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WO2025183275A1 - Suspension d'électrode pour la réparation de fissures, couche de catalyseur pour pile à combustible, ensemble membrane-électrode et pile à combustible - Google Patents

Suspension d'électrode pour la réparation de fissures, couche de catalyseur pour pile à combustible, ensemble membrane-électrode et pile à combustible

Info

Publication number
WO2025183275A1
WO2025183275A1 PCT/KR2024/009439 KR2024009439W WO2025183275A1 WO 2025183275 A1 WO2025183275 A1 WO 2025183275A1 KR 2024009439 W KR2024009439 W KR 2024009439W WO 2025183275 A1 WO2025183275 A1 WO 2025183275A1
Authority
WO
WIPO (PCT)
Prior art keywords
crack
electrode slurry
catalyst layer
region
nanoparticles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/KR2024/009439
Other languages
English (en)
Korean (ko)
Inventor
김정호
김준영
송가영
공낙원
이은수
김형수
이주성
남경식
박찬미
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolon Industries Inc
Original Assignee
Kolon Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020240087823A external-priority patent/KR20250133120A/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Publication of WO2025183275A1 publication Critical patent/WO2025183275A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrode slurry for crack repair, and more particularly, to an electrode slurry for crack repair, a catalyst layer for a fuel cell, a membrane-electrode assembly, and a fuel cell.
  • Fuel cells which directly convert the chemical energy generated by fuel oxidation into electrical energy, are attracting attention as a next-generation energy source due to their high energy efficiency and environmental friendliness with low pollutant emissions. These fuel cells are generally structured with an anode and a cathode formed on either side of a polymer electrolyte membrane, and this structure is called a membrane electrode assembly (MEA). Fuel cells can be classified into alkaline electrolyte fuel cells and polymer electrolyte membrane fuel cells (PEMFC) depending on the type of electrolyte membrane.
  • PEMFC polymer electrolyte membrane fuel cells
  • polymer electrolyte membrane fuel cells are attracting attention as a power source for portable, automotive, and home use due to their advantages such as low operating temperature of less than 100°C, fast start-up and response characteristics, and excellent durability.
  • a representative example of such polymer electrolyte membrane fuel cells is the proton exchange membrane fuel cell (PEMFC), which uses hydrogen gas as fuel.
  • PEMFC proton exchange membrane fuel cell
  • the polymer electrolyte membrane can shrink or expand for various reasons, leading to cracks forming on the electrodes formed on one side of the membrane.
  • commercial electrode slurries are used to repair these cracks, they are applied only to the surrounding area, deepening the cracks.
  • An object of the present invention is to provide an electrode slurry capable of repairing cracks in an electrode.
  • Another object of the present invention is to provide an electrode slurry for crack repair that can improve durability, heat dissipation effect, efficiency of catalytic reaction or moisture retention ability.
  • Another object of the present invention is to provide a membrane-electrode assembly in which both performance and durability are improved.
  • Another object of the present invention is to provide a fuel cell including the membrane-electrode assembly.
  • an electrode slurry for crack repair which comprises at least 60 wt% of a first solvent having a surface tension of 40 mN/m or less at 20 ° C, a surface tension of 65 mN/m or less at 20°C, a viscosity of 100 cP or less at 20°C, and a total solid content of 12 wt% or less.
  • the first solvent may include at least one selected from the group consisting of alcohol, acetic acid, propionic acid, oleic acid, carbon tetrachloride, pyrrole, and pyridine.
  • the crack repair electrode slurry further includes a second solvent having a surface tension of more than 40 mN/m at 20°C, and the content of the second solvent may be 10 wt% or less based on the total weight of the crack repair electrode slurry.
  • a crack repair electrode slurry further comprising functional nanoparticles in any one of the first to third aspects can be provided.
  • the functional nanoparticles may include at least one selected from the group consisting of radical scavengers, catalytic nanoparticles, heat-radiating nanoparticles, and hygroscopic nanoparticles.
  • a crack repair electrode slurry may be provided, which further comprises a binder dispersion comprising a binder in any one of the first to fifth aspects.
  • the binder may be any one selected from the group consisting of a fluorine-based ion conductor, a hydrocarbon-based ion conductor, and a mixture thereof.
  • a catalyst layer for a fuel cell comprising a first catalyst layer including a crack region and a second catalyst layer on the first catalyst layer, wherein a portion of the second catalyst layer corresponding to the crack region extends along the crack surface and includes a first region including a first binder and a second region different from the first region and including a second binder, and wherein a content of the first binder per unit volume of the first region is higher than a content of the second binder per unit volume of the second region.
