WO2009123389A1 - Supports d’électrodes et piles unitaires de type monolithique pour des piles à combustible d’oxyde solide et procédés de fabrication de piles utilisant ces piles unitaires - Google Patents

Supports d’électrodes et piles unitaires de type monolithique pour des piles à combustible d’oxyde solide et procédés de fabrication de piles utilisant ces piles unitaires Download PDF

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Publication number
WO2009123389A1
WO2009123389A1 PCT/KR2008/007465 KR2008007465W WO2009123389A1 WO 2009123389 A1 WO2009123389 A1 WO 2009123389A1 KR 2008007465 W KR2008007465 W KR 2008007465W WO 2009123389 A1 WO2009123389 A1 WO 2009123389A1
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WO
WIPO (PCT)
Prior art keywords
support
gas flow
gas
electrode
unit cell
Prior art date
Application number
PCT/KR2008/007465
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English (en)
Inventor
Jong Sik Chung
Hyun Ki Youn
Original Assignee
Postech Academy-Industry Foundation
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.)
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Application filed by Postech Academy-Industry Foundation filed Critical Postech Academy-Industry Foundation
Publication of WO2009123389A1 publication Critical patent/WO2009123389A1/fr

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Classifications

    • 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
    • H01M8/0206—Metals or alloys
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
    • 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
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
    • 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
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2435—High-temperature cells with solid electrolytes with monolithic core structure, e.g. honeycombs
    • 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 methods of manufacturing unit cells and stacks for solid oxide fuel cells, and more particularly, to a method of manufacturing a monolith type unit cell, including preparing a flat tube type conductive support having gas channels therein and thereon and appropriately applying an electrode layer, an electrolyte layer and an interconnection (IC) layer on part or all of the outer surface of the support, and to a method of manufacturing a stack which enables scale-up thereof with low electric resistance by stacking the unit cells.
  • IC interconnection
  • a solid oxide fuel cell (hereinafter abbreviated to "SOFC"), currently so-called a third-generation fuel cell, adopts thermochemically stable zirconia as an electrolyte with a fuel electrode serving as an anode and an air electrode serving as a cathode attached thereto.
  • SOFC a fuel gas such as hydrogen, methane, methanol, diesel or the like may be used without reformation, and an oxidizing agent such as air or oxygen is employed, and thus the SOFC is receiving attention as high efficiency low pollution electric power generation technology.
  • the SOFC utilizes as an electrolyte yttria-stabilized zirconia having a stable crystalline structure.
  • This material exhibits oxygen ion conductivity which is characteristically governed by temperature, and desired conductivity for the fuel cell is attainable at 800- 1000 0 C. Therefore, the SOFC is typically operable at a temperature of 800- 1000 0 C and thus adopts ceramics for an electrode material as they withstand such a high temperature.
  • a material for a cathode to which air is introduced includes LaSrMnO 3
  • a material for an anode to which hydrogen is introduced includes a Ni-ZrO 2 mixture.
  • a unit cell is formed by respectively coating front and back sides of an electrolyte plate serving as a support with an air electrode material and a fuel electrode material, performing a sintering process, thus forming porous electrolyte-electrode assemblies having a predetermined thickness, and then disposing an interconnector made of a conductive metal material between the electrolyte- electrode assemblies, in which the interconnector acts to electrically connect cathodes and anodes of upper and lower unit cells to be stacked and has gas channels for supplying fuel and air in both sides thereof.
  • Such a planar fuel cell is advantageous because the electrolyte-electrode assembly is thin but uniformity or flatness of the thickness is difficult to adjust due to the properties of the ceramic, thus making it difficult to increase the size of the fuel cell.
  • all of the edge portions of the unit cells should be provided with a gas sealing material.
  • glass useful as the sealing material begins to be softened from about 600 0 C, it is preferred in terms of efficiency that the SOFC be typically operated at a high temperature of about 800 0 C or higher.
