WO2009096624A1 - Electrode supports and monolith type unit cells for solid oxide fuel cells and their manufacturing methods - Google Patents

Electrode supports and monolith type unit cells for solid oxide fuel cells and their manufacturing methods Download PDF

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Publication number
WO2009096624A1
WO2009096624A1 PCT/KR2008/001133 KR2008001133W WO2009096624A1 WO 2009096624 A1 WO2009096624 A1 WO 2009096624A1 KR 2008001133 W KR2008001133 W KR 2008001133W WO 2009096624 A1 WO2009096624 A1 WO 2009096624A1
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WIPO (PCT)
Prior art keywords
support
gas flow
unit cell
layer
electrode layer
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PCT/KR2008/001133
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French (fr)
Inventor
Jong Shik Chung
Jin Yeo Kwon
Nam Woong Kim
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Postech Academy-Industry Foundation
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Publication of WO2009096624A1 publication Critical patent/WO2009096624A1/en

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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04029—Heat exchange using liquids
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04111—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants using a compressor turbine assembly
    • 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
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/40—Combination of fuel cells with other energy production systems
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
    • H01M8/04022—Heating by combustion
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • 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
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/40—Fuel cell technologies in production processes

Definitions

  • the present invention relates to electrode supports and unit cells for fuel cells, and manufacturing methods thereof, and more particularly, relates to a support for solid oxide fuel cells, which is easily manufactured, enables scale-up thereof, facilitates the sealing of a gas and has a drastically increased reaction area, to a monolith type unit cell using the support and to manufacturing methods thereof.
  • a solid oxide fuel cell (hereinafter abbreviated to "SOFC"), presently 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.
  • the SOFC is operated under high-temperature conditions in a hydrogen atmosphere and uses a fuel gas sich as methane, methanol, diesel or the like without reformation, and is thus receiving attention as high efficiency low pollution electric power generation technology.
  • the SOFC utilizes as an electrolyte yttria- stabilized zirconia having a stable crystalline stricture.
  • a material for a cathode to which air is introduced includes LaSrMnO , and a material for an anode to
  • a unit cell is constricted by coating front and back sides of the plate with an air electrode and a fuel electrode, respectively, 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 having gas channels for introducing fuel and air on 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. Further, because the electrolyte-electrode assemblies and the interoonnectors are alternately layered in the unit cell stack, there is a dangerous probability of causing structural instability due to thermal and mechanical stress between the electrolyte-electrode assembly and the interconnector of each unit cell for a fuel cell upon high-temperature operation or during heating or cooling. In order to prevent the mixing of the two gases of the upper and lower unit cells and to seal the cell, all of the edge portions of the unit cells are provided with a gas sealing material.
  • 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 constructed by sequentially layering an air electrode, an electrolyte and a fuel electrode 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 oxur.
  • each cell is formed on a solid support, the fuel cell itself constitutes a strong ceramic stricture, and resistance to thermal expansion is high.
  • an interconnector made of a metal material may be used.
  • Fbwever in order to increase the capacity of the fuel cell, in the case where a plurality of unit cells is connected to each other to thus form a stack, 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.
  • each tube should be provided with an interconnector or wound with a wire. Also, because tubes are disposed at predetermined intervals so as not to be in contact with each other upon formation of the stack, unnecessary spaces are increased, resulting in a lower power density per unit volume.
  • interconnector increases the mechanical strength of the stack and enlarges the contact area of unit cells, thus increasing power density
  • 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.
  • corrosion may oxur due to air on the surface of the interconnector and the volume and weight of the stack are increased compared to the planar cell.
  • the present inventors have solved the aforementioned problems and proposed a novel monolith type unit cell including a flat tube type support using a thin film in lieu of an interconnector and a method of manufacturing a stack using the same, which is patented (Korean Patent No. 727684).
  • 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 present invention further improves the advantages of the above monolith type unit cell and is intended to provide a 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 manufacturing method thereof, and a method of manufacturing a monolith type unit cell using the same.
  • the present invention is devised to solve the problems of conventional planar and cylindrical SOFCs, such as gas sealing, scale-up, mechanical and thermal stability and the like and to maximize electric power generation per unit area.
  • An aspect of the present invention is to provide methods of manufacturing a support and a monolith type unit cell for a SOFC using the same, in which an increase in the size of the unit cell is easy and an electric power generation rate per unit stack area is ⁇ ch 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, whereby a thin film is applied on protrusions between the gas channels of the upper outer surface thereof, without the additional use of an interoonnector, thus forming an electrode layer, an electrolyte layer, gas channels, and an interconnection layer into a single stricture.
  • a further aspect of the present invention is to provide a method of manufacturing a monolith type unit cell for a SOFC having high performance, in which gas channels having an uneven shape are formed on the upper and lower outer surfaces of a flat tube type support, and thus the reaction area is increased up to 200% compared to the planar surface, and also, in which an electrode reaction oxurs on both of the upper and lower outer surfaces of the support other than the upper protrusions on which the interconnection layer is applied, whereby the effective reaction area is increased up to at least 300% oompared to the apparent stack area of conventional flat tube type cells.
  • 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 an upper outer surface and a lower 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 protrusions of the second gas flow channel part of the upper outer surface thereof; an interconnection layer applied on the protrusions of the second gas flow channel part of the upper outer surface of the support; and a second electrode layer (having a polarity opposite that of the first electrode) applied on the electrolyte layer on the outer surface of the support essentially including the lower outer surface so as not to come into contact with the interconnection layer.
  • a porous flat tube type support which is electrically conductive
  • a material for the support may be different from or the same as the material used for the first electrode layer formed on the surface thereof.
  • the support in the case where the support is made of a material for an air electrode or a third material and the first electrode layer is formed of a material for an air electrode, air flows in the first gas flow channel part and a fuel gas flows in the second gas flow channel part.
  • the support in the case where the support is made of a material for a fuel electrode or a third material and the first electrode layer is formed of the material for a fuel electrode, a fuel gas may flow in the first gas flow channel part, and air may flow in the second gas flow channel part.
  • the electrode material used for the air electrode may include for example LSM (LaSrMnO ), and the electrode material used
  • 3 for the fuel electrode may include for example M/YSZ (cermet), in which YSZ indicates yttria- stabilized zirconia.
  • the support may be manufactured by extruding a flat tube having a plurality of first gas flow channels defined by a plurality of ribs mounted therein, and the second gas flow channels may be formed in the central reaction part of the upper outer surface and the lower outer surface of the support other than both end portions thereof.
  • both end portions of the support other than the second gas flow channel part may be used as a sealing part for gas sealing upon stacking of unit cells.
  • 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 may be located outside the reaction furnace chamber.
  • the first gas flow channels inside the support may have a polygonal or circular cross-section in order to realize a stncturally stable configuration, the size of which is 0.1 ⁇ 5 mm.
  • the ribs between the channels may be 0.1 -5 mm thick.
  • the protrusions other than the channels may have an area corresponding to 5-95% of the total area of the reaction part, and may have a height of 0.1-5 mm and a width of 0.1-10 mm.
