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WO2014119926A1 - Procédé de fabrication d'une cellule de pile à combustible - Google Patents

Procédé de fabrication d'une cellule de pile à combustible Download PDF

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Publication number
WO2014119926A1
WO2014119926A1 PCT/KR2014/000853 KR2014000853W WO2014119926A1 WO 2014119926 A1 WO2014119926 A1 WO 2014119926A1 KR 2014000853 W KR2014000853 W KR 2014000853W WO 2014119926 A1 WO2014119926 A1 WO 2014119926A1
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WO
WIPO (PCT)
Prior art keywords
electrode layer
electrode
forming
layer
cell
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/KR2014/000853
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English (en)
Korean (ko)
Inventor
권오웅
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.)
GV FUELCELL Inc
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GV FUELCELL Inc
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Filing date
Publication date
Application filed by GV FUELCELL Inc filed Critical GV FUELCELL Inc
Publication of WO2014119926A1 publication Critical patent/WO2014119926A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a stack for a fuel cell, and more particularly, to a method for manufacturing a cell for a fuel cell that prevents pin hole formation during electrolyte formation of a solid oxide fuel cell.
  • Solid Oxide Fuel Cells operate at the highest temperatures (700–1000 ° C) of fuel cells, using solid oxides with oxygen or hydrogen ion conductivity as electrolytes.
  • solid oxide fuel cells have a simpler structure than other fuel cells because all components are solid, there is no problem of electrolyte loss, replenishment and corrosion, no precious metal catalyst, and fuel supply through direct internal reforming. This is easy.
  • it has the advantage that thermal combined cycle power generation using waste heat is possible because the high-temperature gas is discharged.
  • a typical solid oxide fuel cell is composed of a dense electrolyte layer of oxygen ion conductivity and a porous cathode and anode positioned on both sides thereof.
  • the operating principle is that oxygen permeates through the porous cathode and reaches the electrolyte surface. Oxygen ions generated by the oxygen reduction reaction move to the fuel electrode through the dense electrolyte and react with hydrogen supplied to the porous anode to generate water. At this time, since electrons are generated at the anode and electrons are consumed at the cathode, electricity flows when the two electrodes are connected to each other.
  • the solid oxide fuel cell generates electricity in one cell, but the amount of electricity is very small to be used in real life, so the cells are stacked and used as a large amount of electrical energy. The collection of several cells is called a stack.
  • Figure 1 is a photograph showing a cross-sectional view of a single cell of the anode-supported solid oxide fuel cell according to the prior art 1.
  • a unit cell includes a porous anode support, a cathode functional layer, an electrolyte layer, and a composite air electrode layer, and the composite air electrode layer is composed of a cathode functional layer, an air electrode, and a current collector layer.
  • the metal support-type metal oxide fuel cell of the related art 2 includes a metal support 101; A first electrode 103 formed on one surface of the metal support 101; An electrolyte 107 formed on one surface of the first electrode 103 and a second electrode 109 formed on one surface of the electrolyte 107 are formed in a stacked stack to supply and discharge fuel or air. It includes a manifold 110, the first electrode 103 and the second electrode 109 is composed of different electrodes of the air electrode or fuel electrode.
  • the electrolyte material flows through the pores in the process of forming the electrolyte on the porous support to form pinholes or the like.
  • a separate method is required.
  • the thin film fuel cell 100 based on the conventional porous substrate shown in FIG. 3 in common with the prior arts 1 and 2 has an electrolyte thin film under the influence of the rough electrode (mainly anode) surface during fabrication. Defects such as pinholes may occur in the 120, and these defects may cause problems such as shorting or leakage, which may adversely affect cell performance.
  • the rough electrode mainly anode
  • An object of the present invention is to solve the problems of the prior art as described above, by forming an electrolyte layer on the first electrode layer having a dense structure (pin-hole) is formed in the electrolyte layer It is to provide a method for manufacturing a fuel cell for fuel cells that can prevent the, to reduce the first electrode layer through an oxygen reaction to produce a porous electrode.
