WO2023243778A1 - Électrode hautement active par une commande de microstructure à l'aide d'un procédé de pulvérisation ultrasonore, son procédé de préparation, et pile à combustible à oxyde solide la comprenant - Google Patents

Électrode hautement active par une commande de microstructure à l'aide d'un procédé de pulvérisation ultrasonore, son procédé de préparation, et pile à combustible à oxyde solide la comprenant Download PDF

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WO2023243778A1
WO2023243778A1 PCT/KR2022/017059 KR2022017059W WO2023243778A1 WO 2023243778 A1 WO2023243778 A1 WO 2023243778A1 KR 2022017059 W KR2022017059 W KR 2022017059W WO 2023243778 A1 WO2023243778 A1 WO 2023243778A1
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anode
fuel cell
layer
ultrasonic spray
ultrasonic
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Korean (ko)
Inventor
신태호
이석희
이상원
김수지
김혜영
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Korea Institute of Ceramic Engineering and Technology KICET
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Korea Institute of Ceramic Engineering and Technology KICET
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • 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
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a highly active electrode through microstructure control using an ultrasonic spray method, a manufacturing method thereof, and a solid oxide fuel cell including the same. More specifically, it relates to a single ultrasonic coating and heat treatment using an ultrasonic spray method.
  • the present invention relates to a highly active electrode through microstructure control using an ultrasonic spray method that can improve process yield by forming a catalyst-coated electrode, a method of manufacturing the same, and a solid oxide fuel cell including the same.
  • the national research and development project information for this invention is as follows.
  • a fuel cell is a device that produces electricity by reacting fuel such as hydrogen or natural gas with oxygen. It is one of the major energy technologies of the future due to its characteristics such as high efficiency, pollution-free, and noise-free.
  • a solid oxide fuel cell uses solid oxide as an electrolyte that allows oxygen ions to pass through, and electrolyte materials include zirconia (ZrO 2 )-based oxide, ceria (CeO 2 )-based oxide, and lanthanum-based oxide.
  • electrolyte materials include zirconia (ZrO 2 )-based oxide, ceria (CeO 2 )-based oxide, and lanthanum-based oxide.
  • Strontium-gallium-magnesium oxide (LSGM), etc. are used.
  • Electrolytes are made of yttria (Y 2 O 3 ), ceria (CeO 2 ), scandia (Sc 2 O 3 ), and gadolinium oxide (Gd 2 O 3 ) for the purpose of improving thermal stability and ionic conductivity at high temperatures. Contains some stabilizers.
  • the unit cell of a solid oxide fuel cell is made with a solid electrolyte in between, an air electrode attached to one side, and a fuel electrode attached to the other side.
  • a mixture of nickel oxide (NiO) and yttrium-stabilized zirconia (YSZ) is used as the anode, and as the air electrode, lanthanum-strontium-cobalt oxide (LSC), lanthanum-strontium-manganese oxide (LSM), and lanthanum-strontium-stabilized zirconia (YSZ) are used as anodes.
  • Cobalt-iron oxide (LSCF), barium-strontium-cobalt-iron oxide (BSCF), etc. are used.
  • LSCF lanthanum-strontium-cobalt-iron oxide
  • BSCF barium-strontium-cobalt-iron oxide
  • Air electrodes are widely used.
  • lanthanum-strontium-cobalt-iron oxide (LSCF)-based or barium-strontium-cobalt-iron oxide (BSCF)-based air electrode material has the property of reacting with zirconia (ZrO 2 )-based electrolyte, so the process of sintering the air electrode
  • ZrO 2 zirconia
  • complex oxides with low ionic conductivity such as lanthanum zirconate (La 2 Zr 2 O 7 ) or strontium zirconate (SrZrO 3 ), are formed at the interface between the cathode and the electrolyte.
  • the formation of the above reactive compounds reduces the overall performance of the fuel cell by lowering the rate at which oxygen ions formed at the air electrode diffuse through the electrolyte and react with hydrogen at the anode, and cause differences in thermal expansion coefficients, thereby reducing thermal and mechanical stability. It causes deterioration
  • the purpose of the present invention is to form a catalyst-coated electrode with a single ultrasonic coating and heat treatment using an ultrasonic spray method, thereby improving the process yield by forming a highly active electrode through microstructure control using an ultrasonic spray method, To provide a method for manufacturing the same and a solid oxide fuel cell including the same.
