WO2015093862A1 - Poudre pour électrode de pile à combustible, pile à combustible, et procédés de production associés - Google Patents

Poudre pour électrode de pile à combustible, pile à combustible, et procédés de production associés Download PDF

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Publication number
WO2015093862A1
WO2015093862A1 PCT/KR2014/012515 KR2014012515W WO2015093862A1 WO 2015093862 A1 WO2015093862 A1 WO 2015093862A1 KR 2014012515 W KR2014012515 W KR 2014012515W WO 2015093862 A1 WO2015093862 A1 WO 2015093862A1
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WO
WIPO (PCT)
Prior art keywords
fuel cell
powder
cell electrode
metal
manufacturing
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Application number
PCT/KR2014/012515
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English (en)
Korean (ko)
Inventor
장재명
박주옥
Original Assignee
코닝정밀소재 주식회사
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Publication of WO2015093862A1 publication Critical patent/WO2015093862A1/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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • 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 fuel cell electrode powder, a fuel cell, and a manufacturing method thereof, and more particularly, to a fuel cell electrode powder made of an amorphous metal, a fuel cell using the same as an electrode, and a manufacturing method thereof.
  • Proton Exchange Membrane Fuel Cells among the hydrogen-powered generators are configured as shown in FIG. 1.
  • the anode and the cathode are material layers for oxidizing hydrogen and reducing oxygen.
  • Anodes and cathodes are key elements in power production.
  • the positive electrode and the negative electrode are generally composed of a carbon support (hereinafter Pt / C) in which nano-sized platinum particles are dispersed.
  • the anode and cathode composed of Pt / C are superior to any known materials in terms of power production efficiency.
  • carbon monoxide Carbon Monooxide
  • the present invention has been made to solve the above problems of the prior art, the object of the present invention is to eliminate the use of expensive platinum, to reduce the manufacturing cost of the fuel cell.
  • an object of the present invention is to eliminate the carbon carrier, simplify the electrode manufacturing process, and prevent the oxidation of carbon by carbon monoxide to ensure operational reliability.
  • an object of the present invention is to improve the performance of a fuel cell through maximization of catalytic reactivity.
  • the present invention melting the metal; Powdering the molten metal with rapid cooling to form an amorphous metal powder; Precipitating the amorphous metal powder in an electrolyte solution; And it provides a fuel cell electrode powder manufacturing method comprising the step of applying a current to the electrolyte.
  • the metal comprises any one of Ni, Fe, Co and Zr, and at least two or more of Pd, Pt, P, Be, Si, C, Ag, Mg, Ga, and Al.
  • the step of making the amorphous metal powder comprises the steps of making the molten metal into coarse powder using a vacuum atomizer, and the coarse powder into any one of ball milling, jet milling and high energy milling (SPEX milling). Through the step of making the fine powder.
  • the coarse powder has a particle diameter of 10 ⁇ 30 ⁇ m
  • the fine powder has a particle diameter of 0.5 ⁇ 1 ⁇ m.
  • the electrolyte is an acid solution in which acid is mixed with water and the acid has a concentration of 0.05-0.1 M.
  • the acid comprises at least one of H 2 SO 4 in HCl, HNO 3 .
  • a current of 0.3 ⁇ 1 mA / cm 2 of alternating current 10 ⁇ 100 Hz is applied to the electrolyte.
  • the fuel cell electrode powder has a needle-like protrusion having a protruding length of 1 to 6 nm on its surface.
  • the rapid cooling is cooled to 100 ⁇ 10000 °C / s.
  • the present invention comprises the steps of preparing a fuel cell electrode powder by the fuel cell electrode powder manufacturing method; Preparing a slurry by diluting the fuel cell electrode powder in a solvent; And applying the slurry to a hydrogen conductive membrane to form a fuel cell electrode.
  • the solvent is an aqueous or alcoholic solvent.
  • the fuel cell electrode powder is diluted in a concentration of 20 to 40% by weight in the solvent.
  • the slurry is applied to both surfaces of the hydrogen conductive membrane in a thickness of 1 to 3 ⁇ m by screen printing or ink printing.
  • the solvent is evaporated by heating at 100 to 150 ° C. for 2 hours or more.
  • the present invention is made of a powder of an amorphous metal, the metal is any one of Ni, Fe, Co and Zr, Pd, Pt, P, Be, Si, C, Ag, Mg, Ga, and Al It provides a fuel cell electrode powder comprising at least two or more.
  • the present invention also provides a fuel cell, wherein the fuel cell electrode powder of claim 15 is applied to a hydrogen conductive membrane.
  • the present invention by replacing the conventional Pt / C, by producing an electrode using AM, it is possible to eliminate the use of expensive Pt which is a problem of the conventional Pt / C electrode, the production cost of the fuel cell There is an effect to reduce the.
  • the present invention since the carbon carrier can be removed, when applied to the negative electrode, it is possible to simplify the manufacturing process of the electrode, it is possible to prevent the oxidation of carbon by carbon monoxide, it is possible to secure operating reliability compared to the Pt / C electrode Do.
  • the present invention is easy to maximize the catalyst reactivity through the change in composition and surface treatment, it is possible to continuously improve the performance of the fuel cell.
  • FIG. 1 is a structural diagram of a PEMFC.
  • FIG. 2 is a view showing a degradation mechanism of a conventional Pt / C electrode.
  • FIG 3 is a view showing a contrast between the conventional Pt / C electrode and the manufacturing process of the AM electrode according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram of a cyclic voltametry process.
  • FIG. 5 is a view showing the surface state of the powder (fuel powder) for the fuel cell electrode manufactured according to an embodiment of the present invention.
  • an anode and a cathode for PEMFC are manufactured using an amorphous metal (AM) having excellent electrochemical activity.
  • AM amorphous metal
  • Pt / C electrodes have a problem in that reliability is deteriorated by a deterioration mechanism generated during operation of a fuel cell.
  • agglomeration and crystallization do not occur up to 500-600 ° C. depending on the composition when manufacturing the electrode using AM, and there is no risk of dropping out of the catalyst, which is advantageous for securing reliability.
  • the AM can be produced through rapid cooling (100 to 10000 ° C / s) of molten metal.
  • the composition of the metal includes any one of Ni, Fe, Co, and Zr, and at least two or more of Pd, Pt, P, Be, Si, C, Ag, Mg, Ga, and Al. Therefore, the metal has a composition of at least ternary system or more.
  • the composition is Ni 1-wx M1 w M2 x , Fe 1-wx M1 w M2 x , Co 1-wx M1 w M2 x , or Zr 1-wx M1 w M2 x
  • M1 and M2 are two elements selected from Pt, P, Be, Si, C, Ag, Mg, Ga, and Al.
  • the composition is Ni 1-wxyz M1 w M2 x M3 y M4 z , Fe 1-wxyz M1 w M2 x M3 y M4 z , Co 1-wxyz M1 w M2 x M3 y M4 z , or Zr 1-wxyz M1 w M2 x M3 y M4 z , where M1, M2, M3 and M4 are four elements selected from Pd, Pt, P, Be, Si, C, Ag, Mg, Ga, Al becomes
  • AM may be prepared in the form of a plate or powder by rapid cooling.
  • it is preferable to form an electrode by preparing a powder of 0.5 to 1 ⁇ m in order to improve the performance of the PEMFC.
  • Powder is prepared by using a vacuum atomizer (Vacuum Atomizer) to produce a coarse powder (particle diameter: 10 ⁇ 30 ⁇ m), and fine powder (particle diameter: 0.5 ⁇ 1 ⁇ m using ball milling, jet milling, spex milling, etc.) Manufacture.
  • a vacuum atomizer Vauum Atomizer
  • AM can be applied to various compositions when alloying, it is very free to choose the composition for the performance.
  • AM can secure excellent corrosion resistance and mechanical strength that crystalline metal does not have.
  • AM since AM has excellent electrochemical activity for the oxidation / reduction reaction of fuel and oxygen compared to the crystalline metal, microcrystals are distributed on the metal surface, thereby inducing an excellent electrochemical reaction compared to the crystalline metal.
  • the prepared powder is diluted to a concentration of 20 to 40% by weight in an aqueous or ethanol solvent to prepare a slurry.
  • the slurry is coated on both sides of the hydrogen conductive membrane by screen printing and ink printing to a thickness of 1 to 3 ⁇ m, and then heated at 100 to 150 ° C. for at least 2 hours to evaporate the solvent to fix the electrode.