  • the support may be manufactured in a manner sixh that inlets and outlets of the second gas flow channels formed in eadi of the upper outer surface and the lower outer surface of the support are provided in a direction perpendicular to the gas flow direction of the first gas flow channels, in order to prevent the mixing of gases and to easily supply the gases.
  • the materials for the first electrode layer, the electrolyte layer, the interconnection layer, and the second electrode layer having a polarity opposite that of the first electrode layer may be applied thin at predetermined thicknesses.
  • the first electrode layer and the second electrode layer may be maintained in a porous state so as to facilitate the diffusion of gas after a sintering process.
  • the electrolyte layer and the interconnection layer should be provided in the form of a non- porous and dense film so that the gas does not leak after a sintering process and also that these two layers are brought into contact to partially overlap with each other.
  • the interconnection layer formed on the protrusions is provided so as not to come into contact with the seoond electrode layer formed on the upper and lower side surfaces of the support.
  • a plurality of protrusions and a plurality of grooves are formed on and in the upper and lower outer surfaces of the support, and the protrusions and the grooves may define the seoond gas channels upon stacking of unit cells so that current is simultaneously produced on the upper and lower outer surfaces of the support.
  • the first electrode layer and the electrolyte layer are sequentially formed.
  • the first electrode layer is formed on the upper surface of the unit cell, the electrolyte layer and the interconnection layer are respectively applied on the grooves and the protrusions on the first electrode layer, and the second electrode layer is applied on the upper and lower side surfaces so as not to come into contact with the interconnection layer.
  • the thickness of the electrolyte layer and the electrode layers may be 1000 /an or less, and the interconnection layer may be provided in the form of a thin film having a thickness of 1.0 mm or less using a conductive material.
  • 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 a porous flat tube type support made of a conductive material and having first gas flow channels formed therein; drying and then pre-sintering the extruded support; cutting and grinding the central portion of the upper and lower outer surfaces of the pre- sintered support other than both end portions thereof corresponding to the sealing part, thus forming the second gas channels having an uneven cross-section with a predetermined width and depth; applying a material for a first electrode layer to a predetermined thickness on the entire outer surface of the support having the second gas flow channels; applying an electrolyte layer to a predetermined thickness on the entire outer surface of the support having the first electrode layer, other than the protrusions between the gas channels of the upper outer surface of the support; applying a material for an interconnection layer to a predetermined thickness on the protrusions of the upper outer surface of the support having the electrolyte layer to bring the interconnection layer
  • the support may be manufactured by extruding an electrode material for an anode or a cathode or a third conductive material into a flat tube type using an extrusion machine, and drying and sintering it.
  • the second gas flow channel part may be formed by cutting and grinding the upper and lower outer surfaces of the extruded flat tube type support to a predetermined depth.
  • the support may be additionally subjected to precise processing by more precisely grinding the upper and lower outer surfaces thereof so that the thickness therebetween is maintained uniform, before and/or after forming the second gas flow channels, in order to form a stack of a plurality of supports through vertical stacking.
  • the application of the layers on the support may be performed through application of a slurry solution of metal or metal oxide particles and then thermal sintering, chemical vapor deposition (CVD) using a metal compound, physical vapor deposition (PVD) using metal, electrochemical plating, or thermal and plasma spray.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • sintering may be separately carried out after completion of respective applications or co-sintering may be performed after completion of a plurality of applications.
  • the present invention provides a flat tube type support for a SOFC, which includes first gas flow channels therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof.
  • first gas flow channels therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof.
  • the grooves of the upper outer surfaces may be combined with the grooves of the lower outer surfaces, thus defining second flow passages.
  • the first electrode layer is formed, after which the interconnection layer is formed on the protrusions of the upper outer surface of the support. Further, the electrolyte layer is formed on the entire outer surface of the support other than the interconnection layer to bring the electrolyte layer into contact with the interconnection layer so that they partially overlap with each other, thereby preventing the leakage of gas. Furthermore, the second electrode layer is formed on the electrolyte layer so as not to come into contact with the interconnection layer and to be separated at a slight distance.
  • the gas flowing through the first flow passages formed in the support is diffused to the upper and lower outer surfaces of the support to thus participate in an electric power generation reaction.
  • the present invention provides a fuel cell obtained by stacking supports each of which includes first gas flow channels formed therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof, thus defining second gas flow channels by the grooves, so that the reaction takes place at the same time on the upper and lower outer surfaces of the support.
  • recesses may be formed at regular intervals to form protrusions on the lower unit cell in the stack.
  • the interconnection layer is formed on the protrusions and the electrolyte layer is formed on the grooves.
  • the second electrode layer is formed on the electrolyte layer so as not to come into contact with the interconnection layer.
  • the lower surface of the upper unit cell is formed with grooves at regular intervals to form protrusions, and the first electrode layer, the electrolyte layer and the second electrode layer are sequentially applied thereon.
  • the upper cell and the lower cell are stacked such that the protrusions thereof are symmetrically piled up.
  • the second electrode layer of the upper cell is connected to the interconnection layer of the lower cell, the second gas flow channel part is formed.
  • the support is formed of a porous material, the gas in the first gas channels may be simultaneously diffused toward the upper and lower outer surfaces of the support, and thus the electrode reaction takes place at the same time on the upper and lower outer surfaces thereof.
  • the present invention provides a planar unit cell for a SOFC, which includes a porous flat tube type support having first gas channels formed therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof, the grooves defining second gas channels upon stacking of supports; a first electrode layer, an electrolyte layer and a second electrode layer sequentially formed on the lower surface of the unit cell, and a first electrode layer formed on the upper surface of the unit cell, an electrolyte layer and an interconnection layer respectively formed on the grooves and the protrusions thereof, and a second electrode layer formed on the grooves so as not to come into contact with the interconnection layer, in which the electrolyte layer and the second electrode layer on both side surfaces of the unit cell are respectively connected to the electrolyte layer and the second electrolyte layer of the upper and lower outer surfaces thereof, thus obtaining a final unit cell.
  • a plurality of first gas flow channels is formed in a longitudinal direction in the flat tube type support having a long rectangular parallelepiped cross-section, and also, the second gas flow channels are formed in the upper and lower outer surfaces of the support, and thereby, upon vertical stacking of supports, second gas flow channels defined between the outer surfaces of the supports may result.
  • the support may be manufactured by extruding an electrode material for an anode or a cathode or a third conductive material using an extrusion machine, drying and pre- sintering the extruded body under temperature conditions lower than final sintering conditions, and cutting and grinding the central portion of the upper and lower outer surfaces of the sintered body corresponding to the reaction part other than both end portions thereof, thus forming the second gas flow channels having an uneven cross- section with a predetermined depth and width.
  • the unit cell for a SOFC may be obtained by sequentially applying the materials for the first electrode layer, the interconnection layer, the electrolyte layer, and the second electrode layer to predetermined thicknesses on the support and then separately sintering respective layers or co-sintering respective layers.
  • the first gas flow channel part having flow passages formed between the ribs of the support functions to allow the gas of the air or fuel electrodes to flow.