  • a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method includes a solid electrolyte layer; an anode layer formed on one side of the solid electrolyte layer; and a cathode layer formed on the other side of the solid electrolyte layer, wherein the anode layer has an anode base material and a catalyst material formed on the surface of the anode base material by one ultrasonic coating along with the anode base material.
  • the solid electrolyte layer is formed to a thickness of 200 to 400 ⁇ m.
  • Each of the anode layer and cathode layer is formed to have a thickness of 1 to 15 ⁇ m.
  • the anode base material is formed of a nickel-iron alloy or a composite of nickel and stabilized zirconia, and the catalyst material is formed of cerium oxides.
  • the catalyst material has an average particle diameter of 50 nm or less.
  • the catalyst material is locally dispersed on the surface of the anode base material.
  • the catalyst material may be formed to cover the entire surface of the anode base material.
  • the solid oxide fuel cell further includes a buffer layer formed between the solid electrolyte layer and the anode layer.
  • the buffer layer is formed to have a thickness of 1 to 15 ⁇ m.
  • a method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention to achieve the above object includes forming a solid electrolyte layer; forming an anode layer by ultrasonic spraying an anode mixture spray solution from an ultrasonic spray nozzle on one surface of the solid electrolyte layer and heat treating it; And forming a cathode layer by ultrasonic spraying and heat treating a cathode slurry material from an ultrasonic spray nozzle on the other surface of the solid electrolyte layer, wherein the anode layer includes an anode base material and an anode base material on the surface of the anode base material. It is characterized by having a catalyst material formed by a single ultrasonic coating together.
  • the anode mixed spray solution includes an anode slurry material and a catalyst material mixed with the anode slurry material.
  • the catalyst material is preferably cerium oxides.
  • the heat treatment is performed for 10 to 90 minutes at 1,000 to 1,100°C, respectively.
  • Each of the anode layer and cathode layer is formed to a thickness of 1 to 15 ⁇ m.
  • the solid electrolyte layer is formed to a thickness of 200 to 400 ⁇ m.
  • the step of forming a buffer layer by ultrasonic spraying a buffer slurry material from an ultrasonic spray nozzle on one surface of the solid electrolyte layer and heat treating it is performed.
  • the heat treatment is performed at 1,200 to 1,300°C for 2 to 4 hours.
  • the buffer layer is formed to have a thickness of 1 to 15 ⁇ m.
  • a highly active electrode through microstructure control using an ultrasonic spray method according to the present invention, a manufacturing method thereof, and a solid oxide fuel cell including the same produce an ideal cell using a non-contact ultrasonic spray method sprayed from an ultrasonic spray nozzle. There is meaning in doing it. Additionally, a highly active electrode through microstructure control using an ultrasonic spray method according to the present invention, a method for manufacturing the same, and a solid oxide fuel cell including the same are formed by forming a catalyst-coated electrode through a single ultrasonic coating and heat treatment. High efficiency can be achieved in terms of process.
  • the highly active electrode through microstructure control using the ultrasonic spray method according to the present invention, the manufacturing method thereof, and the solid oxide fuel cell including the same provide electrode ion conductivity by using cerium oxide as a catalyst, thereby chemically By expanding the reaction site, the electrode activity effect is increased, and the performance of the fuel cell can be improved by maintaining and forming an excellent electrode microstructure due to resistance to particle agglomeration.
  • a buffer layer that requires relatively high density is disposed between the anode layer and the solid electrolyte layer. Accordingly, the highly active electrode through microstructure control using the ultrasonic spray method according to the present invention, the manufacturing method thereof, and the solid oxide fuel cell including the same have a buffer layer with a high packing density using the coating characteristics of the ultrasonic spray method. The formation was implemented and optimized.
  • the highly active electrode through microstructure control using the ultrasonic spray method according to the present invention, the manufacturing method thereof, and the solid oxide fuel cell including the same have a buffer layer laminated in a uniform form without agglomeration between particles by ultrasonic coating. Since it acts as a barrier to suppress the formation of secondary phases such as LaNiO 3 , La 2 SrO 4 , LaSrGa 3 O 7 , and LaSrGaO 4 , it is possible to fundamentally block ion diffusion between the solid electrolyte layer and the anode layer.
  • Figure 1 is a cross-sectional view showing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram illustrating an ultrasonic spray device according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram showing an enlarged portion of the ultrasonic spray nozzle of Figure 2.
