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WO2021068318A1 - Procédé de préparation d'une plaque bipolaire en graphite de pile à combustible - Google Patents

Procédé de préparation d'une plaque bipolaire en graphite de pile à combustible Download PDF

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Publication number
WO2021068318A1
WO2021068318A1 PCT/CN2019/115666 CN2019115666W WO2021068318A1 WO 2021068318 A1 WO2021068318 A1 WO 2021068318A1 CN 2019115666 W CN2019115666 W CN 2019115666W WO 2021068318 A1 WO2021068318 A1 WO 2021068318A1
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WO
WIPO (PCT)
Prior art keywords
graphite
bipolar plate
fuel cell
same
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/115666
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English (en)
Chinese (zh)
Inventor
郑法
刘清
阚佳伟
董辉
吴海涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yushi Energy Nantong Co Ltd
Original Assignee
Yushi Energy Nantong Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yushi Energy Nantong Co Ltd filed Critical Yushi Energy Nantong Co Ltd
Publication of WO2021068318A1 publication Critical patent/WO2021068318A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/90—Electrical properties
    • C04B2111/94—Electrically conducting materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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 invention relates to the field of fuel cells, in particular to a method for preparing a graphite bipolar plate of a fuel cell.
  • Graphite bipolar plates also known as graphite collector plates and graphite separators, are one of the important components of fuel cells. Graphite bipolar plates play a role in providing gas flow channels in fuel cells, preventing different gases from colluding, and establishing current paths.
  • Graphite material is a bipolar plate material that was developed and used earlier.
  • the traditional bipolar plate mainly uses non-porous graphite plate, and the groove is processed by machining.
  • the graphite bipolar plate has a low thermal expansion coefficient, good thermal conductivity, stable chemical properties, good corrosion resistance and strong electrical conductivity.
  • the brittleness of graphite causes processing difficulties, and it is easy to produce pores during the manufacturing process, so that the fuel and the oxidant can penetrate each other, so other substances must be added to improve the battery performance.
  • the purpose of the present invention is to provide a method for preparing the graphite bipolar plate of a fuel cell.
  • step (2) Take the expandable graphite, carbon black and polyphenylene sulfide prepared in step (1) and mix them with a mixer, and the mixing time is 20min-25min.
  • the expandable graphite, carbon black and polyphenylene sulfide The mass ratio is 15: (1-1.2): (3.8-4.2);
  • step (3) The mixture obtained in step (2) is added to the solvent absolute ethanol, mixed with mechanical stirring and ultrasonic dispersion, and dried and broken into powder;
  • step (3) Put the powder obtained in step (3) into a mold, and press it to form after a molding pressure of 10-11 MPa at 25-30°C and a pressure for 3 minutes;
  • step (4) Solidify the sample press-formed in step (4) through stepped heating, and finally cool it to obtain a finished product.
  • carbon black is first dispersed in polyphenylene sulfide, and then expandable graphite is added.
  • the quality of the anhydrous ethanol in the step (3) is at least 3 times the quality of the mixture.
  • the stepped temperature rise is to firstly increase to 80°C at a rate of 20°C/h, and then increase to 180°C at a rate of 15°C/h, and keep the temperature for 2-2.5h.
  • the particle size of the natural flake graphite in the step (1) is less than 74 ⁇ m.
  • the particle size of the carbon black in the step (2) is less than 20 ⁇ m.
  • the masses of potassium permanganate and ferric chloride added in the step (1) are both 7%-9% of the mass of graphite.
  • the dehydration in the step (1) is completed under an inert gas.
  • the present invention has the following beneficial effects:
  • natural flake graphite is added to the mixed solution of sulfuric acid and nitric acid and mixed uniformly, and then potassium permanganate and ferric chloride are added.
  • the reaction at a fixed temperature can make the generated expandable graphite reduce the generation of edge compounds and disperse More uniform, dehydration under inert gas prevents reaction with air, thereby affecting the quality of expandable graphite.
  • expandable graphite, carbon black, and polyphenylene sulfide are first mixed with a mixer, and the solvent is added, and then mixed by mechanical stirring and ultrasonic dispersion to reduce the porosity of the finished product and improve the quality of the product.
  • the sample is cured by a stepped heating method, so that the sheet is more compact, and both the electrical conductivity and the flexural strength are improved.
  • step (2) Take the expandable graphite and carbon black obtained in step (1) and mix them for 5 minutes with a mixer, and then add polyphenylene sulfide for 20 minutes.
  • the expandable graphite, carbon black and polyphenylene sulfide The mass ratio of ether is 15:1:3.8, and the particle size of carbon black is less than 20 ⁇ m;
  • step (3) The mixture obtained in step (2) is added to the solvent absolute ethanol, the quality of the absolute ethanol is 4 times that of the mixture, and then mechanical stirring and ultrasonic dispersion are used for mixing, and the mixture is dried and broken into powder;
  • step (3) Put the powder prepared in step (3) into a mold, and press it into a mold at a molding pressure of 10 MPa at 26°C, and press for 3 minutes;
  • step (4) the sample formed in step (4) is cured by stepped heating.
  • the stepped heating is specifically increased to 80°C at a rate of 20°C/h, and then to 180°C at a rate of 15°C/h. Keep the temperature for 2h, and finally cool down to obtain the finished product.