  • the second gas flow channel part formed in the central portion of the upper and lower outer surfaces of the support functions to allow the gas of the opposite electrode to flow.
  • the interconnection layer may be provided in the form of a thin film, and thus there is no need for an additional interconnector used in conventional fuel cells.
  • the shape of the second gas flow channel part provided in the outer surface of the support may be formed so that the upper and lower surfaces thereof are the same as and symmetrical to each other, thereby maintaining the thickness of the unit cell thinner. Upon application and sintering of the electrolyte, the warping of the support may be prevented, thus facilitating the manufacture of a unit cell having a large area.
  • the interconnection layer is applied thin on the protrusions of the second gas flow channel part of the upper outer surface of the support, thus lowering internal electric resistance. Therefore, a semioondixtor metal oxide material may be used in lieu of the conductive metal material, and thus the final unit cell may be entirely made of ceramics, consequently exhibiting high resistance to thermal stress and air corrosion.
  • the SOFC including the monolith type unit cell a ⁇ »rding to the present invention is thinner than general flat tube type SOFCs, and may have an effective reaction area increased up to at least 300%, thereby exhibiting higher output power efficiency per unit stack area.
  • the unit cell can be manufactured in a monolith type because an interoonnector made of a metal material is provided in the form of a thin film and thus can have advantages of a flat type, as well as advantageous of a tube type which is structurally solid and has no gas sealing problems.
  • 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 seoond gas flow channels formed on the upper and lower outer surfaces of the support can be provided in the same shape, thereby preventing the warping of the support upon application of the electrode and electrolyte and making it easy to increase the size of the cell.
  • the fuel cell of the present invention can increase the actual effective reaction area up to at least 300% oompared to the stack area, thus drastically improving performance thereof oompared 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 bar-shaped second gas channels and protrusions are formed in and on the upper and lower outer surfaces thereof according to the present invention
  • FIG. 3 is a perspective view showing the support of FIG. 1 in which rectangular parallelepiped-shaped second gas channels and protrusions are formed in and on the upper and lower outer surfaces thereof according to the present invention
  • FIG. 4 is a cutaway view showing the application state and range of layers applied on the outer surface of the support having the second gas channels in the unit cell 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
  • FIG. 6 is a detailed cross-sectional view showing the stacking state of the unit cells of FIG. 5.
  • 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 typically extruded to have a plurality of first gas flow channels 6 in a longitudinal direction.
  • an electrically conductive porous support is obtained.
  • An example of the material for an anode includes a M- YSZ mixture, in which YSZ is yttria-stabilized zirconia, and an example of the material for a cathode includes LSM (LaSrMnO ).
  • the materials for 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 form, the cross-section of which may have any shape as long as the gas uniformly flows, in particular, a polygonal or circular shape so as to have desired strength and provide uniform gas diffusion, and may have a size of 0.1-10 mm and preferably 0.2 ⁇ 5 mm, and the thickness of the ribs 5 between the channels 6 is set to 0.1 ⁇ 5 mm and preferably 0.2 ⁇ 5 mm.
  • the upper outer surface 8 and the lower outer surface 9 of the support 1 may be further precisely ground so that the thickness therebetween is maintained uniform, before and/or after forming the second gas flow channels.
  • the gas inflow direction 33 into and the gas outflow direction 34 from the seoond gas channels 16, 17 may be formed in a direction opposite a longitudinal direction corresponding to the gas inflow direction 37 into and the gas outflow direction 38 from the first gas flow channels, as shown in FIG. 2, in order to prevent the mixing of two gases and solve the gas sealing problems.
  • the area of the protrusions 18, 19 between the seoond gas flow channels 16, 17 of the support is 5-95% and preferably 10-50% of the entire reaction area thereof.
  • the gas channels 8 of the support 10 having the gas channels is the same as that of the channels 17 and the protrusions 19 of the lower outer surface 9 thereof, the gas channels may be uniformly formed upon stacking of supports and the upper and lower outer surfaces may be uniformly subjected to stress upon application of each layer material, thus preventing the warping of the support.
  • the process of manufacturing the unit cell 30 for a SOFC includes sequentially applying a first electrode layer, an electrolyte layer, an interconnection layer, and a second electrode layer at a predetermined thickness on specific portions of the support 10 having the gas channels and then sintering them.
  • the application procedure 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 material for the first electrode layer 41 is applied to a predetermined thickness over the entire outer surface of the support 10 having the gas channels.
  • the electrolyte layer 42 is uniformly applied on the first electrode layer, in particular, applied densely on the entire outer surface of the support 10 other than the protrusions 18 of the upper outer surface 8 so that gas does not leak.
  • the electrolyte layer may be formed by uniformly applying the electrolyte over the entire outer surface of the support 10 and then mechanically wiping the electrolyte off the areas on the protrusions 18 of the upper outer surface 8 of the support to which it had been applied.
  • the interconnection layer 43 is applied to a predetermined thickness on the protrusions 18 of the upper outer surface 8 of the support, in particular, applied densely so as to sufficiently overlap with the electrolyte layer so that gas does not leak.
  • the interconnection layer 43 in a thin film form may be formed through various methods, for example, application of a slurry solution of interconnection particles and then thermal sintering, CVD and PVD using metal and metal compounds, electrochemical plating, or thermal and plasma spray.
  • the material for the interconnection layer 43 should be electrically conductive enough for electrical connection between the electrode of the upper cell and the opposite electrode of the lower cell upon vertical stacking of the unit cells, should have gas impermeability after application and sintering processes and long thermal stability at operation temperatures of the fuel cell, and should be structurally stable at high temperatures in a hydrogen/oxygen atmosphere.
  • any material may be used regardless of the component thereof, as long as it exhibits the above functions, and is exemplified by metal materials sush as Ag or FeCr alloy, or metal oxides such as LaCrO , LaSrCrO or LSM.
  • a plurality of layers may be applied using a material particularly resistant to a hydrogen/oxygen atmosphere.
  • the second electrode layer 44 is applied to a predetermined thickness on the electrolyte layer of the reaction part 22 of the support 10 other than the interconnection layer 43 of the upper outer surface 8 thereof.
  • the second electrode layer is essentially applied on the lower outer surface of the support and preferably on both upper and lower outer surfaces thereof, and is separated at a predetermined distance (d) so as not to be electrically connected to the interconnection layer 43 of the upper outer surface 8 of the support, as shown in FIG. 6.
  • the monolith type unit cells 30 for a SOFC thus manufactured eliminate a need for an interconnector for gas channels used in conventional SOFCs.
  • a sealing material 49 is additionally applied on the sealing part 21 of the unit cell 30, and then such unit cells are vertically stacked as desired, after which cathode and anode collectors 111, 112 are attached thereto, thus completing a fuel cell stack 100.
  • the sealing part 21 provided at both end portions of the cell 30 other than the reaction part 22 is located outside the reaction furnace chamber 105, the end thereof is connected to a pipe part for inflow and outflow of the first gas, and the second gas flowing in the reaction furnace chamber is sealed inside the reaction furnace chamber.