  • the planar cell is required to be further improved in terms of various aspects in order for it to be commercialized.
  • a cylindrical cell is disclosed in US 6207311 Bl and US 6248468 Bl.
  • the cylindrical cell has slightly lower stack power density but is much higher in terms of strength and gas sealing.
  • a unit fuel cell using the cylindrical cell is formed by sequentially disposing an air electrode, an electrolyte, a fuel electrode and an IC layer on a porous support tube made of zirconium oxide.
  • the cylindrical cell is advantageous because there is no need for a gas sealing material in the cell, and thereby ceramic sealing problems as in the planar cell do not occur.
  • each cell is formed on a solid support, the fuel cell itself constitutes a strong ceramic structure, and resistance to thermal expansion is high.
  • an interconnector made of a metal material may be used.
  • power current flows along a thin electrode surface in a longitudinal direction, undesirably increasing internal resistance, making it impossible to increase the size of the fuel cell.
  • the inside or outside of each tube should be provided with an interconnector or wound with a wire.
  • tubes should be disposed at predetermined intervals so as not to be in contact with each other upon connection of the plurality of unit cells, unnecessary spaces are increased, resulting in a loss of the high power density per unit volume.
  • Such an interconnector increases the mechanical strength of the stack and enlarges the contact area of unit cells, thus increasing power density, but because the interconnector is made of a metal, mechanical and thermal stress undesirably occurs between the electrolyte-electrode assemblies made of ceramic upon high-temperature operation. Upon long use at high temperatures, corrosion may occur due to air on the surface of the interconnector and the volume and weight of the stack are undesirably increased compared to the planar cell.
  • the present inventors have proposed a unit cell module for a SOFC using a novel flat tube type support able to solve the aforementioned problems and a method of manufacturing an improved stack using the same, which is patented (Korean Patent No. 10-2007-0727684).
  • the upper outer surface of the flat tube type support is extruded in a state in which gas channels are formed, and an interconnector layer is applied on protrusions between the channels, so that the unit electrode and the interconnector are integratedly formed, thereby completing a monolith type unit cell.
  • the above patent is problematic because both sealing parts should be reprocessed and the interconnector layer should be selectively applied only on the protrusions, which is cumbersome.
  • the present invention further improves on the method of manufacturing the monolith type flat tube type unit cell and is intended to provide a method of designing and manufacturing a novel flat tube type support, which is easily manufactured and processed, facilitates the fabrication of a large unit cell through application and sealing, and has an enlarged reaction area, and provide a monolith type unit cell using the same. Disclosure of Invention Technical Problem
  • An aspect of the present invention is to provide a method of designing and manufacturing a support for a SOFC, and methods of manufacturing a monolith type unit cell and a stack for a SOFC using the same, in which an increase in the size of the unit cell is easy and an electric power generation per stack area of unit cells is much higher than that of a conventional unit cell for a SOFC while exhibiting advantages of the cylindrical cell which is easily manufactured, generates economic benefits, is readily sealed and has superior mechanical stability.
  • Another aspect of the present invention is to provide a method of manufacturing a monolith type unit cell for a SOFC, in which fuel gas and air flow channels are formed outside and inside a flat tube type support, and a first electrode layer, an electrolyte layer, a second electrode layer, and an IC layer are applied in the form of a thin film on part or all of the upper and lower outer surfaces thereof and then sintered, so that the electrodes, the electrolyte, the gas channels, and the IC are formed into a single structure.
  • a further aspect of the present invention is to provide a monolith type unit cell for a
  • SOFC having high performance, in which gas channels having an uneven shape are formed on the upper outer surface of a flat tube type support, and thus the effective reaction area is increased up to 200% compared to the planar surface, resulting in high efficiency, and also provide a method of manufacturing a stack, in which unit cells are stacked one on another, thus exhibiting operation properties similar to the planar cells.