  • the height of the first region in a direction intersecting the direction in which the crack surface extends may be greater than 0 ⁇ m and less than or equal to 2 ⁇ m.
  • a membrane-electrode assembly comprising a catalyst layer for a fuel cell according to the seventh or eighth aspect is provided.
  • a fuel cell comprising a membrane-electrode assembly according to the ninth aspect.
  • the problem of the crack actually becoming deeper because it is applied only to the area surrounding the crack can be solved.
  • an electrode slurry can be provided that improves the performance and durability of a membrane-electrode assembly due to a repaired crack.
  • an electrode slurry having improved chemical durability, heat dissipation effect, catalytic reaction efficiency, or moisture retention ability can be provided.
  • FIG. 1a is a cross-sectional view of a catalyst layer for a fuel cell with a crack repaired according to one embodiment of the present invention.
  • Figure 1b is an enlarged view of a portion of the second catalyst layer positioned at a position corresponding to the crack area of Figure 1a.
  • Figure 2 is a schematic diagram illustrating a fuel cell according to one embodiment of the present invention.
  • Figure 3 is an optical microscope photograph of a catalyst layer for a fuel cell in which cracks have been repaired according to Example 1 and Comparative Example 1.
  • Figure 4 is a graph showing the performance of membrane-electrode assemblies according to Comparative Examples 1 and 2 and Example 1.
  • At least one of a, b and c may include a, b or c alone, or a combination of two or more selected from the group consisting of a, b and c.
  • the embodiments may be combined unless specifically stated otherwise.
  • the effects of the present invention may be defined as including the effects derived from each embodiment and the effects resulting from the organic combination of the embodiments.
  • Embodiments 1 and 2 may be organically combined with each other, unless the context clearly indicates otherwise, and the effects of the present invention may include the effects resulting from the combination of Embodiments 1 and 2.
  • the numerical range indicated by the term "to" in this specification refers to a numerical range that includes the values described before and after the term as the lower limit and the upper limit, respectively.
  • the numerical range disclosed in this specification can be understood as any numerical range that has any one of the multiple lower limit values and any one of the multiple upper limit values as the lower limit and the upper limit, respectively.
  • a to b, or c to d is described in the specification, it can be understood that a or more and b or less, a or more and d or less, c or more and d or less, or c or more and b or less is described.
  • the term "layer" or film may include cases where it is formed not only over the entire area when observing the area where the layer or film exists, but also cases where it is formed over only a portion of the area.
  • the surface of the layer or film may be defined to include a flat shape, a non-flat shape, and a combination thereof; or a continuous shape, a discontinuous shape, and a combination thereof.
  • the coverage of the other element on the surface of the one element may be defined as 1% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more.
  • a layer can also be a term that includes a shape in which the surface is irregularly or randomly formed.
  • the average particle diameter of the particles can be defined as the particle diameter (D 50 ) when the cumulative percentage becomes 50% in the volume-based particle size distribution curve when measured by a laser diffraction particle size distribution measuring device.
  • the average particle diameter of the particles can be calculated by dispersing the target particles in a dispersion medium, introducing them into a commercially available laser diffraction particle size measuring device (e.g., Microtrac S3500), and measuring the difference in diffraction pattern according to particle size when the particles pass through a laser beam.
  • an electrode slurry for crack repair which comprises at least 60 wt% of a solvent having a surface tension of 40 mN/m or less at 20 ° C, a surface tension of 65 mN/m or less at 20°C, a viscosity of 100 cP or less at 20°C, and a total solids content of 12 wt% or less.
  • the problem that the depth of the crack actually deepens because it is applied only to the peripheral area of the crack can be solved, and an electrode slurry can be provided in which the performance and durability of a membrane-electrode assembly are improved due to the repaired crack.
  • the electrode slurry for crack repair according to the present invention comprises at least 60 wt% of a first solvent having a surface tension of 40 mN/m or less at 20°C.
  • the surface tension refers to the property of the force by which the surface of the solvent contracts on its own to take up as small an area as possible, and can be measured using the capillary rise method or the Du Nouy tensiometer.
  • the first solvent is a factor that controls the viscosity and surface tension of the electrode slurry, and as a result, the crack repair effect can vary depending on the content of the first solvent.
  • the surface tension of the first solvent may be 5 to 40 mN/m at 20°C, and more specifically, 7 to 39 mN/m, 10 to 35 mN/m, 15 to 30 mN/m, 18 to 25 mN/m, 20 to 24 mN/m, or 21 to 23 mN/m. If the surface tension of the first solvent is outside the above numerical range, the electrode slurry may be applied only to the peripheral area of the crack, and as the depth of the crack deepens, it may become difficult to repair the crack formed in the electrode.
