preferable to go through a stabilization process for cyclization.
  • the fiber in the step of stabilizing the precursor fiber through the heat treatment, the fiber can be stabilized by applying a tension of 0.1 to 40 MPa per fiber and maintaining it within the temperature range of 180 to 350 ° C. for 0.5 to 6 hours.
  • an inert gas such as nitrogen or argon or air, a carbon dioxide mixed gas, oxygen-nitrogen or oxygen-argon mixed gas may be used.
  • the step of stabilizing the precursor fiber through the heat treatment may be omitted.
  • the present invention may include impregnating the precursor fiber in a coating solution containing a metal catalyst in the form of a metal ion or a ligand bound to a metal ion.
  • the impregnation may refer to a process of allowing the precursor fibers to penetrate into the coating solution through a roller or a guide roller.
  • the metal catalyst of the present invention is preferably in the form of a metal ion or a ligand bound to a metal ion, but is not limited thereto.
  • the metal catalyst of the present invention may be metal nanoparticles having an average particle diameter of 1 to 100 nm.
  • the metal catalyst of the present invention is used in the form of metal ions, and more specifically, metal chloride (X a Cl b ), metal acetyl acetonate (X a (acac) b ) and ferrician compound (X a CN b ) ,X a Cl b (NH 3 ) It may be at least one selected from the group consisting of c .
  • a, b, and c are coefficient ratios and may be changed according to the type of metal.
  • X is a metal having excellent solubility in water, and includes aluminum, chromium, iron, zinc, rhodium, gold, silver, indium, tin, tungsten, osmium, antimony, iridium, rhenium, copper, cobalt, nickel, ruthenium, and It may be one selected from the group consisting of palladium.
  • the metal catalyst of the present invention is coordinated with at least one selected from the group consisting of phenanthroline, oleate, diethyl triamine, and ethylenediaminetetraacetic acid (EDTA). may be added.
  • the ligands interact with the polymer chain with respect to the metal having high solubility to prevent the metal catalyst from being dissolved in water.
  • the metal catalyst of the present invention may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the carbon fiber precursor, but this may be adjusted according to process conditions.
  • the step of coagulating the precursor fiber impregnated in the coating solution is additionally performed.
  • the coagulation may be to perform a process of passing through the coagulation bath such as the primary, secondary, through rollers or guide rollers.
  • the coagulation bath preferably contains an organic solvent such as methanol or ethanol at room temperature, but is not limited thereto.
  • the present invention may include coating the metal catalyst by heating and stretching the precursor fiber impregnated in the coating solution.
  • the heating stretching may be a process of stretching the precursor fiber impregnated in the coating solution with heating by using a primary or secondary roller, a heating roller, or high-temperature steam.
  • the metal catalyst may be sufficiently supported or coated on the outer surface of the precursor fiber.
  • the step of coating the metal catalyst by heating and stretching the precursor fiber impregnated in the coating solution of the present invention is preferably performed by heating and stretching within the range of 50 to 300 °C.
  • heating and stretching within the range of 50 to 300 °C.
  • a problem may occur that the metal catalyst is not sufficiently coated on the surface of the precursor fiber. There may be a problem of sticking to the rollers.
  • the present invention may include heat-treating the precursor fiber coated with the metal catalyst under an inert gas atmosphere.
  • the step of heat-treating the precursor fiber coated with the metal catalyst of the present invention under an inert gas atmosphere is a step of carbonizing the precursor fiber coated with the metal catalyst to finally prepare a carbon fiber supported or coated with a metal catalyst.
  • the inert gas of the present invention may be at least one gas selected from the group consisting of helium, nitrogen, argon, neon, and krypton, but is not limited thereto.
  • the inert gas of the present invention may be supplied in the range of 0.5 to 5 L / min in the heat treatment step.
  • heat treatment is preferably performed within the range of 200 to 3000 °C, more preferably heat treatment within the range of 1200 to 1800 °C .
  • the heat treatment temperature is less than 200 ° C, carbonization of the precursor fiber coated with the metal catalyst does not occur sufficiently, which may cause structural instability and reduced conductivity.