  • the area of the uneven cross-section of the second gas flow channels 16, 17 may be increased up to 200% compared to that of a planar cross-section. Because the reaction occurs on both the upper outer surface 8 and the lower outer surface 9 of the support, even though the area of the interconnection layer 43 of the upper outer surface of the support is set to 50% of the area of the reaction part of the upper outer surface, the reaction area is increased up to at least 150% on each of the upper and lower outer surfaces, and thus the effective reaction area can be increased up to at least 300% based on the reaction area of a final stack.
  • the unit cell according to the present invention is expected to have performance dramatically increased compared to conventional flat tube type fuel cells.

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Abstract

Disclosed is a support for a solid oxide fuel cell, which is easily manufactured, enables scale-up, facilitates gas sealing and has a drastically increased reaction area, a monolith type unit cell using the support, and manufacturing methods thereof. In the unit cell for the fuel cell, first gas channels are formed in a porous flat tube type support made of a conductive material, and a plurality of protrusions formed on upper and lower outer surfaces thereof forms second gas channels upon stacking of unit cells, thus simultaneously producing current on both the upper and lower outer surfaces of the support. On the lower surface of the unit cell, a first electrode layer, an electrolyte layer, and a second layer are sequentially formed, whereas a first electrode layer is formed on the upper surface of the unit cell, an electrolyte layer and an interconnection layer are respectively formed on recesses and protrusions thereof, and a second electrode layer is formed on recesses so as not to come into contact with the interconnection layer. Also provided are methods of manufacturing a support and a monolith type unit cell for a solid oxide fuel cell, which are structurally stable, enable scale-up, and have no gas sealing problems and an effective reaction area increased up to 300 % compared to an apparent stack area, thus drastically improving cell performance.

Description

Description
ELECTRODE SUPPORTS AND MONOLITH TYPE UNIT CELLS FOR SOLID OXIDE FUEL CELLS AND THEIR MANUFACTURING METHODS
Technical Field
[1] The present invention relates to electrode supports and unit cells for fuel cells, and manufacturing methods thereof, and more particularly, relates to a support for solid oxide fuel cells, which is easily manufactured, enables scale-up thereof, facilitates the sealing of a gas and has a drastically increased reaction area, to a monolith type unit cell using the support and to manufacturing methods thereof. Background Art
[2] A solid oxide fuel cell (hereinafter abbreviated to "SOFC"), presently 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. The SOFC is operated under high-temperature conditions in a hydrogen atmosphere and uses a fuel gas sich as methane, methanol, diesel or the like without reformation, and is thus receiving attention as high efficiency low pollution electric power generation technology. The SOFC utilizes as an electrolyte yttria- stabilized zirconia having a stable crystalline stricture. This material exhibits oxygen ion conductivity which is characteristically governed by temperature, and desired conductivity for the fuel cell is attainable at 800- 10000C. Therefore, the SOFC is typically operable at a temperature of 800- 10000C and thus adopts ceramics for an electrode material as they withstand such a high temperature. For example, a material for a cathode to which air is introduced includes LaSrMnO , and a material for an anode to
3 which hydrogen is introduced includes a N-ZrO mixture.
2
[3] In a conventional planar SOFC using an electrolyte plate as a support, a unit cell is constricted by coating front and back sides of the plate with an air electrode and a fuel electrode, respectively, 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 having gas channels for introducing fuel and air on 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. Further, because the electrolyte-electrode assemblies and the interoonnectors are alternately layered in the unit cell stack, there is a dangerous probability of causing structural instability due to thermal and mechanical stress between the electrolyte-electrode assembly and the interconnector of each unit cell for a fuel cell upon high-temperature operation or during heating or cooling. In order to prevent the mixing of the two gases of the upper and lower unit cells and to seal the cell, all of the edge portions of the unit cells are provided with a gas sealing material. Fbwever, because glass useful as the sealing material begins to be softened from about 6000C, there are high risks of emitting a gas due to the softening of the sealing material during high-temperature operation. In severe cases, there is a concern about the breakage of a fuel cell module. Therefore, the planar cell is required to be further improved in terms of various aspects in order to commercialize it.
[4] With the goal of solving the problems of the planar cell, a cylindrical cell is disclosed in US 6207311 Bl and US 6248468 Bl. Compared to the planar cell, the cylindrical cell has slightly lower stack power density but is much higher in terms of strength and gas sealing. Accordingly, a unit fuel cell using the cylindrical cell is constructed by sequentially layering an air electrode, an electrolyte and a fuel electrode 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 oxur. Further, each cell is formed on a solid support, the fuel cell itself constitutes a strong ceramic stricture, and resistance to thermal expansion is high. Furthermore, because contact between the cells occurs in a reducible atmosphere, an interconnector made of a metal material may be used. Fbwever, in order to increase the capacity of the fuel cell, in the case where a plurality of unit cells is connected to each other to thus form a stack, 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.
[5] To draw out current in a radius direction in order to solve the above problems, inside or outside each tube should be provided with an interconnector or wound with a wire. Also, because tubes are disposed at predetermined intervals so as not to be in contact with each other upon formation of the stack, unnecessary spaces are increased, resulting in a lower power density per unit volume.
[6] Recently, in order to solve the problems of SOFCs using the planar cell and the cylindrical cell, there have been developed a unit cell and a unit cell stack using a flat tube type stricture for increasing power density while solving the sealing problems of the planar cell by manufacturing a fuel cell module 1 having both a planar cell structure and a cylindrical cell stricture, as disclosed in Korean Patent Unexamined Publication No. 10-2005-0021027 and US 6416897 and US 6429051. Even in this case, however, gas flow passages for introdudng air or fuel electrode gases and an in- terconnector should be essentially provided to the outside of the flat tube type cell. Although such an interconnector increases the mechanical strength of the stack and enlarges the contact area of unit cells, thus increasing power density, 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 oxur due to air on the surface of the interconnector and the volume and weight of the stack are increased compared to the planar cell.
[7] Therefore, the present inventors have solved the aforementioned problems and proposed a novel monolith type unit cell including a flat tube type support using a thin film in lieu of an interconnector and a method of manufacturing a stack using the same, which is patented (Korean Patent No. 727684). Specifically, 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.
[8] The present invention further improves the advantages of the above monolith type unit cell and is intended to provide a 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 manufacturing method thereof, and a method of manufacturing a monolith type unit cell using the same.
Disclosure of Invention Technical Problem
[9] Therefore, the present invention is devised to solve the problems of conventional planar and cylindrical SOFCs, such as gas sealing, scale-up, mechanical and thermal stability and the like and to maximize electric power generation per unit area. An aspect of the present invention is to provide methods of manufacturing a support and a monolith type unit cell for a SOFC using the same, in which an increase in the size of the unit cell is easy and an electric power generation rate per unit stack area is ππch 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.
[10] 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, whereby a thin film is applied on protrusions between the gas channels of the upper outer surface thereof, without the additional use of an interoonnector, thus forming an electrode layer, an electrolyte layer, gas channels, and an interconnection layer into a single stricture.