  • the present invention provides a unit cell for a SOFC, including a porous flat tube type support made of an electrically conductive material; a first gas flow channel part having one or more gas flow passages formed in the support; a second gas flow channel part having flow passages of an opposite electrode gas formed in the reaction part located at the center of the upper outer surface of the support; a first electrode layer applied on the entire outer surface of the support; an electrolyte layer applied on the entire outer surface of the support other than the center of the lower outer surface of the support corresponding in location to the reaction part of the upper outer surface thereof; an IC layer applied on the center of the lower outer surface of the support having no electrolyte layer; and a second electrode layer applied on the second gas flow channel part of the reaction part of the upper outer surface of the support having the electrolyte layer.
  • the present invention provides a support and a unit cell for a SOFC to generate electric power using a fuel gas and air, including a porous flat tube type support which is electrically conductive; a first gas flow channel part having a plurality of gas flow passages formed in the support; a second gas flow channel part having flow passages of an opposite electrode gas formed in the reaction part located at the center of the upper outer surface of the support; a first electrode layer applied on the entire outer surface of the support; an IC layer applied on the center of the lower outer surface of the support; an electrolyte layer applied on the entire outer surface of the support other than the IC layer of the lower outer surface of the support; and a second electrode layer (having a polarity opposite that of the first electrode) applied on the reaction part located at the center of the upper outer surface of the support.
  • a porous flat tube type support which is electrically conductive
  • a first gas flow channel part having a plurality of gas flow passages formed in the support
  • a second gas flow channel part having flow passages
  • the present invention provides a method of manufacturing the support for a
  • SOFC to generate electric power using a fuel gas and air, which includes extruding an electrically conductive porous flat tube type support so that first gas flow channels are formed therein; drying the extruded support and then pre- sintering it at low temperature; grinding the upper and lower outer surfaces of the pre- sintered support to a predetermined thickness, as necessary; cutting and grinding the center of the upper outer surface of the support processed to a predetermined thickness, thus forming the second gas channels having an uneven cross-section of a predetermined width and depth; applying a first electrode material to a predetermined thickness on the entire outer surface of the support having the second gas flow channels; applying an IC layer to a predetermined thickness on the center of the lower outer surface of the support having the first electrode layer; applying an electrolyte layer to a predetermined thickness on the entire outer surface of the support other than the IC layer of the lower outer surface of the support; and applying the second electrode layer to a predetermined thickness on the reaction part having the second gas channels located at the center of the upper outer surface of the support having
  • a method of manufacturing the monolith type unit cell for a solid oxide fuel cell to generate electric power using a fuel gas and air includes preparing a support having a plurality of flow passages of a first gas flow channel part therein; processing a reaction part located at the center of the upper outer surface of the support, thus forming a plurality of protrusions to define flow passages of a second gas flow channel part in the support; applying a first electrode layer on the entire outer surface of the support; applying an electrolyte layer on the entire outer surface of the support other than the center of the lower outer surface of the support corresponding in location to the reaction part of the upper outer surface of the support; applying an IC layer on the center of the lower outer surface of the support having no electrolyte layer; and uniformly applying a second electrode layer on the protrusions of the second gas channel part of the reaction part located at the center of the upper outer surface of the support having the electrolyte layer.
  • the flat tube type support has the first gas flow channels formed in a longitudinal direction therein, and also, has the second gas flow channels formed in the reaction part located at the center of the upper outer surface thereof.
  • the support may be easily manufactured by extruding an electrode material for an anode or a cathode or a third conductive material using an extrusion machine, thus obtaining an extruded support, which is then dried and pre- sintered, followed by cutting and grinding the reaction part located at the center of the upper outer surface of the support other than both ends of the upper outer surface thereof, thus forming second gas flow channels having an uneven cross-section of a predetermined depth and width.
  • grinding may be additionally performed before or after processing the channels, if necessary.