  • the heat treatment temperature exceeds 3000 ° C, the metal catalyst Carbonization of the coated precursor fiber may be excessively advanced, causing damage to the fiber itself and deterioration of mechanical properties.
  • the heat treatment temperature in the heat treatment is within the range of 1200 to 1800 ° C.
  • carbonization of the precursor fiber coated with the metal catalyst is sufficiently made to exhibit excellent electrical conductivity.
  • the heat treatment may be appropriately controlled according to the type of metal catalyst under the heat treatment temperature range.
  • the carbonization point varies depending on the type of metal or metal catalyst. It is advisable to proceed while observing.
  • the microstructure of the fiber can be confirmed by X-ray diffraction analysis (XRD), and mechanical properties can be confirmed through a tensile test.
  • the step of heat-treating the precursor fiber coated with the metal catalyst of the present invention under an inert gas atmosphere it is preferable to carbonize the precursor fiber by heat-treating by applying a tension of 0.1 to 10.0 MPa per fiber. It is more preferable to carbonize the precursor fiber by heat treatment by applying a tension of 2.5 to 7.5 MPa per strand. For example, if the tension is less than 0.1 MPa in the heat treatment step, carbonization of the precursor fiber coated with the metal catalyst does not occur sufficiently, which may cause structural instability and reduced conductivity. In this case, excessive carbonization of the precursor fiber coated with the metal catalyst may cause damage to the fiber itself and decrease in catalytic activity due to mechanical properties and ruthenium desorption.
  • the heat treatment of the precursor fiber coated with the metal catalyst of the present invention under an inert gas atmosphere is preferably heat-treated for 1 to 10 hours under the conditions of the temperature and tension, but is not limited thereto.
  • the present invention further discloses a carbon fiber coated with a metal catalyst prepared by the method for producing a carbon fiber coated with a metal catalyst according to the present invention.
  • the carbon fiber coated with such a metal catalyst has excellent electrochemical properties, it can be utilized for manufacturing an electrode required for an electrochemical reaction.
  • the electrochemical reaction includes an oxygen reduction reaction (ORR), a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER), a nitrogen reduction reaction (NRR), and hydrogen oxidation.
  • ORR oxygen reduction reaction
  • HER hydrogen evolution reaction
  • OER oxygen evolution reaction
  • NRR nitrogen reduction reaction
  • hydrogen oxidation There are reactions that can cause electron exchange in the electrolyte, such as hydrogen oxidation reaction (HOR), chlorine evolution reaction (CER), and carbon dioxide reduction reaction (CO2 RR).
  • the water electrolytic electrode made of carbon fiber according to the present invention has the advantage of excellent stability of the electrode regardless of the pH of the electrolyte because the metal catalyst is supported or coated.
  • the present invention prepares a precursor fiber containing a carbon fiber precursor and an organic solvent, and then coats a metal catalyst in the form of a metal ion or a ligand bound to a metal ion on the outer surface of the precursor fiber. Accordingly, metal desorption or elution is small, so that the stability of the metal catalyst can be improved. As a result, the carbon fiber coated with the metal catalyst of the present invention has excellent mechanical properties and electrochemical characteristics, so it can be actively used in a large-area electrochemical reaction device including a water electrolysis electrode. It has a fairly advantageous effect.
  • Example 1 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 1200 °C
  • the solution discharged at a speed of 7 m/min passes through an air gap (air layer) of about 10 mm, passes through 17 m/min roller 1 in the primary coagulation bath, and 17.5 m/min roller 2, 18.5 m in the secondary coagulation bath. It was wound on the winder at 21 m/min via roller 3 /min.
  • the temperature of the primary coagulation bath was 10 °C
  • the temperature of the secondary coagulation bath was 23 °C
  • methanol was used as a non-solvent in the two coagulation baths.
  • RuCl 3 (0.5 g), phenanthroline (1.32 g) and solvent DMF (9.44 g) were mixed and stirred at 50 rpm at room temperature for 6 hours so that RuCl 3 could form a coordinate bond.