  • Figure 4 is a schematic diagram illustrating an ultrasonic coating process using an ultrasonic spray device according to an embodiment of the present invention.
  • Figure 5 is a schematic diagram illustrating the process of forming the anode base material and catalyst material with one coating.
  • Figure 6 is an enlarged schematic diagram showing an example of an anode layer.
  • Figure 7 is an enlarged schematic diagram showing another example of an anode layer.
  • Figure 8 is a process flow chart showing a method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention.
  • Figure 9 is a graph showing the results of evaluating the electrical characteristics of the SOFC unit cell sample manufactured according to Example 1.
  • Figure 10 is a graph showing the results of evaluating the electrical properties of the SOFC unit cell sample manufactured according to Example 2.
  • Figure 11 is an SEM photograph showing the anode layer of the SOFC unit cell sample manufactured according to Example 1.
  • Figure 1 is a cross-sectional view showing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention.
  • a solid oxide fuel cell 100 including a highly active electrode through microstructure control using an ultrasonic spray method includes a solid electrolyte layer 120 and an anode layer 140. and a cathode layer 160.
  • the solid oxide fuel cell 100 including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention has a buffer layer formed between the solid electrolyte layer 120 and the anode layer 140. It further includes (180).
  • the solid electrolyte layer 120 is used as a substrate for the solid oxide fuel cell 100.
  • This solid electrolyte layer 120 must not permeate gas, has no electronic conductivity, but must have high oxygen ion conductivity.
  • the solid electrolyte layer 120 can be formed by manufacturing a solid electrolyte material using a solid-state method or a press manufacturing method and sintering it at 1,400 to 1,600°C for 4 to 8 hours. Accordingly, the solid electrolyte layer 120 is formed to have a thickness of 200 to 400 ⁇ m.
  • this solid electrolyte layer 120 As the material used for this solid electrolyte layer 120 , one or more types selected from lanthanum-strontium-gallium-magnesium oxide (LSGM), zirconia (ZrO 2 )-based oxide, and ceria (CeO 2 )-based oxide may be used. . Among these, it is preferable to use lanthanum-strontium-gallium-magnesium oxide (LSGM) as the solid electrolyte layer 120.
  • LSGM lanthanum-strontium-gallium-magnesium oxide
  • the anode layer 140 is formed on one surface 120a of the solid electrolyte layer 120.
  • oxygen receives electrons to become oxygen ions and passes through the solid electrolyte layer 120, and in the cathode layer 160, oxygen ions emit electrons and react with hydrogen gas to form water vapor.
  • This anode layer 140 is preferably formed to have a thickness of 1 to 15 ⁇ m, and a more preferable range may have a thickness of 5 to 10 ⁇ m.
  • the anode layer 140 has an anode base material and a catalyst material formed on the surface of the anode base material by one ultrasonic coating along with the anode base material.
  • the detailed configuration of the anode layer 124 will be described later.
  • the cathode layer 160 is formed on the other surface 120b of the solid electrolyte layer 120.
  • Materials used as the cathode layer 160 include samarium-strontium-cobalt oxide (SSC), lanthanum-strontium-manganese oxide (LSM), lanthanum-strontium-cobalt oxide (LSC), and lanthanum-strontium-cobalt oxide (LSC).
  • SSC samarium-strontium-cobalt oxide
  • LSM lanthanum-strontium-manganese oxide
  • LSC lanthanum-strontium-cobalt oxide
  • LSC lanthanum-strontium-cobalt oxide
  • LSC lanthanum-strontium-cobalt oxide
  • LSCF lithium-cobalt-iron oxide
  • BSCF barium-strontium-cobalt-iron oxide
  • This cathode layer 160 is preferably formed to have a thickness of 1 to 15 ⁇ m, and a more preferable range may have a thickness of 5 to 10 ⁇ m.
  • the buffer layer 180 is formed on one surface 120a of the solid electrolyte layer 120 and is disposed between the solid electrolyte layer 120 and the anode layer 140. At this time, the buffer layer 180 serves to fundamentally block ion diffusion between the solid electrolyte layer 120 and the anode layer 140.
  • ceria-based oxide as a material for the buffer layer 180, more preferably lanthanum (La)-doped ceria (LDC), gadolinium (Gd)-doped ceria (GDC), and samarium (Sm).