[11] A further aspect of the present invention is to provide a method of manufacturing a monolith type unit cell for a SOFC having high performance, in which gas channels having an uneven shape are formed on the upper and lower outer surfaces of a flat tube type support, and thus the reaction area is increased up to 200% compared to the planar surface, and also, in which an electrode reaction oxurs on both of the upper and lower outer surfaces of the support other than the upper protrusions on which the interconnection layer is applied, whereby the effective reaction area is increased up to at least 300% oompared to the apparent stack area of conventional flat tube type cells. Technical Solution
[12] In order to accomplish the technical problem, 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 an upper outer surface and a lower 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 protrusions of the second gas flow channel part of the upper outer surface thereof; an interconnection layer applied on the protrusions of the second gas flow channel part of the upper outer surface of the support; and a second electrode layer (having a polarity opposite that of the first electrode) applied on the electrolyte layer on the outer surface of the support essentially including the lower outer surface so as not to come into contact with the interconnection layer.
[13] In the present invention, a material for the support may be different from or the same as the material used for the first electrode layer formed on the surface thereof. In the embodiment of the present invention, in the case where the support is made of a material for an air electrode or a third material and the first electrode layer is formed of a material for an air electrode, air flows in the first gas flow channel part and a fuel gas flows in the second gas flow channel part. Conversely, in the case where the support is made of a material for a fuel electrode or a third material and the first electrode layer is formed of the material for a fuel electrode, a fuel gas may flow in the first gas flow channel part, and air may flow in the second gas flow channel part. [14] In the embodiment of the present invention, the electrode material used for the air electrode may include for example LSM (LaSrMnO ), and the electrode material used
3 for the fuel electrode may include for example M/YSZ (cermet), in which YSZ indicates yttria- stabilized zirconia.
[15] In the embodiment of the present invention, the support may be manufactured by extruding a flat tube having a plurality of first gas flow channels defined by a plurality of ribs mounted therein, and the second gas flow channels may be formed in the central reaction part of the upper outer surface and the lower outer surface of the support other than both end portions thereof.
[16] In a preferred embodiment of the present invention, both end portions of the support other than the second gas flow channel part may be used as a sealing part for gas sealing upon stacking of unit cells. In the embodiment of the present invention, 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 may be located outside the reaction furnace chamber.
[17] In the embodiment of the present invention, the first gas flow channels inside the support may have a polygonal or circular cross-section in order to realize a stncturally stable configuration, the size of which is 0.1 ~5 mm. The ribs between the channels may be 0.1 -5 mm thick. In the cross-section of the second gas flow channels, the protrusions other than the channels may have an area corresponding to 5-95% of the total area of the reaction part, and may have a height of 0.1-5 mm and a width of 0.1-10 mm.
[18] In the present invention, the support may be manufactured in a manner sixh that inlets and outlets of the second gas flow channels formed in eadi of the upper outer surface and the lower outer surface of the support are provided in a direction perpendicular to the gas flow direction of the first gas flow channels, in order to prevent the mixing of gases and to easily supply the gases. [19] On the outer surface of the support, the materials for the first electrode layer, the electrolyte layer, the interconnection layer, and the second electrode layer having a polarity opposite that of the first electrode layer may be applied thin at predetermined thicknesses. The first electrode layer and the second electrode layer may be maintained in a porous state so as to facilitate the diffusion of gas after a sintering process. The electrolyte layer and the interconnection layer should be provided in the form of a non- porous and dense film so that the gas does not leak after a sintering process and also that these two layers are brought into contact to partially overlap with each other. The interconnection layer formed on the protrusions is provided so as not to come into contact with the seoond electrode layer formed on the upper and lower side surfaces of the support.
[20] In the embodiment of the present invention, a plurality of protrusions and a plurality of grooves are formed on and in the upper and lower outer surfaces of the support, and the protrusions and the grooves may define the seoond gas channels upon stacking of unit cells so that current is simultaneously produced on the upper and lower outer surfaces of the support. On the lower surface of the unit cell, the first electrode layer and the electrolyte layer are sequentially formed. On the other hand, the first electrode layer is formed on the upper surface of the unit cell, the electrolyte layer and the interconnection layer are respectively applied on the grooves and the protrusions on the first electrode layer, and the second electrode layer is applied on the upper and lower side surfaces so as not to come into contact with the interconnection layer.
[21] In the embodiment of the present invention, the thickness of the electrolyte layer and the electrode layers may be 1000 /an or less, and the interconnection layer may be provided in the form of a thin film having a thickness of 1.0 mm or less using a conductive material.
[22] In addition, 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 a porous flat tube type support made of a conductive material and having first gas flow channels formed therein; drying and then pre-sintering the extruded support; cutting and grinding the central portion of the upper and lower outer surfaces of the pre- sintered support other than both end portions thereof corresponding to the sealing part, thus forming the second gas channels having an uneven cross-section with a predetermined width and depth; applying a material for a first electrode layer to a predetermined thickness on the entire outer surface of the support having the second gas flow channels; applying an electrolyte layer to a predetermined thickness on the entire outer surface of the support having the first electrode layer, other than the protrusions between the gas channels of the upper outer surface of the support; applying a material for an interconnection layer to a predetermined thickness on the protrusions of the upper outer surface of the support having the electrolyte layer to bring the interconnection layer into contact with the electrolyte layer so that they partially overlap with each other; and applying the second electrode layer on the electrolyte layer on the outer surface of the support having the interconnection layer essentially including the lower outer surface so as not to come into contact with the interconnection layer.
[23] In the present invention, the support may be manufactured by extruding an electrode material for an anode or a cathode or a third conductive material into a flat tube type using an extrusion machine, and drying and sintering it. The second gas flow channel part may be formed by cutting and grinding the upper and lower outer surfaces of the extruded flat tube type support to a predetermined depth. In a preferred embodiment of the present invention, the support may be additionally subjected to precise processing by more precisely grinding the upper and lower outer surfaces thereof so that the thickness therebetween is maintained uniform, before and/or after forming the second gas flow channels, in order to form a stack of a plurality of supports through vertical stacking.
[24] The application of the layers on the support may be performed through application of a slurry solution of metal or metal oxide particles and then thermal sintering, chemical vapor deposition (CVD) using a metal compound, physical vapor deposition (PVD) using metal, electrochemical plating, or thermal and plasma spray. In order to exhibit intrinsic functions of these layers, sintering may be separately carried out after completion of respective applications or co-sintering may be performed after completion of a plurality of applications.
[25] In addition, the present invention provides a flat tube type support for a SOFC, which includes first gas flow channels therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof. As such, upon stacking of such supports, the grooves of the upper outer surfaces may be combined with the grooves of the lower outer surfaces, thus defining second flow passages.
[26] In the present invention, on the outer surface of the flat tube type support, the first electrode layer is formed, after which the interconnection layer is formed on the protrusions of the upper outer surface of the support. Further, the electrolyte layer is formed on the entire outer surface of the support other than the interconnection layer to bring the electrolyte layer into contact with the interconnection layer so that they partially overlap with each other, thereby preventing the leakage of gas. Furthermore, the second electrode layer is formed on the electrolyte layer so as not to come into contact with the interconnection layer and to be separated at a slight distance.