  • a precursor fiber which is a filament, unwound from the unwinder at a speed of 3 m/min by roller 1, was impregnated with a coating solution at room temperature through a guide roller.
  • the coating solution passes through three guide rollers and then passes through a coagulation bath filled with methanol at room temperature through 3 m/min roller 2 and 5 m/min roller 3 to pass a polymer containing a metal catalyst in the coating solution.
  • the complex was allowed to coagulate.
  • the precursor fiber which is a filament that has exited the coagulation bath, is wound by roller 4 and heated through a heating roller 1 at 8 m/min, 115 °C, a heating roller 1 at 24 m/min, and a heating roller 2 at 158 °C to increase mechanical properties and orient the molecular chains. has been renewed
  • the metal catalyst-coated precursor fibers were heat treated at 260° C. for 5 hours in an air atmosphere (2 L/min) to stabilize the PAN structure. Afterwards, for carbonization, the metal catalyst-coated precursor fiber was heated to 1200° C. under a nitrogen gas atmosphere, and a tension of 5.0 MPa per fiber was applied for 2 hours, followed by heat treatment for 2 hours. A fiber (hereinafter referred to as 'Example 1') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 2 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 1400 °C
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the metal catalyst-coated precursor fiber was heat-treated at 1400° C. instead of 1200° C. under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 2') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 3 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 1600 °C
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the metal catalyst-coated precursor fiber was heat-treated at 1600° C. instead of 1200° C. under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 3') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 4 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 1700 °C
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the precursor fiber coated with the metal catalyst was heat-treated at 1700°C instead of 1200°C under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 4') was obtained.
  • Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 5 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 1800 ° C.
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the metal catalyst-coated precursor fiber was heat-treated at 1800° C. instead of 1200° C. under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 5') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 6 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 2000 °C
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the metal catalyst-coated precursor fiber was heat-treated at 2000° C. instead of 1200° C. under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 6') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 7 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 2200 °C
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the precursor fiber coated with the metal catalyst was heat-treated at 2200° C. instead of 1200° C. under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 7') was obtained.
  • Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 8 Carbon fiber coated with a metal catalyst when the heat treatment temperature is 2500 °C
  • the metal catalyst of the present invention was prepared in the same manner as in Example 1, except that the metal catalyst-coated precursor fiber was heat-treated at 2500° C. instead of 1200° C. under a nitrogen gas atmosphere.
  • a coated carbon fiber (hereinafter referred to as 'Example 8') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 9 Carbon fiber coated with a metal catalyst when the tension during heat treatment is 2.5 MPa and the heat treatment temperature is 1200° C.
  • Example 9 The same as in Example 1, except that in the carbon fiber heat treatment step, the metal catalyst-coated precursor fiber was heat-treated under a nitrogen gas atmosphere by applying a tension of 2.5 MPa instead of a tension of 5.0 MPa per fiber. It was possible to obtain a carbon fiber coated with the metal catalyst of the present invention (hereinafter referred to as 'Example 9') prepared by the method. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Comparative Example 1 Carbon fiber prepared by spinning a mixed solution containing a carbon fiber precursor and a metal catalyst, and containing a metal catalyst when the heat treatment temperature is 1000 ° C.
  • Stabilized ruthenium fibers are carbonized by applying a tension of 5.0 MPa at 1000 °C for 2 hours under a nitrogen gas atmosphere to obtain carbon fibers having a metal catalyst uniformly distributed inside and outside (hereinafter referred to as 'Comparative Example 1'). could Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • the carbon fiber heat treatment step except that the ruthenium fiber was heat-treated at 1100° C. instead of 1000° C. under a nitrogen gas atmosphere, the carbon fiber was prepared in the same manner as in Comparative Example 1 and the metal catalyst was uniformly distributed inside and outside. (hereinafter referred to as 'Comparative Example 2') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Comparative Example 3 Carbon fiber prepared by spinning a mixed solution containing a carbon fiber precursor and a metal catalyst, and containing a metal catalyst when the heat treatment temperature is 1200 ° C.