  • LDC lanthanum-doped ceria
  • GDC gadolinium
  • Sm samarium
  • SDC doped ceria
  • YDC yttrium doped ceria
  • the buffer layer 180 is preferably formed to a thickness of 1 to 15 ⁇ m, and a more preferable range may be 5 to 10 ⁇ m. If the thickness of the buffer layer 180 is less than 1 ⁇ m, the thickness is too thin and it may be difficult to properly function as a barrier to suppress the formation of secondary phases. On the other hand, if the thickness of the buffer layer 180 exceeds 15 ⁇ m, it is not desirable because it may act as a factor in increasing resistance.
  • Figure 2 is a schematic diagram for explaining an ultrasonic spray device according to an embodiment of the present invention
  • Figure 3 is a schematic diagram showing an enlarged portion of the ultrasonic spray nozzle of Figure 2.
  • Figure 4 is a schematic diagram for explaining the ultrasonic coating process using an ultrasonic spray device according to an embodiment of the present invention
  • Figure 5 is a schematic diagram for explaining the process of forming the anode base material and catalyst material with one coating.
  • the ultrasonic spray device 200 includes a heating plate 210 for heating the substrate 110 to a set temperature and an ultrasonic generator for generating ultrasonic waves. It includes (220) and an ultrasonic spray nozzle 230 for spraying the anode mixed spray solution converted into a fine mist by mechanical vibration caused by ultrasonic waves generated from the ultrasonic generator 220 onto the upper part of the substrate 110.
  • the ultrasonic spray device 200 of the present invention sprays the anode mixed spray solution converted into mist from the ultrasonic spray nozzle 230 onto the substrate 110, and heats it to a temperature set by the heating plate 210. It can be done.
  • the ultrasonic spray device 200 supplies a syringe 240 for controlling the supply amount of the solution supplied to the ultrasonic spray nozzle 230 and a compressed carrier gas to the ultrasonic spray nozzle 230 to create an anode mixed spray solution. It may further include a carrier gas supply unit 250 for pressurizing. In addition, although not shown in the drawing, the ultrasonic spray device 200 may further include a temperature controller for controlling the temperature of the heating plate 210 and a power supply unit for supplying power to the heating plate 210.
  • the anode mixed spray solution is ultrasonic sprayed from the ultrasonic spray nozzle 230 on one surface of the solid electrolyte layer 120 and heat treated to form the anode layer 140.
  • the anode layer 140 has an anode base material 140a and a catalyst material 140b formed on the surface of the anode base material 140a by one ultrasonic coating along with the anode base material 140a.
  • the anode base material 140a is made of a nickel-iron alloy or a composite of nickel and stabilized zirconia, and the catalyst material 140b is made of cerium oxides.
  • the catalyst material 140b preferably has an average particle diameter of 50 nm or less, and a more preferable range may be 1 to 30 nm. This is because if the average particle diameter of the catalyst material 140b exceeds 50 nm, nozzle clogging of the ultrasonic spray nozzle 230 may be caused.
  • This ultrasonic spray device 200 is applied to many fields. It is mainly used as a coating method by spraying liquid droplets. However, in the present invention, the anode mixed spray solution is sprayed using ultrasonic coating, which is different from the existing coating method. That is, by taking advantage of the characteristics of the ultrasonic spray coating method, it is possible to secure an effective coating area and thickness by finely stacking solid powder on the solid electrolyte layer 120.
  • the present invention was applied to electrode coating of the solid oxide fuel cell (100).
  • a method of introducing a catalyst into the electrode to improve the performance of the solid oxide fuel cell 100 includes an infiltration method in which a solution containing metal ions is dropped onto an existing electrode and then heat treated to form a catalyst.
  • the ultrasonic spray coating method is based on the infiltration method and sprays a solution containing metal ions to form a catalyst on the electrode.
  • This infiltration method is applied over unit cells where electrode formation has been completed.
  • a substrate on which the catalyst will be formed is essential, and this is a technology applied after the process of coating and heat treating the electrode on the substrate. Because of this, an additional heat treatment process is required to introduce the catalyst, which is disadvantageous in terms of production and processing.
  • the process begins with the substrate before forming the electrode.
  • the anode mixed spray solution sprays together an anode slurry material in which solid powder to form an electrode is dispersed and a catalyst material (metal ion) for catalyst formation.
  • electrode and catalyst formation can be performed with one ultrasonic coating and heat treatment.