  • the unit cell for a SOFC may be manufactured by thinly applying the material of each of the first electrode layer, the electrolyte layer, the IC layer and the second electrode layer on all or part of the outer surfaces of the support having the channels, and then sintering the layers.
  • the sintering process may be performed in a manner such that sintering is separately carried out after completion of respective applications or co- sintering is performed after completion of a plurality of applications.
  • the first gas flow channel part having flow passages formed between the ribs of the support functions to allow the gas of the air electrode or fuel electrode to flow.
  • the second gas flow channel part formed in the upper outer surface of the support functions to allow the gas of the opposite electrode to flow.
  • the IC layer may be provided in the form of a thin film, and thus there is no need for an additional thick interconnector made of a metal material for forming gas channels used in conventional fuel cells.
  • the SOFC including the monolith type unit cell according to the present invention is advantageous because the metal interconnector is not used and thus the cell is thinner, compared to general flat tube type SOFCs. Further, because the reaction part of the upper outer surface of the support is processed to be uneven, and thus an effective reaction area may be increased up to 200%, much higher output power efficiency is exhibited.
  • the stack for a SOFC includes unit cells stacked one on another, each unit cell including an extruded support having first gas flow passages therein and second gas flow passages additionally formed in the center of the upper outer surface thereof; a first porous electrode layer uniformly formed on the entire outer surface of the support, an electrolyte layer non-porously and densely formed on the entire outer surface of the support other than the center of the lower outer surface thereof on which an IC layer is to be formed, a second porous electrode layer formed on the second gas flow passages on the electrolyte layer, an IC layer non-porously and densely formed on the center of the lower outer surface of the support corresponding in location to the second gas flow passages, a sealing material applied on both ends of the support.
  • the IC layer provided on the center of the lower outer surface of the support may be formed such that it is in contact with or partially overlaps with the electrolyte layer adjacent thereto to achieve gas sealing, and is preferably applied to be thicker than the adjacent electrolyte layer.
  • the sealing material may be additionally applied on the electrolyte layer at both ends of the lower outer surface of the support, such that the entire lower outer surface of the support has a uniform thickness.
  • the electrode material used for the air electrode may include for example LSM (LaSrMnO 3 ), and the electrode material used for the fuel electrode may include for example Ni/YSZ (cermet), in which YSZ indicates yttria-stabilized zirconia.
  • the second gas flow channel part of the support may be located in a reaction furnace chamber for a fuel cell, and the sealing part thereof may be located inside or outside the wall of the reaction furnace chamber.
  • the electrolyte layer and the IC layer should be maintained in the form of a non-porous and dense film so that the gas does not leak through the applied layers, whereas the electrode layers should be maintained in the form of a porous film to facilitate the diffusion of gas.
  • the thickness of the electrolyte layer and the electrode layers may be set to 1000 ⁇ m or less, and the IC layer may be provided in the form of a single film or a multiple film having properties as soft as possible without deteriorating at high temperature in a hydrogen/oxygen atmosphere using a conductive material, and the thickness thereof may be set to 1.0 mm or less
  • the unit cell can be manufactured as a monolith type because an interconnector made of a metal material is provided in the form of a thin film, while having the advantages of a tube type which is structurally solid and has no gas sealing problems.
  • the unit cells are stacked one on another to thus constitute a stack, electric power can be conducted in a vertical direction, and thus advantages of a planar type having low electric resistance even upon scale-up can be exhibited.
  • the unit cell can be entirely made of ceramics, thus solving high- temperature corrosion or thermal stress problems due to the metal interconnector occurring in conventional SOFCs.
  • the actual effective reaction area upon stacking of the unit cells, the actual effective reaction area can be increased up to 200% compared to the apparent stack area, thus drastically improving performance thereof compared to conventional flat tube type cells.