  • the present invention comprises the steps of: forming a first electrode layer having a dense structure using an oxide; Forming an electrolyte layer on the first electrode layer; Reducing the first electrode layer to have porosity; And forming a second electrode layer on the electrolyte layer.
  • oxide forming the first electrode layer in the present invention may be NiO-based.
  • the first electrode layer reduction step in the present invention can be carried out through a hydrogen atmosphere.
  • the electrolyte layer forming step in the present invention is a physical vapor deposition (Physical vapor deposition, PVD), chemical vapor deposition (CVD: Chemical Vapor Deposition), screen printing (screen printing), spin coating, spraying (spraying), brush painting (brush painting) can be carried out by any one method.
  • a pin-hole is formed in the thin film electrolyte layer by forming a thin film electrolyte layer on a flat surface of the first electrode layer having a dense structure without pores. It is prevented from being, and the first electrode layer has the effect of reducing the hydrogen atmosphere to produce a porous electrode.
  • FIG. 1 is a cross-sectional view of a single cell of a cathode support solid oxide fuel cell according to the related art.
  • FIG. 2 is a cross-sectional view showing an example of a metal support-type solid oxide fuel cell according to the prior art 2.
  • FIG 3 is a reference diagram showing a state in which a pin hole is formed in the electrolyte layer in the prior art.
  • FIG. 4 is a block diagram of a fuel cell manufacturing method according to a first embodiment of the present invention.
  • 5A to 5D are process charts illustrating a method for manufacturing a fuel cell according to a first embodiment of the present invention.
  • the present invention comprises the steps of: forming a first electrode layer having a dense structure using an oxide; Forming an electrolyte layer on the first electrode layer; Reducing the first electrode layer to have porosity; And forming a second electrode layer on the electrolyte layer.
  • oxide forming the first electrode layer in the present invention may be NiO-based.
  • the first electrode layer reduction step in the present invention can be carried out through a hydrogen atmosphere.
  • the electrolyte layer forming step in the present invention is a physical vapor deposition (Physical vapor deposition, PVD), chemical vapor deposition (CVD: Chemical Vapor Deposition), screen printing (screen printing), spin coating, spraying (spraying), brush painting (brush painting) can be carried out by any one method.
  • FIG. 4 is a block diagram showing a fuel cell manufacturing method according to a first embodiment of the present invention
  • Figure 5a to 5d is a flowchart showing a fuel cell manufacturing method according to a first embodiment of the present invention. .
  • the fuel cell manufacturing method is a dense electrode material preparation step (S200), the first electrode layer forming step (S210), the electrolyte layer forming step (S220), the electrode reduction step (S230) ) And a second electrode layer forming step (S240).
  • the dense electrode material preparation step (S200) is a step of preparing the dense electrode material by using an oxide such as NiO-based to form the first electrode layer 310 having a dense structure.
  • the electrode material may be prepared through a combination of various ion conductive materials and oxides of metals that contribute to the role of catalyst and electron conductor.
  • the electrode material is prepared in a suitable form such as a target, precursor, nano powder, etc. according to the process to be performed in the first electrode layer forming step to be described later.
  • the first electrode layer forming step (S210) is a step of forming the first electrode layer 310 having a dense structure, that is, a high density structure, using a dense electrode material. (See Figure 5A)
  • the first electrode layer forming step (S210) is an oxide-based material of a high performance metal catalyst such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), and sputtering
  • a high performance metal catalyst such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), and sputtering
  • CVD Chemical Vapor Deposition
  • PVD physical vapor deposition
  • ALD atomic layer deposition
  • PLD pulsed laser deposition
  • a pellet-type anode is formed by forming a first electrode layer 310, which is an anode electrode, or preparing a metal oxide-based electrode material in the form of nano powder, followed by die pressing, sintering, or the like. Forming a first electrode layer.