  • an electrode into which a catalyst is ideally introduced is formed through one heat treatment after ultrasonic coating.
  • the use of droplets to introduce the coating and catalyst required for the electrode can be reduced to one method, and the electrode and catalyst can be formed simultaneously through a single heat treatment process.
  • the present invention achieves high efficiency in terms of process by forming the anode layer 140, which is a catalyst-coated electrode, with a single ultrasonic coating and heat treatment using a non-contact ultrasonic spray method sprayed from an ultrasonic spray nozzle. can be secured.
  • Figure 6 is an enlarged schematic diagram showing an example of an anode layer
  • Figure 7 is an enlarged schematic diagram showing another example of an anode layer.
  • the anode layer 140 has an anode base material 140a and a catalyst material 140b formed on the surface of the anode base material 140a by one ultrasonic coating along with the anode base material 140a. .
  • the catalyst material 140b may be locally dispersed and disposed on the surface of the anode base material 140a.
  • cerium oxide which is the catalyst material 140b, is formed in a dispersed manner on the surface of the anode base material 140a, thereby providing electrode ion conductivity and creating an excellent electrode microstructure to improve the performance of the fuel cell. It becomes possible.
  • the anode layer 140 includes an anode base material 140a and a catalyst material 140b formed by one ultrasonic coating together with the anode base material 140a on the surface of the anode base material 140a. ) has.
  • the catalyst material 140b is formed to cover the entire surface of the anode base material 140a.
  • This catalytic material 140b may be formed on the surface of the anode base material 140a to a thickness of 100 nm or less, and may cover the entire surface of the anode base material 140a.
  • cerium oxide which is the catalyst material 140b, is formed to cover the entire surface of the anode base material 140a, thereby providing electrode ion conductivity and creating an excellent electrode microstructure, thereby improving the performance of the fuel cell. can be improved.
  • the solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method manufactures an ideal cell using a non-contact ultrasonic spray method sprayed from an ultrasonic spray nozzle. There is meaning in doing it. Additionally, a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention forms a catalyst-coated electrode through a single ultrasonic coating and heat treatment, thereby improving the process aspect. It is possible to secure high efficiency.
  • the solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method provides electrode ion conductivity by using cerium oxide as a catalyst, thereby providing a site for electrochemical reaction.
  • the electrode activity effect is increased by expanding, and the performance of the fuel cell can be improved by maintaining and forming an excellent electrode microstructure due to resistance to particle agglomeration.
  • the solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method uses the coating characteristics of the ultrasonic spray method to form a buffer layer with a high packing density. Implemented and optimized.
  • the solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method has a buffer layer laminated in a uniform form without agglomeration between particles by ultrasonic coating. Since it acts as a barrier to suppress the formation of secondary phases such as 3 , La 2 SrO 4 , LaSrGa 3 O 7 , and LaSrGaO 4 , it is possible to fundamentally block ion diffusion between the solid electrolyte layer and the anode layer.
  • Figure 8 is a process flow chart showing a method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention.
  • the method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method includes a solid electrolyte layer forming step (S110) and an anode layer. It includes a forming step (S120) and a cathode layer forming step (S130).
  • a solid electrolyte layer to be used as a substrate for a solid oxide fuel cell is formed.
  • the solid electrolyte layer can be formed by manufacturing a solid electrolyte material using a solid-state method and a press manufacturing method and sintering it at 1,400 to 1,600°C for 4 to 8 hours. Accordingly, the solid electrolyte layer is formed to a thickness of 200 to 400 ⁇ m.
  • lanthanum-strontium-gallium-magnesium oxide LSGM
  • zirconia ZrO 2
  • ceria CeO 2
  • an anode mixed spray solution is ultrasonic sprayed from an ultrasonic spray nozzle on one surface of the solid electrolyte layer and heat treated to form an anode layer.
  • heat treatment is preferably performed at 1,000 to 1,100°C for 10 to 90 minutes.
  • the thickness can be adjusted by adjusting the spray time, spray amount, and carrier gas input amount. Accordingly, the anode layer is formed to have a thickness of 1 to 15 ⁇ m.
  • the anode mixed spray solution includes an anode slurry material and a catalyst material mixed with the anode slurry material.
  • the anode slurry material may be a nickel-iron alloy or a composite of nickel and stabilized zirconia mixed with polyvinyl butyral, a dispersant, ethanol, and isopropyl alcohol, but is limited thereto. That is not the case.