  • FIG. 1 is a perspective view showing an extruded support for use in a SOFC according to the present invention
  • FIG. 2 is a perspective view showing the support of FIG. 1 in which second gas channels and protrusions are formed in and on the upper outer surface thereof according to the present invention
  • FIG. 3 is a perspective view showing the support of FIG. 1 in which zigzag-shaped second gas channels and protrusions are formed in and on the upper outer surface thereof according to the present invention
  • FIG. 4 is a cutaway view showing the application state and range of layers applied on the support for a SOFC according to the present invention
  • FIG. 5 is a cross-sectional view showing a power generation stack formed by stacking unit cells for a SOFC according to the present invention.
  • cathode collector 112 anode collector
  • the flat tube type support 1 for a SOFC is made of a material for a fuel electrode (anode) or an air electrode (cathode) and is formed through typical extrusion so that a plurality of first gas flow channels 6 is provided in a longitudinal direction in the support.
  • an electrically conductive porous support is finally obtained.
  • An example of the material for the anode includes a Ni-YSZ mixture, in which YSZ is yttria-stabilized zirconia, and an example of the material for the cathode includes LSM (LaSrMnO 3 ).
  • the materials for the air and fuel electrodes are merely illustrative, and the present invention is not limited thereto.
  • any other third conductive material may be used so long as it has no problems in regard to the application and bonding of the electrode layer.
  • the first gas flow channels 6 are provided in a honeycomb formation, and the cross-section thereof may have any shape as long as the gas uniformly flows, and preferably has a polygonal or circular shape so as to achieve desired strength and uniform gas diffusion.
  • the size of the channels may be set to 0.1-10 mm and preferably 0.5-5 mm.
  • the thickness of the ribs 5 between the channels 6 is set to 0.1-5 mm and preferably 0.5-5 mm.
  • the upper outer surface 8 and the lower outer surface 9 of the support 1 may be further precisely ground so that a final thickness therebetween may be maintained uniform, before and/or after forming the second gas flow channels.
  • the second gas channels 16 of the reaction part 22 of the upper outer surface of the final support 10 may be formed in a manner such that a second gas inlet 33 and a second gas outlet 34 are formed in a direction perpendicular to a longitudinal direction which is the direction of a first gas inlet and outlet, as shown in FIG. 3, in order to prevent the mixing of two gases and solve the aforementioned gas sealing problems.
  • the depth of the second gas flow channels 16 may be set to
  • 0.1-10 mm, and preferably 0.2-5 mm, and the width thereof may be set to 0.1-10 mm and preferably 0.2-5 mm.
  • the area of the protrusions 18 between the second gas flow channels 16 of the reaction part 22 of the upper outer surface of the support is 5-95% and preferably 20-70% of the entire reaction area of the upper outer surface thereof.
  • the process of manufacturing the unit cell 30 for a SOFC includes sequentially applying a first electrode layer, an electrolyte layer, an IC layer, and a second electrode layer at a predetermined thickness on specific portions of the final support 10 and then sintering them at a specific temperature.
  • the application process when the material for the support is the same as the material for the first electrode, the application of the first electrode may be omitted.
  • a predetermined thickness of a material for the first electrode layer 41 is applied over the entire outer surface of the final support 10.
  • a predetermined thickness of the electrolyte layer 42 is uniformly applied on the entire outer surface of the support 10 other than the center of the lower outer surface 9 of the support 10 corresponding in location to the reaction part 22 located at the center of the upper outer surface of the support.
  • the second electrode layer 43 is uniformly applied to a predetermined thickness on the entire uneven surface of the reaction part 22 having the second gas channels of the upper outer surface 8 of the support.
  • the IC layer 44 is applied to a predetermined thickness on the center of the lower outer surface 9 of the support having no electrolyte layer 42, so as to partially overlap with the electrolyte layer 42 such that a first gas inside the channels is not mixed with a second gas outside the channels.
  • high-temperature sintering may be carried out, if necessary.