  • the ruthenium fiber was heat-treated at 1200° C. instead of 1000° C. under a nitrogen gas atmosphere, it was prepared in the same manner as in Comparative Example 1, and the metal catalyst was uniformly distributed inside and outside the carbon fiber (hereinafter referred to as 'Comparative Example 3') was obtained.
  • Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • the carbon fiber heat treatment step except that the ruthenium fiber was heat-treated at 1300 ° C instead of 1000 ° C in a nitrogen gas atmosphere, the carbon fiber was prepared in the same manner as in Comparative Example 1, and the metal catalyst was uniformly distributed inside and out. (hereinafter referred to as 'Comparative Example 4') was obtained. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Example 5 The same as in Example 1, except that in the carbon fiber heat treatment step, the metal catalyst-coated precursor fiber was heat-treated by applying a tension of 10.0 MPa per fiber instead of a tension of 5.0 MPa per fiber under a nitrogen gas atmosphere. It was possible to obtain a carbon fiber coated with a metal catalyst (hereinafter referred to as 'Comparative Example 5') prepared by this method. Carbon fibers that had undergone carbonization were manufactured as electrodes without special treatment.
  • Thermogravimetric analysis was used to confirm the thermal stability of the fibers and the metal content contained therein.
  • the analysis equipment As the analysis equipment, the Q200 model of TA Instruments of the United States was used, and the analysis was performed at a rate of 10 °C/min.
  • X-ray photoelectron spectroscopy XPS
  • XRD X-ray diffraction
  • Figure 4 shows a structure of a cross-section of a carbon fiber according to an embodiment and a comparative example of the present invention. More specifically, Figure 4a shows the structure of the cross section of the carbon fiber coated with the metal catalyst of Examples 1 to 9, and Figure 4b shows the structure of the cross section of the carbon fiber containing the metal catalyst of Comparative Examples 1 to 4 will be. 4, in the case of the carbon fiber coated with the metal catalyst according to the present invention, it can be confirmed that the metal catalyst is coated with a uniform thickness on the outer surface of the carbon fiber with the circular polymer carbon fiber as the center.
  • a metal catalyst is uniformly included inside and outside the circular polymer carbon fiber by spinning a spinning solution mixed with a carbon polymer and a metal catalyst to form a fiber can be checked
  • metal particles uniformly distributed in the fiber cannot be utilized for the catalytic reaction, so that relatively many catalysts are wasted.
  • an additional process of separately etching the fiber surface through oxygen plasma treatment is required.
  • the metal particles distributed inside the fiber act as a defect in the fiber structure, so that the fiber may break while being used as an electrode.
  • FIG. 5 is a view showing a TEM image of the carbon fiber according to an embodiment and a comparative example of the present invention taken. More specifically, FIG. 5a is a TEM image of a carbon fiber coated with a metal catalyst according to an embodiment of the present invention at a specific temperature, and FIG. 5b is a metal according to a comparative example of the present invention at a specific temperature. It is shown by taking a TEM image of the carbon fiber containing the catalyst.
  • ruthenium which is a metal catalyst, is coated with a uniform thickness on the outer surface of the carbon fiber centered on the polymer carbon fiber.
  • the metal catalyst is uniformly included inside and outside the polymer carbon fiber.
  • FIG. 6 is a view illustrating an SEM image of carbon fibers according to an embodiment and a comparative example of the present invention. More specifically, FIG. 6a shows an SEM image of a carbon fiber coated with a metal catalyst according to an embodiment of the present invention at 1400° C., and FIG. 6b is a metal according to a comparative example of the present invention at 1400° C. It is shown by taking an SEM image of the carbon fiber containing the catalyst. Referring to FIG. 6 , in the case of carbon fiber containing a metal catalyst according to one comparison of the present invention, aggregation of ruthenium particles, which is a metal catalyst, occurs at 1400 ° C.
  • FIG. 7 is a graph showing the measurement results of X-ray diffraction analysis (X-Ray Diffraction, XRD) for each heat treatment temperature of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention.