  • cerium oxides be used as the catalyst material.
  • These catalyst materials preferably have an average particle diameter of 50 nm or less, and a more preferable range may be 1 to 30 nm. This is because if the average particle diameter of the catalyst material exceeds 50 nm, it may cause nozzle clogging of the ultrasonic spray nozzle.
  • the anode layer has an anode base material and a catalyst material formed on the surface of the anode base material by one ultrasonic coating together with the anode base material.
  • the catalyst material may be locally dispersed and disposed on the surface of the anode base material.
  • cerium oxide which is a catalyst material, is formed in a dispersed manner on the surface of the anode base material, thereby providing electrode ion conductivity and creating an excellent electrode microstructure, thereby improving the performance of the fuel cell.
  • the catalyst material may be formed to cover the entire surface of the anode base material.
  • This catalyst material may be formed on the surface of the anode base material to a thickness of 100 nm or less, and may cover the entire surface of the anode base material.
  • the cerium oxide which is a catalyst material, to cover the entire surface of the anode base material layer, it is possible to improve the performance of the fuel cell by providing electrode ion conductivity and creating an excellent electrode microstructure.
  • the anode layer is formed by ultrasonic spraying using an ultrasonic spray device, it is possible to form a buffer layer with a thin and uniform thickness, and precise adjustment can be made using various patterning methods.
  • the ultrasonic spray nozzle of the present invention unlike the air spray nozzle, forms fine particles in which the metal powder and solvent are well dispersed, so when coating by ultrasonic spraying, the specific surface area is higher than when spraying with an air spray nozzle. You will have
  • the anode mixed spray solution used was an anode slurry material in which solid powder to form an electrode was dispersed and a catalyst material (metal ion) for catalyst formation.
  • electrode and catalyst formation can be performed with one ultrasonic coating and heat treatment.
  • an electrode into which a catalyst is ideally introduced is formed through one heat treatment after ultrasonic coating.
  • the use of droplets to introduce the coating and catalyst required for the electrode can be reduced to one method, and the electrode and catalyst can be formed simultaneously through a single heat treatment process.
  • the present invention can secure high efficiency in terms of process by forming a catalyst-coated electrode through one-time ultrasonic coating and heat treatment using a non-contact ultrasonic spray method sprayed from an ultrasonic spray nozzle.
  • the ultrasonic spray method is a non-contact method that sprays from an ultrasonic spray nozzle spaced apart from the substrate. Therefore, by using the ultrasonic spray method, it is possible to coat the anode layer in a thin and uniform form on the solid electrolyte layer, and the coating is achieved without agglomeration between dispersed particles, thereby ensuring high packing density.
  • a cathode slurry material is ultrasonic sprayed from an ultrasonic spray nozzle on the other side of the solid electrolyte layer and heat treated to form a cathode layer.
  • heat treatment is preferably performed at 1,000 to 1,100°C for 10 to 90 minutes.
  • the thickness can be adjusted by adjusting the spray time, spray amount, carrier gas input amount, etc. Accordingly, the cathode layer, like the anode layer, is formed to have a thickness of 1 to 15 ⁇ m.
  • the cathode slurry material may be a mixture of the raw material samarium strontium cobalt oxide (SSC), polyvinyl butyral, dispersant, ethanol, and isopropyl alcohol, but is limited to this. It doesn't work.
  • SSC samarium strontium cobalt oxide
  • polyvinyl butyral polyvinyl butyral
  • dispersant ethanol
  • isopropyl alcohol but is limited to this. It doesn't work.
  • the raw materials for the cathode slurry material include samarium-strontium-cobalt oxide (SSC), lanthanum-strontium-manganese oxide (LSM), lanthanum-strontium-cobalt oxide (LSC), and lanthanum-strontium cobalt oxide (SSC).
  • SSC samarium-strontium-cobalt oxide
  • LSM lanthanum-strontium-manganese oxide
  • LSC lanthanum-strontium-cobalt oxide
  • SSC lanthanum-strontium cobalt oxide
  • One or more types selected from lithium-cobalt-iron oxide (LSCF), barium-strontium-cobalt-iron oxide (BSCF), etc. may be used.
  • this cathode layer like the anode layer, is formed by an ultrasonic spray method using an ultrasonic spray device, it is possible to form the cathode layer with a thin and uniform thickness, and precise adjustment can be made using various patterning methods.