  • the electrolyte layer forming step (S220) is a step of forming the electrolyte layer 320 on the relatively flat first electrode layer 310, and since the first electrode layer 310 is a dense electrode, an electrolyte layer forming step (S220) will be described later. When performing the pin hole may be prevented from being formed in the electrolyte layer 320. (See Figure 5b)
  • the electrolyte layer 320 may include zirconium oxide (Zr x O y ), cerium oxide (Ce x O y ), lanthanum galate, barium cerate, and barium zirconate. ), Bismuth-based oxides or ionic conductors such as oxygen ion conducting materials such as various doping phases of these materials, or proton conducting materials Can be.
  • the electrolyte layer 320 may be an electrolyte material such as Gd-doped CeO 2 (GDC) or Yttria-stabilized zirconia (YSZ).
  • the electrode reduction step (S230) is a step of reducing the first electrode layer 310 to have a porosity, and more particularly, reducing the first electrode layer 310 in a hydrogen atmosphere to infiltrate gas through the electrode and to enlarge the reaction area. It is to have a porous (porous). (See Figure 5c)
  • the electrode reduction step S230 may increase the reaction rate by having a porosity in the first electrode layer 310.
  • the first electrode layer 310 is formed of an oxide such as NiO-based, when the hydrogen is reacted with the dense electrode material constituting the first electrode layer 310, the NiO-based oxide is reduced to Ni metal, thereby reducing H 2. O molecules are produced. (NiO + H 2- > Ni + H 2 O)
  • the second electrode layer forming step (S240) is a step of forming the second electrode layer 330 on the thin film electrolyte layer 320 formed without pinhole defects, and includes platinum (platinum, Pt), palladium (Pd), and nickel (Ni). And electrode materials composed of mixed ionic electronic conductors (MIEC) such as LSC, LSCF, BSCF, etc., as well as high-performance metal catalysts such as ruthenium (Ru), Chemical Vapor Deposition (CVD), screen printing, spin coating, spraying, such as physical vapor deposition (PVD), atomic layer deposition (ALD), etc. The deposition is performed by spraying, brush painting, or the like to form the second electrode layer 330 which is a cathode electrode. (See FIG. 5D)
  • the fuel cell 300 manufactured by the fuel cell manufacturing method of the present invention includes a first electrode layer 310, an electrolyte layer 320, and a second electrode layer 330.
  • the electrolyte layer 320 provides a flow path of ions between the electrodes, but blocks the movement of electrons and separates fuel and oxygen, and the first electrode layer 310 and the second formed by the catalyst
  • the electrode layer 330 serves to provide a large surface area for the electrochemical reaction to occur and to provide a movement path for the electrons generated at this time.
  • the first electrode layer 310 is an anode electrode, an oxide-based material of a high performance metal catalyst such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), sputter,
  • a high performance metal catalyst such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), sputter
  • Anode-based electrode layers are formed by depositing by a vacuum-based thin film formation method such as Pulsed Laser Deposition (PLD) and Atomic Layer Deposition (ALD), or the metal oxide-based electrode material is nano-powdered. It is prepared in the form to form a pellet-type anode first electrode layer through a process such as die pressing, sintering and the like.
  • PLD Pulsed Laser Deposition
  • ALD Atomic Layer Deposition
  • the first electrode layer 310 is reduced by the oxygen reaction to have a porous (porous) in order to penetrate the gas and to enlarge the reaction area, and before the formation of the thin film electrolyte layer 320 to form an oxide such as NiO-based Since the first electrode layer 310 is formed of the dense electrode material, the pin hole in the thin film electrolyte layer may be prevented.
  • the electrolyte layer 320 is formed on the first electrode layer 310 having a flat surface, and includes zirconium oxide (Zr x O y ), cerium oxide (Ce x O y ), lanthanum galate, and barium cerate ( Ion conductors such as oxygen ion conducting materials, such as Barium Cerate, Barium Zirconate, bismuth-based oxides or various doping phases of these materials, or Proton conducting materials You can choose from a range of categories.
  • the electrolyte layer 320 may be an electrolyte material such as Gd-doped CeO 2 (GDC) or Yttria-stabilized zirconia (YSZ).
  • the second electrode layer 330 is a cathode electrode formed on the electrolyte layer 320 and includes LSC including high performance metal catalysts such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), and the like.