  • the conditions and procedure for the sintering process may vary depending on the type of support material, the type of application layer material, and the application process.
  • co-sintering may be performed after the completion of a plurality of applications.
  • the electrode layers 41, 43 should remain porous for purposes of the diffusion of gas, whereas the electrolyte layer 42 and the IC layer 44 should remain non-porous and dense so as to prevent mutual mixing of the first gas and the second gas.
  • the process of applying the layers on the support may be performed through various methods. For example, application of a slurry solution of particles and then thermal sintering may be performed, or alternatively chemical vapor deposition (CVD) and physical vapor deposition (PVD) using a metal and a metal compound, electrochemical plating, and thermal and plasma spray may be employed.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the material for the IC layer 44 should be electrically conductive enough for the making of an electrical connection between the anode of the upper cell and the cathode of the lower cell upon stacking of the unit cells 30 one on another, should have gas impermeability after application or after application and sintering and long thermal stability at the operation temperature of the fuel cell, and should be structurally stable at high temperature in a hydrogen/oxygen atmosphere.
  • any material may be used regardless of the component thereof, as long as it exhibits the above functions.
  • the application layer may be provided in the form of a single layer or a multiple layer made of one or more components.
  • the monolith type unit cells 30 for a SOFC thus manufactured obviate a need for a metal interconnector for forming gas channels used in conventional SOFCs.
  • Such unit cells are stacked one on another as desired, after which cathode and anode collectors are attached thereto, thus completing a fuel cell stack.
  • FIG. 5 shows a longitudinal cross-sectional view of the unit cell stack mounted in a reaction furnace chamber.
  • the sealing parts 21 provided at both ends of the cell 30 other than the reaction part 22 are located outside the wall of the reaction furnace chamber 105, and both edges thereof are connected to pipe ports for inflow and outflow of the first gas.
  • the second gas flowing in the reaction furnace chamber is sealed inside the reaction furnace chamber, and the second gas flows in the direction perpendicular to the direction of flow of the first gas and then outflows in the opposite direction.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Sustainable Energy (AREA)
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Abstract

L’invention concerne un procédé de fabrication d’un support et un procédé de fabrication d’une pile unitaire du type monolithique ayant un haut rendement pour une pile à combustible d’oxyde solide utilisant cette pile unitaire, qui est fabriquée facilement, permet une extrapolation, facilite l’étanchéité aux gaz et est structurellement stable et dans laquelle une électrode/un électrolyte, des canaux de gaz et une couche d’interconnexion sont formés en tant que type monolithique. La pile unitaire comprend un support de type tube plat poreux réalisé en un matériau pour une cathode ou une anode ou un troisième matériau conducteur, une première partie formant canal d’écoulement de gaz comportant des passages d’écoulement formés dans le support, une seconde partie formant canal d’écoulement de gaz comportant des passages d’écoulement formés entre des protubérances sur une partie de réaction au centre de la surface extérieure supérieure du support, une première couche d’électrode appliquée sur la surface extérieure entière du support, une couche d’électrolyte appliquée sur la surface extérieure entière du support autre que le centre de la surface extérieure inférieure du support correspondant à l’emplacement de la partie de réaction de la surface extérieure supérieure de celui-ci, une couche d’interconnexion appliquée sur le centre de la surface extérieure inférieure du support, et une seconde couche d’électrode appliquée sur la partie de réaction de la surface extérieure supérieure du support comportant la couche d’électrode. L’invention concerne un procédé de fabrication d’une pile par l’empilage de piles unitaires.