  • XRD X-ray Diffraction
  • Electrochemical reaction measurements were performed in a standard three-electrode cell with a computer connected to a potential stat (1470E, Solartron, UK).
  • a carbon rod was used as a counter electrode, and an Ag/AgCl electrode dipped in saturated KCl solution was used as a reference electrode.
  • Two methods were used for the catalytic electrode part, one was measured by contacting the copper tape as it is as a fiber, and 4 ⁇ g of the metal catalyst standard was placed on the glassy carbon (GC) in the form of a film on the glassy carbon (GC) by making a powder dispersion. The measurement method was used.
  • the concentration of the dispersion was 5 g/L, and the solvent was a mixed solution containing 20 ⁇ L of Nafion (5%) per 1 mL of ethanol. If the carbon fiber according to a comparative example of the present invention is not well made into a powder or is not well dispersed, it is measured by increasing the dispersibility by O 2 plasma treatment (200 W, 5 min). In the case of hydrogen evolution reaction for reliable evaluation, the evaluation was carried out after nitrogen was injected into the electrolyte for 30 minutes, and 0.5 MH 2 SO 4 and 1.0 M KOH electrolyte were used for performance evaluation in various ranges (pH 0.3 to 14). did. In addition, for a comparative measure of performance, a commercial catalyst (Pt/C, Sigma Aldrich) in which platinum was supported on 20% carbon was used to increase data reliability.
  • Table 1 shows the amount of change in the metal catalyst and the change in electrical conductivity according to the heat treatment temperature of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention.
  • the amount of ruthenium (Ru), a metal catalyst remaining in each heat treatment temperature section was investigated through thermogravimetric analysis (TGA).
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 7
  • Heat treatment temperature (°C) 260 1200 1400 1600 1700 1800 2000 2200 2500 Ru amount (wt. %) 1.64 3.75 4.96 5.21 5.00 4.12 3.07 2.88 2.72
  • Electrical conductivity (S/cm) - 132.81 147.86 170.99 186.62 192.33 231.22 239.77 257.07
  • the amount of ruthenium (Ru) gradually increases as the heat treatment temperature increases, and then it can be confirmed that it gradually decreases around 1700 ° C. This is because the ruthenium particles gradually grew on the outer surface of the carbon fiber during heat treatment and desorption occurred due to the diameter of the reduced fiber. Therefore, from the above experimental results, it can be inferred that ruthenium, the metal catalyst of the carbon fiber coated with the metal catalyst of the present invention, was exposed to the maximum at 1700 °C.
  • the electrical conductivity of the carbon fiber coated with the metal catalyst of the present invention continuously increases as the heat treatment temperature increases, because the crystal structure of carbon inside the fiber develops to facilitate electron transfer. In general, when carbon fiber is used as an electrode, it is known that the electrical conductivity is preferably 150 to 200 S/cm.
  • FIG. 8 is a graph showing the hydrogen evolution reaction (HER) measurement results of carbon fibers according to an embodiment and a comparative example of the present invention. More specifically, Figure 8a is a graph showing the result of measuring hydrogen generation at 20 mA cm -2 of the carbon fiber coated with a metal catalyst according to an embodiment of the present invention, Figure 8b is a comparative example of the present invention A graph showing the results of measuring hydrogen evolution at 20 mA cm -2 of carbon fibers containing a metal catalyst according to Referring to FIG. 8 , the carbon fiber containing the metal catalyst according to one comparison of the present invention shows an overvoltage of 55 to 70 mV for each heat treatment temperature, whereas the metal catalyst according to an embodiment of the present invention is coated.
  • HER hydrogen evolution reaction
  • the carbon fiber exhibits an overvoltage of 70 to 90 mV for each heat treatment temperature (it shows the lowest 89 mV overvoltage when the heat treatment temperature is 1700 °C). That is, it can be seen that in the case of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention, hydrogen generation is stably performed and excellent performance is shown.
  • the mass activity is a current curve calculated based on the mass of the catalyst, and is an index that can compare the electrochemical performance per catalyst usage.