Abstract

La présente invention concerne un procédé de production d'une poudre pour une électrode de pile à combustible comprenant les étapes consistant à : faire fondre un métal ; produire une poudre de métal amorphe par pulvérisation, tout en refroidissant rapidement le métal fondu ; mettre en suspension la poudre de métal amorphe dans un électrolyte ; et appliquer un courant à l'électrolyte. En outre, la présente invention concerne un procédé de production d'une pile à combustible comprenant les étapes consistant à : produire une poudre pour une électrode de pile à combustible au moyen dudit procédé pour produire une poudre d'une électrode de pile à combustible ; produire une suspension en diluant la poudre pour une électrode de pile à combustible au moyen d'un solvant ; et créer une électrode de pile à combustible en étalant la suspension sur une membrane conductrice de l'hydrogène. En outre, la présente invention concerne une poudre pour une électrode de pile à combustible comprenant la poudre d'un métal amorphe, le métal comprenant l'un quelconque parmi Ni, Fe, Co et Zr, et deux ou plus parmi Pd, Pt, P, Be, Si, C, Ag, Mg, Ga, et Al.
PCT/KR2014/012515 2013-12-18 2014-12-18 Poudre pour électrode de pile à combustible, pile à combustible, et procédés de production associés WO2015093862A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20130157889 2013-12-18
KR10-2013-0157889 2013-12-18

Publications (1)

Publication Number Publication Date
WO2015093862A1 true WO2015093862A1 (fr) 2015-06-25

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002100374A (ja) * 2000-07-21 2002-04-05 Japan Storage Battery Co Ltd 燃料電池用電極およびその製造方法
JP2003331855A (ja) * 2002-05-16 2003-11-21 Tokyo Inst Of Technol 固体高分子形燃料電池用カソード電極触媒および固体高分子形燃料電池
KR20100108055A (ko) * 2009-03-27 2010-10-06 삼성전자주식회사 연료전지용 전극 촉매, 그의 제조방법 및 상기 전극 촉매를포함하는 전극을 구비한 연료전지
JP2011092940A (ja) * 2010-12-27 2011-05-12 Furukawa Electric Co Ltd:The 燃料電池用カソード電極触媒及びこれを用いた燃料電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002100374A (ja) * 2000-07-21 2002-04-05 Japan Storage Battery Co Ltd 燃料電池用電極およびその製造方法
JP2003331855A (ja) * 2002-05-16 2003-11-21 Tokyo Inst Of Technol 固体高分子形燃料電池用カソード電極触媒および固体高分子形燃料電池
KR20100108055A (ko) * 2009-03-27 2010-10-06 삼성전자주식회사 연료전지용 전극 촉매, 그의 제조방법 및 상기 전극 촉매를포함하는 전극을 구비한 연료전지
JP2011092940A (ja) * 2010-12-27 2011-05-12 Furukawa Electric Co Ltd:The 燃料電池用カソード電極触媒及びこれを用いた燃料電池

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