  • the ultrasonic spray nozzle of the present invention suppresses agglomeration of particles through continuous ultrasonic treatment during the ultrasonic spray process. Accordingly, since the solvent and particles form fine particles well dispersed, when the particles are coated by ultrasonic spraying, a higher specific surface area is obtained.
  • the ultrasonic spray method is a non-contact method that sprays from an ultrasonic spray nozzle spaced apart from the substrate. Therefore, by using the ultrasonic spray method, it is possible to coat the cathode layer on the buffer layer in a thin and uniform form, and the coating is done without agglomeration between dispersed particles, thereby ensuring packing density.
  • the method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method is performed between the solid electrolyte layer forming step (S110) and the anode layer forming step (S120). It further includes a buffer layer forming step (not shown) performed in .
  • a buffer slurry material is ultrasonic sprayed from an ultrasonic spray nozzle on one surface of the solid electrolyte layer and heat treated to form a buffer layer.
  • heat treatment is preferably performed at 1,200 to 1,300°C for 2 to 4 hours.
  • the thickness can be adjusted by adjusting the spray time, spray amount, carrier gas input amount, etc.
  • the buffer layer is preferably formed to a thickness of 1 to 15 ⁇ m, and a more preferable range may be 5 to 10 ⁇ m.
  • the buffer slurry material may be a mixture of ceria-based oxide as a raw material and polyvinyl butyral, a dispersant, ethanol, and isopropyl alcohol, but is not limited thereto.
  • Ceria-based oxides include lanthanum (La)-doped ceria (LDC), gadolinium (Gd)-doped ceria (GDC), samarium (Sm)-doped ceria (SDC), and yttrium (Y)-doped ceria ( YDC), etc. may be used.
  • LDC lanthanum-doped ceria
  • GDC gadolinium
  • Sm samarium
  • SDC samarium
  • Y yttrium
  • the buffer layer is formed using an ultrasonic spray method, it is possible to form it with a thin and uniform thickness, and precise adjustment can be made using various patterning methods. In this way, a relatively high-density buffer layer coated by ultrasonic spraying is disposed between the anode layer and the solid electrolyte layer.
  • a buffer layer laminated in a uniform form without agglomeration between particles by ultrasonic coating serves as a barrier to suppress the formation of secondary phases such as LaNiO 3 , La 2 SrO 4 , LaSrGa 3 O 7 , and LaSrGaO 4 . Therefore, it is possible to fundamentally block ion diffusion between the solid electrolyte layer and the anode layer.
  • the method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention uses a non-contact ultrasonic spray method spraying from an ultrasonic spray nozzle. It is meaningful in manufacturing an ideal cell using Additionally, the method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention involves forming a catalyst-coated electrode through a single ultrasonic coating and heat treatment. High efficiency can be achieved in terms of process.
  • the method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method provides electrode ion conductivity by using cerium oxide as a catalyst, thereby providing electrochemical properties.
  • the electrode activity effect is increased, and the performance of the fuel cell can be improved by maintaining and forming an excellent electrode microstructure due to resistance to particle agglomeration.
  • the method for manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method is to produce a buffer layer with a high packing density by using the coating characteristics of the ultrasonic spray method. The formation was implemented and optimized.
  • the method of manufacturing a solid oxide fuel cell including a highly active electrode through microstructure control using an ultrasonic spray method according to an embodiment of the present invention is a buffer layer laminated in a uniform form without agglomeration between particles by ultrasonic coating. Since it acts as a barrier to suppress the formation of secondary phases such as LaNiO 3 , La 2 SrO 4 , LaSrGa 3 O 7 , and LaSrGaO 4 , it is possible to fundamentally block ion diffusion between the solid electrolyte layer and the anode layer.
  • LSGM Lanthanum-strontium-gallium-magnesium oxide
  • a buffer slurry material was ultrasonic sprayed from an ultrasonic spray nozzle on one side of the solid electrolyte layer and then heat treated for 3 hours at 1,250°C to form a 5 ⁇ m thick buffer layer made of LDC (La 0.4 Ce 0.6 O 2 ) material. .
  • an anode mixed spray solution containing cerium oxide with an average particle diameter of 20 nm was ultrasonic sprayed onto the anode slurry material from the ultrasonic spray nozzle of the ultrasonic spray device on the buffer layer, and then heat treated for 1 hour at 1,000°C to form a Ni-Fe alloy. A 10 ⁇ m thick anode layer coated with cerium oxide was formed.