PCT/KR2008/007465 2008-03-31 2008-12-17 Supports d’électrodes et piles unitaires de type monolithique pour des piles à combustible d’oxyde solide et procédés de fabrication de piles utilisant ces piles unitaires WO2009123389A1 (fr)

Applications Claiming Priority (2)

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KR1020080030004A KR100976506B1 (ko) 2008-03-31 2008-03-31 고체산화물 연료전지용 전극 지지체와 일체형 단위 셀 및이를 이용한 스텍 제작 방법
KR10-2008-0030004 2008-03-31

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WO2009123389A1 true WO2009123389A1 (fr) 2009-10-08

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EP2424028A2 (fr) * 2009-04-20 2012-02-29 POSTECH Academy-Industry Foundation Bloc pour une pile à combustible à oxyde solide utilisant une structure tubulaire plate
CN102971901A (zh) * 2010-04-09 2013-03-13 浦项工科大学校产学协力团 平管型固体氧化物燃料电池用巨大电池堆及其制备方法
US8962202B2 (en) 2010-06-14 2015-02-24 Postech Academy-Industry Foundation Internal reforming tubular solid oxide fuel cell stack and manufacturing method therefor
EP2631979A4 (fr) * 2010-10-19 2015-12-09 Mim Ceramics Co Ltd Pile à combustible à oxyde solide
CN107112568A (zh) * 2014-12-19 2017-08-29 燃料电池能有限公司 高效熔融碳酸盐燃料电池系统和方法

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WO2012015113A1 (fr) * 2010-07-30 2012-02-02 한국에너지기술연구원 Empilement plat de piles à oxyde solide de forme tubulaire
WO2017184877A1 (fr) 2016-04-21 2017-10-26 Fuelcell Energy, Inc. Système de pile à combustible haute performance à exportation d'hydrogène et de gaz de synthèse
US10573907B2 (en) 2017-03-10 2020-02-25 Fuelcell Energy, Inc. Load-following fuel cell system with energy storage
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CN113745618B (zh) * 2021-08-28 2023-06-16 山东工业陶瓷研究设计院有限公司 一种sofc电池及其制备方法
CN114940625B (zh) * 2022-05-26 2023-05-30 西安交通大学 一端自密封的陶瓷扁管支撑型固体氧化物燃料电池/电解池的制备方法
CN114914507B (zh) * 2022-05-26 2024-07-05 西安交通大学 一种导电扁管支撑型固体氧化物燃料电池/电解池及其制备方法以及电池堆结构
CN115458765B (zh) * 2022-11-09 2023-01-31 武汉氢能与燃料电池产业技术研究院有限公司 一种金属空心支撑型固体氧化物燃料电池电堆及发电模块

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* Cited by examiner, † Cited by third party
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EP2424028A2 (fr) * 2009-04-20 2012-02-29 POSTECH Academy-Industry Foundation Bloc pour une pile à combustible à oxyde solide utilisant une structure tubulaire plate
EP2424028A4 (fr) * 2009-04-20 2013-07-24 Postech Acad Ind Found Bloc pour une pile à combustible à oxyde solide utilisant une structure tubulaire plate
US9608285B2 (en) 2009-04-20 2017-03-28 Postech Academy-Industry Foundation Stack for a solid oxide fuel cell using a flat tubular structure
CN102971901A (zh) * 2010-04-09 2013-03-13 浦项工科大学校产学协力团 平管型固体氧化物燃料电池用巨大电池堆及其制备方法
US9379400B2 (en) 2010-04-09 2016-06-28 Postech Academy-Industry Foundation Huge stack for flat-tubular solid oxide fuel cell and manufacturing method thereof
US8962202B2 (en) 2010-06-14 2015-02-24 Postech Academy-Industry Foundation Internal reforming tubular solid oxide fuel cell stack and manufacturing method therefor
EP2631979A4 (fr) * 2010-10-19 2015-12-09 Mim Ceramics Co Ltd Pile à combustible à oxyde solide
CN107112568A (zh) * 2014-12-19 2017-08-29 燃料电池能有限公司 高效熔融碳酸盐燃料电池系统和方法
CN107112568B (zh) * 2014-12-19 2021-03-16 燃料电池能有限公司 高效熔融碳酸盐燃料电池系统和方法

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