[27] In the embodiment of the present invention, the gas flowing through the first flow passages formed in the support is diffused to the upper and lower outer surfaces of the support to thus participate in an electric power generation reaction.
[28] In addition, the present invention provides a fuel cell obtained by stacking supports each of which includes first gas flow channels formed therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof, thus defining second gas flow channels by the grooves, so that the reaction takes place at the same time on the upper and lower outer surfaces of the support.
[29] In the fuel cell according to the present invention, recesses may be formed at regular intervals to form protrusions on the lower unit cell in the stack. After the first electrode layer is formed, the interconnection layer is formed on the protrusions and the electrolyte layer is formed on the grooves. Also, the second electrode layer is formed on the electrolyte layer so as not to come into contact with the interconnection layer. The lower surface of the upper unit cell is formed with grooves at regular intervals to form protrusions, and the first electrode layer, the electrolyte layer and the second electrode layer are sequentially applied thereon.
[30] The upper cell and the lower cell are stacked such that the protrusions thereof are symmetrically piled up. Upon stacking, while the second electrode layer of the upper cell is connected to the interconnection layer of the lower cell, the second gas flow channel part is formed. Also, because the support is formed of a porous material, the gas in the first gas channels may be simultaneously diffused toward the upper and lower outer surfaces of the support, and thus the electrode reaction takes place at the same time on the upper and lower outer surfaces thereof.
[31] In addition, the present invention provides a planar unit cell for a SOFC, which includes a porous flat tube type support having first gas channels formed therein and grooves at regular intervals to form protrusions on the upper and lower outer surfaces thereof, the grooves defining second gas channels upon stacking of supports; a first electrode layer, an electrolyte layer and a second electrode layer sequentially formed on the lower surface of the unit cell, and a first electrode layer formed on the upper surface of the unit cell, an electrolyte layer and an interconnection layer respectively formed on the grooves and the protrusions thereof, and a second electrode layer formed on the grooves so as not to come into contact with the interconnection layer, in which the electrolyte layer and the second electrode layer on both side surfaces of the unit cell are respectively connected to the electrolyte layer and the second electrolyte layer of the upper and lower outer surfaces thereof, thus obtaining a final unit cell.
[32] In the unit cell for a SOFC according to the present invention, a plurality of first gas flow channels is formed in a longitudinal direction in the flat tube type support having a long rectangular parallelepiped cross-section, and also, the second gas flow channels are formed in the upper and lower outer surfaces of the support, and thereby, upon vertical stacking of supports, second gas flow channels defined between the outer surfaces of the supports may result.
[33] The support may be manufactured by extruding an electrode material for an anode or a cathode or a third conductive material using an extrusion machine, drying and pre- sintering the extruded body under temperature conditions lower than final sintering conditions, and cutting and grinding the central portion of the upper and lower outer surfaces of the sintered body corresponding to the reaction part other than both end portions thereof, thus forming the second gas flow channels having an uneven cross- section with a predetermined depth and width.
[34] The unit cell for a SOFC may be obtained by sequentially applying the materials for the first electrode layer, the interconnection layer, the electrolyte layer, and the second electrode layer to predetermined thicknesses on the support and then separately sintering respective layers or co-sintering respective layers.
[35] In the SOFC of the present invention, the first gas flow channel part having flow passages formed between the ribs of the support functions to allow the gas of the air or fuel electrodes to flow. When the unit cells are stacked, the second gas flow channel part formed in the central portion of the upper and lower outer surfaces of the support functions to allow the gas of the opposite electrode to flow. The interconnection layer may be provided in the form of a thin film, and thus there is no need for an additional interconnector used in conventional fuel cells.
[36] In the SOFC of the present invention, the shape of the second gas flow channel part provided in the outer surface of the support may be formed so that the upper and lower surfaces thereof are the same as and symmetrical to each other, thereby maintaining the thickness of the unit cell thinner. Upon application and sintering of the electrolyte, the warping of the support may be prevented, thus facilitating the manufacture of a unit cell having a large area.
[37] In the SOFC of the present invention, the interconnection layer is applied thin on the protrusions of the second gas flow channel part of the upper outer surface of the support, thus lowering internal electric resistance. Therefore, a semioondixtor metal oxide material may be used in lieu of the conductive metal material, and thus the final unit cell may be entirely made of ceramics, consequently exhibiting high resistance to thermal stress and air corrosion.
[38] The SOFC including the monolith type unit cell aα»rding to the present invention is thinner than general flat tube type SOFCs, and may have an effective reaction area increased up to at least 300%, thereby exhibiting higher output power efficiency per unit stack area.
Advantageous Effects
[39] According to the present invention, the unit cell can be manufactured in a monolith type because an interoonnector made of a metal material is provided in the form of a thin film and thus can have advantages of a flat type, as well as advantageous of a tube type which is structurally solid and has no gas sealing problems. In particular, when a conductive metal oxide material is used for the interconnector, 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.
[40] Also, the seoond gas flow channels formed on the upper and lower outer surfaces of the support can be provided in the same shape, thereby preventing the warping of the support upon application of the electrode and electrolyte and making it easy to increase the size of the cell.
[41] Also, when the unit cells are stacked, the fuel cell of the present invention can increase the actual effective reaction area up to at least 300% oompared to the stack area, thus drastically improving performance thereof oompared to conventional flat tube type cells. Brief Description of Drawings
[42] FIG. 1 is a perspective view showing an extruded support for use in a SOFC according to the present invention;
[43] FIG. 2 is a perspective view showing the support of FIG. 1 in which bar-shaped second gas channels and protrusions are formed in and on the upper and lower outer surfaces thereof according to the present invention;
[44] FIG. 3 is a perspective view showing the support of FIG. 1 in which rectangular parallelepiped-shaped second gas channels and protrusions are formed in and on the upper and lower outer surfaces thereof according to the present invention;
[45] FIG. 4 is a cutaway view showing the application state and range of layers applied on the outer surface of the support having the second gas channels in the unit cell according to the present invention; [46] 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; and [47] FIG. 6 is a detailed cross-sectional view showing the stacking state of the unit cells of FIG. 5.
[48] <Description of the Reference Numerals in the Drawings>
[49] 1 : extruded support for SOFC
[50] 5: rib 6: first gas flow channel
[51] 8 : upper outer surface of support
[52] 9: lower outer surface of support
[53] 10: support for SOFC having external channels
[54] 16: second gas flow channel provided on upper outer surface of support
[55] 17: seoond gas flow channel provided on lower outer surface of support
[56] 18: protrusion between second gas flow channels on upper outer surface of support
[57] 19: protrusion between second gas flow channels on lower outer surface of support
[58] 21: gas sealing part
[59] 22: fuel cell reaction part
[60] 30: unit cell for SOFC
[61] 33: inflow direction of seoond gas
[62] 34: outflow direction of seoond gas
[63] 37: inflow direction of first gas
[64] 38: outflow direction of first gas
[65] 41: first electrode layer 42: electrolyte layer
[66] 43: interconnection layer 44: seoond electrode layer
[67] 49: gas sealing layer
[68] 100: unit cell stack for SOFC
[69] 105: reaction furnace chamber
[70] 111: anode collector 112: cathode oollector
Best Mode for Carrying out the Invention
[71] Hereinafter, a detailed description will be given of the preferred embodiments of the present invention with reference to the accompanying drawings.