  • the cathode slurry material was ultrasonic sprayed on the other side of the solid electrolyte layer from an ultrasonic spray nozzle at 1,000°C for 1 hour to form a 10 ⁇ m thick cathode layer made of SSC (Sm 0.5 Sr 0.5 CoO 3 ) material, forming a SOFC unit.
  • Cell samples were prepared.
  • each slurry material is prepared by adding 0.045 g of polyvinyl butyral, 0.015 g of dispersant, 2.7 g of ethanol, and 6.3 g of isopropanol to 1.5 g of raw material. was used.
  • a SOFC unit cell sample was prepared in the same manner as in Example 1, except that an anode mixed spray solution containing cerium oxide with an average particle diameter of 30 nm was added to the anode slurry material and subjected to ultrasonic spraying and heat treatment at 1,050°C for 60 minutes. .
  • a SOFC unit cell sample was prepared in the same manner as in Example 1, except that an anode mixed spray solution containing cerium oxide with an average particle diameter of 10 nm was added to the anode slurry material and subjected to ultrasonic spraying and heat treatment at 1,000°C for 30 minutes. .
  • the anode slurry material was ultrasonic sprayed and then heat treated at 1,000°C for 1 hour to form an anode layer with a thickness of 10 ⁇ m using only Ni-Fe alloy in the same manner as in Example 1.
  • a SOFC unit cell sample was prepared.
  • Table 1 shows the results of evaluating the electrical properties of SOFC unit cell samples prepared according to Examples 1 to 3 and Comparative Example 1.
  • cerium oxide a catalyst material
  • it provides electrode ion conductivity and creates an excellent electrode microstructure, improving the performance of the fuel cell. was confirmed to improve.
  • Figures 9 and 10 are graphs showing the results of evaluating the electrical characteristics of the SOFC unit cell sample manufactured according to Example 1.
  • Figure 9 shows the electrical characteristic values for a SOFC unit cell sample in which 3 wt% H 2 O - 97 wt% H 2 was supplied to the anode layer in fuel cell mode
  • Figure 10 shows electrical characteristics in electrolysis and fuel cell mode. This shows the electrical characteristic values for a SOFC/SOEC unit cell sample in which 50wt% H 2 O - 50wt% H 2 was supplied to the anode layer.
  • the fuel cell using an electrode coated with cerium oxide on a Ni-Fe alloy exhibits an excellent power density of 1.40 W cm -2 at 1073 K and 1.01 It can be confirmed that the electrolysis performance is Acm -2 @1.3V.
  • Figure 11 is an SEM photograph showing the anode layer of the SOFC unit cell sample manufactured according to Example 1.
  • the microstructure of the anode layer of the SOFC unit cell sample prepared according to Example 1 is shown. At this time, it can be confirmed that cerium oxide, which is a catalyst material, is uniformly distributed with an average diameter of 50 nm or less on the surface of the Ni-Fe alloy, which is the anode base material, by ultrasonic coating.

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Abstract

Sont divulgués une électrode hautement active par une commande de microstructure à l'aide d'un procédé de pulvérisation ultrasonore, son procédé de préparation, et une pile à combustible à oxyde solide la comprenant, un rendement de processus pouvant être amélioré par la formation d'une électrode sur laquelle un catalyseur est revêtu par revêtement ultrasonore en une fois à l'aide du procédé de pulvérisation ultrasonore et d'un traitement thermique. La pile à combustible à oxyde solide comprenant l'électrode hautement active par une commande de microstructure à l'aide du procédé de pulvérisation ultrasonore, selon la présente invention, comprend : une couche d'électrolyte solide ; une couche d'anode sur une surface de la couche d'électrolyte solide ; et une couche de cathode sur l'autre surface de la couche d'électrolyte solide, la couche d'anode comprenant : un matériau de base d'anode ; et un matériau catalytique formé conjointement avec le matériau de base d'anode sur la surface du matériau de base d'anode par revêtement par ultrasons en une fois.
PCT/KR2022/017059 2022-06-16 2022-11-02 Électrode hautement active par une commande de microstructure à l'aide d'un procédé de pulvérisation ultrasonore, son procédé de préparation, et pile à combustible à oxyde solide la comprenant Ceased WO2023243778A1 (fr)

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