  • the content of the first solvent may be greater than 60 wt%, more specifically 61 to 95 wt%, 62 to 94 wt%, 63 to 90 wt%, 64 to 85 wt%, 65 to 80 wt%, 65 to 75 wt%, 65 to 70 wt%, 65 to 68 wt%, 65 to 67 wt%, or 65 to 66 wt%, based on the total weight of the crack repair electrode slurry. If the content of the first solvent is outside the above numerical range, the electrode slurry may be applied only to the peripheral area of the crack, and as the depth of the crack deepens, it may become difficult to repair the crack formed in the electrode.
  • the first solvent is not particularly limited, but may specifically include one or more selected from the group consisting of alcohol, acetic acid, propionic acid, oleic acid, carbon tetrachloride, pyrrole, and pyridine, and may specifically be alcohol, and more specifically may be ethanol.
  • the electrode slurry for crack repair may further comprise a second solvent having a surface tension of more than 40 mN/m at 20°C.
  • the second solvent may be a factor that controls the viscosity and surface tension of the electrode slurry for crack repair.
  • the dispersion effect of the catalyst nanoparticles in the electrode slurry may be further improved.
  • the content of the second solvent may be 10 wt% or less, and specifically 1 to 9 wt%, 2 to 8 wt%, 3 to 7 wt%, 4 to 6 wt%, or 5 to 6 wt%, based on the total weight of the electrode slurry for crack repair.
  • the content of the second solvent satisfies the numerical range, cracks in the electrode formed by shrinkage or expansion of the polymer electrolyte membrane can be effectively repaired.
  • the second solvent is not particularly limited and may specifically include one or more selected from the group consisting of water, glycerol, and an aqueous sodium chloride solution of about 5 M or more.
  • the crack repair electrode slurry according to the present invention has a surface tension of 65 mN/m or less at 20°C, specifically 15 to 62 mN/m, and more specifically 20 to 60 mN/m, 30 to 60 mN/m, 35 to 59 mN/m, 40 to 55 mN/m, or 43 to 50 mN/m. If the surface tension of the crack repair electrode slurry at 20°C is outside the above numerical range, the electrode slurry may be applied only to the peripheral area of the crack, and the depth of the crack may actually deepen, making it difficult to repair the crack formed in the electrode. The surface tension of the crack repair electrode slurry may be measured using the capillary rise method or a Du nouy tensiometer.
  • the electrode slurry for crack repair according to the present invention has a viscosity of 100 cP or less at 20°C, specifically 10 to 90 cP, and more specifically 15 to 85 cP, 20 to 80 cP, 25 to 75 cP, 30 to 70 cP, 35 to 65 cP, 38 to 60 cP, 38 to 50 cP, or 38 to 48 cP. If the viscosity of the electrode slurry for crack repair is outside the above numerical range, the electrode slurry is applied only to the peripheral area of the crack, and the depth of the crack actually deepens, making it difficult to repair the crack formed in the electrode. The viscosity of the electrode slurry for crack repair can be measured using a viscosity meter commonly used in the relevant technical field.
  • the total solid content based on the total weight of the crack repair electrode slurry according to the present invention is 12 wt% or less, and specifically, may be 11 wt% or less, 10 wt% or less, 0.1 to 10 wt%, 1 to 10 wt%, 2 to 10 wt%, 3 to 10 wt%, 4 to 10 wt%, 5 to 10 wt%, 6 to 10 wt%, 7 to 10 wt%, 8 to 10 wt%, or 9 to 10 wt%.
  • the total solid content in the crack repair electrode slurry may be the content excluding the first and second solvents and the dispersion medium included in the binder dispersion.
  • the electrode slurry may be applied only to the surrounding area of the crack, and the depth of the crack may actually deepen, making it difficult to repair the crack formed in the electrode.
  • the electrode slurry for crack repair may further comprise functional nanoparticles.
  • the functional nanoparticles may comprise, for example, at least one selected from the group consisting of radical scavengers, catalytic nanoparticles, heat-dissipating nanoparticles, and hygroscopic nanoparticles.
  • the functional nanoparticles may comprise catalytic nanoparticles and further comprise at least one selected from the group consisting of radical scavengers, heat-dissipating nanoparticles, and hygroscopic nanoparticles.
  • the radical scavenger can capture oxygen radicals generated during operation of the fuel cell.
  • the radical scavenger can be, for example, any one selected from the group consisting of a transition metal, an ion of a transition metal, an oxide of a transition metal, a complex of a transition metal, a noble metal, an ion of a noble metal, an oxide of a noble metal, a complex of a noble metal, and combinations thereof.