  • Electrode material composed of mixed ionic electronic conductors (MIEC) such as LSCF, BSCF, etc., physical vapor deposition (PVD), atomic layer deposition such as sputtering, pulsed laser deposition (PLD), etc.
  • Chemical Vapor Deposition (CVD) such as Atomic Layer Deposition (ALD), screen printing, spin coating, spraying, brush painting, etc. And a cathode electrode formed by vapor deposition.
  • the present invention relates to a method for manufacturing a cell for a fuel cell, the present invention comprising: forming a first electrode layer having a dense structure using an oxide; Forming an electrolyte layer on the first electrode layer; Reducing the first electrode layer to have porosity; And forming a second electrode layer on the electrolyte layer.
  • a pin-hole is formed in the thin film electrolyte layer by forming a thin film electrolyte layer on a flat surface of the first electrode layer having a dense structure without pores. It is prevented from being, and the first electrode layer has the effect of reducing the hydrogen atmosphere to produce a porous electrode.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une cellule de pile à combustible. La présente invention comprend : une étape de formation d'une première couche d'électrode possédant une structure dense par l'utilisation d'un oxyde ; une étape de formation d'une couche électrolytique sur la première couche d'électrode ; une étape de réduction de la première couche d'électrode de façon à rendre celle-ci poreuse ; et une étape de formation d'une seconde couche d'électrode sur la couche électrolytique. Lorsque la présente invention est utilisée, l'avantage est qu'une électrode poreuse peut être fabriquée par la formation d'une couche électrolytique en couche mince sur la surface plate de la première couche d'électrode possédant une structure dense sans pores, de sorte que des trous d'épingle ne peuvent pas être formés dans la couche électrolytique en couche mince, puis par la réduction de la première couche d'électrode au moyen d'une atmosphère d'hydrogène.
PCT/KR2014/000853 2013-01-29 2014-01-29 Procédé de fabrication d'une cellule de pile à combustible Ceased WO2014119926A1 (fr)

Applications Claiming Priority (2)

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KR20130009591 2013-01-29
KR10-2013-0009591 2013-01-29

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WO2014119926A1 true WO2014119926A1 (fr) 2014-08-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349333A (ja) * 1998-06-03 1999-12-21 Toto Ltd Ｎｉ／酸化物複合膜の成膜方法
JP2004087415A (ja) * 2002-08-29 2004-03-18 Araco Corp 燃料電池用電極基材とその製造方法
KR20040026180A (ko) * 2002-09-23 2004-03-30 한국과학기술연구원 초소형 전기화학 장치를 위한 다공성 전극 및 박막 전해질제조 방법
KR20070032358A (ko) * 2004-08-19 2007-03-21 도꾸리쯔교세이호징 가가꾸 기쥬쯔 신꼬 기꼬 금속 산화물 전극촉매
KR20100037648A (ko) * 2007-07-31 2010-04-09 쇼와 덴코 가부시키가이샤 금속 산화물 전극 촉매 및 그 용도, 및 금속 산화물 전극 촉매의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349333A (ja) * 1998-06-03 1999-12-21 Toto Ltd Ｎｉ／酸化物複合膜の成膜方法
JP2004087415A (ja) * 2002-08-29 2004-03-18 Araco Corp 燃料電池用電極基材とその製造方法
KR20040026180A (ko) * 2002-09-23 2004-03-30 한국과학기술연구원 초소형 전기화학 장치를 위한 다공성 전극 및 박막 전해질제조 방법
KR20070032358A (ko) * 2004-08-19 2007-03-21 도꾸리쯔교세이호징 가가꾸 기쥬쯔 신꼬 기꼬 금속 산화물 전극촉매
KR20100037648A (ko) * 2007-07-31 2010-04-09 쇼와 덴코 가부시키가이샤 금속 산화물 전극 촉매 및 그 용도, 및 금속 산화물 전극 촉매의 제조 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIM, HYUK ET AL.: "Fabrication of highly porous yttria-stabilized zirconia by acid leaching nickel from a nickel-yttria-stabilized zirconia cermet", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 85, no. 6, June 2002 (2002-06-01), pages 1473 - 1476 *

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