[72] As shown in FIG. 1, the flat tube type support 1 for a SOFC according to the present invention is made of a material for a fuel electrode (anode) or an air electrode (cathode) and is typically extruded to have a plurality of first gas flow channels 6 in a longitudinal direction. Through extrusion, drying and then pre-sintering at a temperature lower than that of a final sintering process, an electrically conductive porous support is obtained. An example of the material for an anode includes a M- YSZ mixture, in which YSZ is yttria-stabilized zirconia, and an example of the material for a cathode includes LSM (LaSrMnO ).
[73] In the support 1, the materials for air and fuel electrodes are merely illustrative, and the present invention is not limited thereto. Alternatively, 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.
[74] In the support 1, the first gas flow channels 6 are provided in a honeycomb form, the cross-section of which may have any shape as long as the gas uniformly flows, in particular, a polygonal or circular shape so as to have desired strength and provide uniform gas diffusion, and may have a size of 0.1-10 mm and preferably 0.2~5 mm, and the thickness of the ribs 5 between the channels 6 is set to 0.1 ~5 mm and preferably 0.2~5 mm.
[75] As shown in FIGS. 2 and 3, the central reaction part of the upper outer surface 8 and the lower outer surface 9 of the support 1 is cut and ground, thus forming seoond gas flow channels 16, 17 having an uneven cross-section, thereby completing a support 10 having final channels.
[76] If necessary, the upper outer surface 8 and the lower outer surface 9 of the support 1 may be further precisely ground so that the thickness therebetween is maintained uniform, before and/or after forming the second gas flow channels.
[77] In the support 10 having the gas channels, the gas inflow direction 33 into and the gas outflow direction 34 from the seoond gas channels 16, 17 may be formed in a direction opposite a longitudinal direction corresponding to the gas inflow direction 37 into and the gas outflow direction 38 from the first gas flow channels, as shown in FIG. 2, in order to prevent the mixing of two gases and solve the gas sealing problems.
[78] In the support 10 having the gas channels, the depth of the second gas flow channels
16, 17 may be set to 0.1-5 mm, and preferably 0.2-3 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, 19 between the seoond gas flow channels 16, 17 of the support is 5-95% and preferably 10-50% of the entire reaction area thereof.
[79] When the shape of the channels 16 and the protrusions 18 of the upper outer surface
8 of the support 10 having the gas channels is the same as that of the channels 17 and the protrusions 19 of the lower outer surface 9 thereof, the gas channels may be uniformly formed upon stacking of supports and the upper and lower outer surfaces may be uniformly subjected to stress upon application of each layer material, thus preventing the warping of the support.
[80] In addition, according to the present invention, the process of manufacturing the unit cell 30 for a SOFC includes sequentially applying a first electrode layer, an electrolyte layer, an interconnection layer, and a second electrode layer at a predetermined thickness on specific portions of the support 10 having the gas channels and then sintering them. In the application procedure, 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.
[81] As shown in FIG. 4, a material for the first electrode layer 41 is applied to a predetermined thickness over the entire outer surface of the support 10 having the gas channels.
[82] Then, the electrolyte layer 42 is uniformly applied on the first electrode layer, in particular, applied densely on the entire outer surface of the support 10 other than the protrusions 18 of the upper outer surface 8 so that gas does not leak. Alternatively, the electrolyte layer may be formed by uniformly applying the electrolyte over the entire outer surface of the support 10 and then mechanically wiping the electrolyte off the areas on the protrusions 18 of the upper outer surface 8 of the support to which it had been applied.
[83] Then, the interconnection layer 43 is applied to a predetermined thickness on the protrusions 18 of the upper outer surface 8 of the support, in particular, applied densely so as to sufficiently overlap with the electrolyte layer so that gas does not leak.
[84] Hence, the interconnection layer 43 in a thin film form may be formed through various methods, for example, application of a slurry solution of interconnection particles and then thermal sintering, CVD and PVD using metal and metal compounds, electrochemical plating, or thermal and plasma spray.
[85] The material for the interconnection layer 43 should be electrically conductive enough for electrical connection between the electrode of the upper cell and the opposite electrode of the lower cell upon vertical stacking of the unit cells, should have gas impermeability after application and sintering processes and long thermal stability at operation temperatures of the fuel cell, and should be structurally stable at high temperatures in a hydrogen/oxygen atmosphere. For the interconnection layer 43, any material may be used regardless of the component thereof, as long as it exhibits the above functions, and is exemplified by metal materials sush as Ag or FeCr alloy, or metal oxides such as LaCrO , LaSrCrO or LSM. Alternatively, a plurality of layers may be applied using a material particularly resistant to a hydrogen/oxygen atmosphere.
[86] Then, the second electrode layer 44 is applied to a predetermined thickness on the electrolyte layer of the reaction part 22 of the support 10 other than the interconnection layer 43 of the upper outer surface 8 thereof. As surfi, the second electrode layer is essentially applied on the lower outer surface of the support and preferably on both upper and lower outer surfaces thereof, and is separated at a predetermined distance (d) so as not to be electrically connected to the interconnection layer 43 of the upper outer surface 8 of the support, as shown in FIG. 6.
[87] After the completion of the respective application processes, in order to realize intrinsic functions of the respective layers and to efficiently adhere adjacent layers, high-temperature sintering is carried out. The conditions and procedure for the sinterin g process may vary depending on the type of support material and the types and properties of respective layer materials to be applied. If necessary, co-sintering may be performed after the completion of a plurality of application processes.
[88] The monolith type unit cells 30 for a SOFC thus manufactured eliminate a need for an interconnector for gas channels used in conventional SOFCs. As shown in FIG. 5, a sealing material 49 is additionally applied on the sealing part 21 of the unit cell 30, and then such unit cells are vertically stacked as desired, after which cathode and anode collectors 111, 112 are attached thereto, thus completing a fuel cell stack 100.
[89] In the stack 100, the sealing part 21 provided at both end portions of the cell 30 other than the reaction part 22 is located outside the reaction furnace chamber 105, the end thereof is connected to a pipe part for inflow and outflow of the first gas, and the second gas flowing in the reaction furnace chamber is sealed inside the reaction furnace chamber.
[90] In the unit cell 30 for a SOFC according to the present invention, the area of the uneven cross-section of the second gas flow channels 16, 17 may be increased up to 200% compared to that of a planar cross-section. Because the reaction occurs on both the upper outer surface 8 and the lower outer surface 9 of the support, even though the area of the interconnection layer 43 of the upper outer surface of the support is set to 50% of the area of the reaction part of the upper outer surface, the reaction area is increased up to at least 150% on each of the upper and lower outer surfaces, and thus the effective reaction area can be increased up to at least 300% based on the reaction area of a final stack. Ultimately, the unit cell according to the present invention is expected to have performance dramatically increased compared to conventional flat tube type fuel cells.