  • the heat treatment temperature is 1200° C.
  • the carbon fiber coated with the metal catalyst according to an embodiment of the present invention is on the outer surface of the fiber compared to the carbon fiber containing the metal catalyst according to a comparative example of the present invention.
  • the ruthenium particles are intensively distributed, the use of unnecessary metal catalysts can be reduced, and it can be confirmed that excellent electrochemical performance is exhibited with a relatively small amount.
  • FIG. 10 is a graph showing the measurement results of X-ray diffraction analysis (X-Ray Diffraction, XRD) according to the tension during the manufacture of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention.
  • X-ray Diffraction X-Ray Diffraction
  • FIG. 11 shows a change in the diameter of the carbon fiber according to the tension during the manufacture of the carbon fiber coated with the metal catalyst according to an embodiment of the present invention, the amount of the remaining metal catalyst derived by thermogravimetric analysis (TGA), and hydrogen generation.
  • TGA thermogravimetric analysis
  • the test results are shown graphically. More specifically, Figure 11a shows the diameter change of the carbon fiber according to the tension during the manufacture of the carbon fiber coated with the metal catalyst of Examples 1, 9 and Comparative Example 5, the residual metal catalyst derived by thermogravimetric analysis (TGA). The amount is shown as a graph, and FIG. 11b is a graph showing the results of hydrogen generation according to the tension during the manufacture of the carbon fibers coated with the metal catalysts of Examples 1, 9 and Comparative Example 5.
  • the heat treatment step is to apply a tension of 0.1 to 10.0 MPa per fiber to carbonize the precursor fiber by heat treatment It can be seen that it is more preferable to carbonize the precursor fiber by heat treatment by applying a tension of 2.5 to 7.5 MPa per fiber.
  • the method for producing a carbon fiber coated with a metal catalyst of the present invention is prepared by coating a metal catalyst in the form of a metal ion or in a form in which a ligand is bound to a metal ion on the surface of the polymer carbon fiber. There is an effect of producing a carbon fiber exhibiting uniform and excellent mechanical and electrochemical properties.
  • the carbon fiber coated with the metal catalyst prepared according to the method for producing the carbon fiber coated with the metal catalyst of the present invention can not only increase the area with a small amount of energy, but also the metal catalyst and the carbon fiber are integrated to stably use the metal catalyst. Since it exhibits stable electrochemical properties even in water for a long period of time by supporting it, it has the effect of being used as a water electrolytic electrode.
  • the carbon fiber coated with the metal catalyst prepared according to the method for producing the carbon fiber coated with the metal catalyst of the present invention can not only increase the area with little energy, but also integrate the metal catalyst and the carbon fiber to stably support the metal catalyst. Since it exhibits stable electrochemical properties even in water for a long period of time, it can be used as a water electrolysis electrode.

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Abstract

La présente invention comprend les étapes consistant à : préparer une fibre précurseur comprenant un précurseur de fibre de carbone et un solvant organique ; imprégner la fibre précurseur dans une solution de revêtement contenant un catalyseur métallique sous la forme d'un ion métallique ou d'un ligand lié à un ion métallique ; revêtir le catalyseur métallique par chauffage et étirement de la fibre précurseur imprégnée dans la solution de revêtement ; et traiter thermiquement la fibre précurseur revêtue du catalyseur métallique sous une atmosphère de gaz inerte. Selon la présente invention, en tant que catalyseur métallique sous la forme d'un ion métallique ou sous la forme d'un ligand lié à un ion métallique est revêtu sur la surface d'une fibre de carbone polymère, il est possible de fabriquer la fibre de carbone qui est morphologiquement uniforme et présente d'excellentes propriétés mécaniques et électrochimiques.
PCT/KR2021/009270 2021-04-08 2021-07-19 Procédé de fabrication d'une fibre de carbone revêtue d'un catalyseur métallique, et fibre de carbone pour la production d'une électrode fabriquée par ce procédé WO2022215809A1 (fr)

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