  • step (2) Take the expandable graphite and carbon black obtained in step (1) and mix them for 5 minutes with a blender, and then add polyphenylene sulfide, the mixing time is 25 minutes, the expandable graphite, carbon black and polyphenylene sulfide
  • the mass ratio of ether is 15:1.1:4, and the particle size of carbon black is less than 20 ⁇ m;
  • step (3) The mixture obtained in step (2) is added to the solvent absolute ethanol, the quality of the absolute ethanol is 4.5 times that of the mixture, and then mechanical stirring and ultrasonic dispersion are used for mixing, and the mixture is dried and broken into powder;
  • step (3) Put the powder obtained in step (3) into a mold, and press it into a mold at a molding pressure of 10 MPa at 27°C, and press for 3 minutes;
  • step (4) the sample formed in step (4) is cured by stepped heating.
  • the stepped heating is specifically increased to 80°C at a rate of 20°C/h, and then to 180°C at a rate of 15°C/h. Keep the temperature for 2h, and finally cool down to obtain the finished product.
  • step (2) Take the expandable graphite and carbon black obtained in step (1) and mix them for 5 minutes with a mixer, and then add polyphenylene sulfide for 30 minutes.
  • the expandable graphite, carbon black and polyphenylene sulfide The mass ratio of ether is 15:1.2:4.1, and the particle size of carbon black is less than 20 ⁇ m;
  • step (3) The mixture obtained in step (2) is added to the solvent absolute ethanol, the quality of the absolute ethanol is 5 times that of the mixture, and then mechanical stirring and ultrasonic dispersion are used for mixing, and the mixture is dried and broken into powder;
  • step (3) The powder prepared in step (3) is put into a mold, the molding pressure is 10 MPa at 30°C, and the pressure is continued for 3 minutes, and then it is pressed into shape;
  • step (4) Curing the sample formed by step (4) through stepped heating.
  • the stepped temperature rise is first to increase to 80°C at a rate of 20°C/h, and then to 180°C at a rate of 15°C/h. , Heat preservation for 3h, and finally cool to make the finished product.
  • the natural flake graphite, carbon black and phenolic resin are mixed uniformly according to the mass ratio of 10:6:2, and then the mixture is put into the mold at room temperature and 10 MPa pressure for 3 minutes to press the molding, and then solidify and increase the temperature for solidification treatment. After cooling The prepared sample is obtained.
  • the samples prepared in the above examples were processed into samples of 60mm ⁇ 5mm ⁇ 2mm, and the bending strength of each sample was measured by the LWK-250 micro-control electronic tensile testing machine and the three-point bending method.
  • the span was 40mm and the impact
  • the moving speed of the head is 1.0 mm/min.
  • the morphology of the sample was observed with JSM-6700F scanning electron microscope.
  • the flexural strength of the samples of Examples 1-3 are all greater than 60Mpa, the electrical conductivity is greater than 80S/cm, the flexural strength of the comparative example is 15.5MPa, and the electrical conductivity is 18.3S/cm, it can be seen that the method of the present invention is used to prepare The resulting bipolar plate material has better performance, higher strength and better performance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Est divulgué, un procédé de préparation d'une plaque bipolaire en graphite de pile à combustible, le procédé consistant : à ajouter du graphite lamellaire naturel à une solution mixte d'acide sulfurique et d'acide nitrique et à agiter ladite solution pendant le processus d'ajout ; après l'ajout du graphite lamellaire naturel, à ajouter du permanganate de potassium et du trichlorure ferrique, à maintenir la température entre 24 et 26 °C, à agiter ladite solution pendant 30 à 40 min, puis à séparer ladite solution par centrifugation, à laver ladite solution à l'eau jusqu'à devenir neutre puis à déshydrater ladite solution de manière à préparer un graphite expansible ; à mélanger le graphite expansible préparé avec du noir de carbone et du sulfure de polyphénylène à l'aide d'un mélangeur pendant un temps de mélange de 20 min à 25 min, et à ajouter le mélange résultant à un solvant, c'est-à-dire de l'éthanol anhydre, à mélanger ledit mélange jusqu'à devenir uniforme par agitation mécanique et dispersion ultrasonore, et à sécher et broyer ledit mélange en une poudre, à placer la poudre préparée dans un moule, et à moudre cette dernière à la presse à 25-30 °C avec une pression de moulage de 10-11 MPa après que la mise sous pression a été maintenue pendant 3 minutes ; puis à soumettre un échantillon obtenu après moulage à la presse à un traitement de durcissement par élévation de température progressive, et enfin à faire refroidir ledit échantillon de manière à obtenir un produit fini. Les avantages de la présente invention résident en ce que la plaque bipolaire préparée présente une résistance à la flexion supérieure et de meilleures performances de conductivité.
PCT/CN2019/115666 2019-10-12 2019-11-05 Procédé de préparation d'une plaque bipolaire en graphite de pile à combustible Ceased WO2021068318A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910968427.3A CN110590230B (zh) 2019-10-12 2019-10-12 一种燃料电池石墨双极板制备方法
CN201910968427.3 2019-10-12

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Cited By (1)

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CN115050984A (zh) * 2022-06-15 2022-09-13 一汽解放汽车有限公司 一种改性氧化石墨烯涂层双极板的制备方法及其应用

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CN114824342B (zh) * 2021-01-28 2024-08-09 上海神力科技有限公司 一种石墨极板的制备方法、石墨极板、燃料电池以及车辆
CN118738427A (zh) * 2024-08-27 2024-10-01 辽宁科京新材料有限公司 一种供电子型复合材料双极板及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
CN115050984A (zh) * 2022-06-15 2022-09-13 一汽解放汽车有限公司 一种改性氧化石墨烯涂层双极板的制备方法及其应用

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CN110590230A (zh) 2019-12-20

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