[91] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims

Claims
[1] A unit cell for a solid oxide fuel cell to generate electric power using a fuel gas and air, comprising: a porous flat tube type support made of a conductive material; a first gas flow channel part having one or more flow passages formed in the support; a second gas flow channel part having flow passages of an opposite electrode gas formed in a central reaction part of each of an upper outer surface and a lower 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 protrusions between second gas flow channels of the upper outer surface of the support; an interconnection layer applied on the protrusions between the second gas flow channels of the upper outer surface of the support; and a second electrode layer applied on the reaction part of the outer surface of the support essentially including the lower outer surface so as not to come into contact with the interconnection layer.
[2] The unit cell according to claim 1, wherein when the support is made of a material for an air electrode or a third material and the first electrode layer is formed of a material for an air electrode, air flows in the first gas flow channel part and a fuel gas flows in the second gas flow channel part, and whereas when the support is made of a material for a fuel electrode or a third material and the first electrode layer is formed of a material for a fuel electrode, a fuel gas flows in the first gas flow channel part and air flows in the second gas flow channel part.
[3] The unit cell according to claim 1, wherein the support is manufactured by extruding a flat tube having a plurality of first gas flow channels defined by a plurality of ribs mounted therein, and the second gas flow channels are formed in the reaction part of the upper outer surface and the lower outer surface of the support other than both end portions thereof.
[4] The unit cell according to claim 3, wherein both end portions of the support other than the second gas flow channel part are used as a sealing part for gas sealing upon formation of a unit cell stack.
[5] The unit cell according to claim 1, wherein the first gas flow channels of the support have a stncturally stable polygonal or circular cross-section, a size of which is 0.1 ~5 mm.
[6] The unit cell according to claim 5, wherein the ribs between the channels of the support have a thickness of 0.1-5 mm.
[7] The unit cell according to claim 1, wherein the support is manufactured svch that inlets and outlets of the second gas flow channels formed in each of the upper outer surface and the lower outer surface of the support are provided in a direction opposite a longitudinal direction which is a gas flow direction of the first gas flow channels.
[8] The unit cell according to claim 7, wherein a cross-section of the second gas flow channels has a height of 0.1~5 mm and a width of 0. l~10 mm, and an area of the protrusions other than the channels is 5~95% of a total area of the reaction part.
[9] The unit cell according to claim 1 , wherein materials for the first electrode layer, the electrolyte layer, the interconnection layer, and the second electrode layer having a polarity opposite that of the first electrode layer are applied thin at predetermined thicknesses on predetermined portions of the outer surface of the support.
[10] The unit cell according to claim 9, wherein the first electrode layer and the second electrode layer are maintained in a porous state in order to facilitate gas diffusion after a sintering process.
[11] The unit cell according to claim 9, wherein the electrolyte layer and the interconnection layer are formed sich that they are non-porous and are brought into contact to partially overlap with each other, in order to prevent gas leakage after a sintering process.
[12] The unit cell according to claim 9, wherein the electrolyte layer and the electrode layers have a thickness of 1000 μm or less.
[13] The unit cell according to claim 9, wherein the interconnection layer has a thickness of 1.0 mm or less.
[14] A method of manufacturing a monolith type unit cell for a solid oxide fuel cell to generate electric power using a fuel gas and air, comprising: preparing a support having a plurality of flow passages of a first gas flow channel part therein; processing a central portion of each of an upper outer surface and a lower outer surface of the support, corresponding to a reaction part, other than both end portions thereof, corresponding to a sealing part, thus forming a plurality of protrusions to define flow passages of a second gas flow channel part in a support stack; applying a first electrode layer on an entire outer surface of the support; applying an electrolyte layer on the entire outer surface of the support other than the protrusions of the upper outer surface of the support; applying an interconnection layer on the protrusions of the upper outer surface of the support; and applying a second electrode layer on the electrolyte layer of the reaction part of the outer surface of the support essentially including the lower outer surface so as not to be electrically connected to the interconnection layer.
[15] The method according to claim 14, wherein the support is manufactured by extruding an electrode material for an anode or a cathode or a third conductive material into a flat tube type using an extrusion machine and then performing drying and sintering.
[16] The method according to claim 14, wherein the second gas flow channel part and the protrusions thereof are formed by cutting and grinding the upper outer surface and the lower outer surface of the support to a predetermined depth.
[17] The method according to claim 14, wherein the respective layers are applied through application of a slurry solution of metal or metal oxide particles and then thermal sintering, chemical vapor deposition using a metal compound, physical vapor deposition using metal or metal oxide, electrochemical plating, or thermal and plasma spray.
[18] The method according to claim 14, wherein the respective layers are formed by separately performing sintering after completion of respective applications or by performing co-sintering after completion of a plurality of applications, in order to exhibit intrinsic functions of the respective layers.
[19] A flat tube type support for a solid oxide fuel cell, comprising first gas flow channels formed therein, and recesses at regular intervals to form protrusions on a central reaction part of each of an upper outer surface and a lower outer surface of the support other than both end portions thereof svch that second gas flow passages are defined by the recesses in a support stack.
[20] The support according to claim 19, which is additionally subjected to precise grinding svch that the upper outer surface and lower outer surface thereof are more precisely ground to maintain a thickness therebetween uniform, before and/ or after forming the second gas flow channels.
[21] The support according to claim 19, wherein a first electrode layer is formed on an entire outer surface of the flat tube type support, an interconnection layer is formed on the protrusions of the upper outer surface of the support having the first electrode layer, an electrolyte layer is formed on the entire outer surface of the support other than the protrusions to bring the electrolyte layer into contact with the interconnection layer so that they partially overlap with each other, and a seoond electrode layer is formed on the electrolyte layer of the reaction part so as not to come into contact with the interconnection layer.
[22] The support according to claim 21, wherein a first gas in the first gas flow channels is diffused to the first electrode layer of the reaction part of each of the upper outer surface and the lower outer surface of the support, thus causing an electric power generation reaction.
[23] The support according to claim 21, wherein the second gas flow channels are formed between the lower outer surface of an upper support and the upper outer surface of a lower support in a support stack.
[24] The support according to claim 21, wherein a second gas in the second gas flow channels is diffused to the second electrode layer of the reaction part of each of the lower outer surface of an upper support and the upper outer surface of a lower support in a support stack, thus causing an electric power generation reaction.
[25] The support according to claim 21, wherein the first electrode layer of a lower support in a support stack is electrically connected to the second electrode layer of a lower outer surface of an upper support through the interconnection layer on the protrusions of the upper outer surface of the lower support.
PCT/KR2008/001133 2008-01-31 2008-02-27 Electrode supports and monolith type unit cells for solid oxide fuel cells and their manufacturing methods WO2009096624A1 (en)

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