  • the transition metal can be any one selected from the group consisting of cerium (Ce), manganese (Mn), tungsten (W), cobalt (Co), vanadium (V), nickel (Ni), chromium (Cr), zirconium (Zr), yttrium (Y), iridium (Ir), iron (Fe), titanium (Ti), molybdenum (Mo), lanthanum (La), and neodymium (Nd).
  • the above precious metal may be any one selected from the group consisting of silver (Ag), platinum (Pt), ruthenium (Ru), palladium (Pd), and rhodium (Rh).
  • the above catalyst nanoparticle may be any one selected from the group consisting of platinum-based nanoparticles, OER (Oxygen evolution reaction) catalyst nanoparticles, and combinations thereof.
  • platinum-based nanoparticles are catalytic nanoparticles that participate in the reaction of the battery, and may be, for example, at least one selected from the group consisting of platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), and platinum-M (Pt-M).
  • the M may be at least one selected from the group consisting of palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), silver (Ag), gold (Au), zinc (Zn), tin (Sn), molybdenum (Mo), tungsten (W), lanthanum (La), and rhodium (Rh).
  • the platinum alloy may be any one selected from the group consisting of Pt-Pd, Pt-Sn, Pt-Mo, Pt-W, Pt-Ru, Pt-Ru-W, Pt-Ru-Mo, Pt-Ru-Rh-Ni, Pt-Ru-Sn-W, Pt-Co, Pt-Co-Ni, Pt-Co-Fe, Pt-Co-Ir, Pt-Co-S, Pt-Co-P, Pt-Fe, Pt-Fe-Ir, Pt-Fe-S, Pt-Fe-P, Pt-Au-Co, Pt-Au-Fe, Pt-Au-Ni, Pt-Ni, Pt-Ni-Ir, Pt-Cr, Pt-Cr-Ir, and combinations thereof.
  • the platinum-based nanoparticles may be supported on a carrier.
  • the carrier may be, for example, one selected from the group consisting of a carbon-based carrier, a porous inorganic oxide, a zeolite, and a combination thereof.
  • the carbon-based carrier may be, for example, selected from the group consisting of graphite, Super P, carbon fiber, carbon sheet, carbon black, Ketjen black, Denka black, acetylene black, carbon nanotube (CNT), carbon sphere, carbon ribbon, fullerene, activated carbon, carbon nanofiber, carbon nanowire, carbon nanoball, carbon nanohorn, carbon nanocage, carbon nanoring, carbon aerogel, graphene, stabilized carbon, activated carbon, and a combination of at least one or more thereof, but is not limited thereto.
  • the porous inorganic oxide may correspond to at least one selected from the group consisting of, for example, zirconia, alumina, titania, silica, and ceria.
  • the surface area of the carrier may preferably be 50 m 2 /g or more, and the average particle diameter may be 10 to 300 nm. If the surface area of the carrier is less than the above numerical range, a uniform distribution of metal nanoparticles may not be obtained.
  • the OER (oxygen evolution reaction) catalyst nanoparticles are nanoparticles that promote a reaction that generates oxygen gas and electrons through the oxidation reaction of water.
  • the OER catalyst nanoparticles may be, for example, any one selected from the group consisting of ruthenium oxide (RuO 2 ), iridium oxide (IrO 2 ), and combinations thereof.
  • the heat-dissipating nanoparticles are nanoparticles that transfer heat generated during fuel cell operation to the outside of the catalyst layer, and may be, for example, one or more selected from the group consisting of metal nanoparticles, ceramic nanoparticles, and carbon nanoparticles.
  • the metal nanoparticles may be selected from the group consisting of Al, Mg, Cu, Ni, Ag, and core-shell nanoparticles having excellent thermal conductivity.
  • a metal or metalloid belonging to groups 2 to 15 of the periodic table may be used as the core, and a metal having excellent thermal conductivity or being relatively stable may be used as the shell.
  • the core-shell nanoparticles may be, for example, Cu@Ag, Fe@Al, or Cu@Au.
  • the ceramic nanoparticles may be one or more selected from the group consisting of boron nitride, aluminum nitride, aluminum oxide, silicon carbide, and beryllium oxide.
  • the ceramic nanoparticles have excellent thermal conductivity, so they can easily transfer heat to the outside of the catalyst layer and have the effect of preventing moisture within the catalyst layer from evaporating.
  • the boron nitride may be hexagonal boron nitride (h-BN).
  • h-BN hexagonal boron nitride
  • the hexagonal boron nitride has properties and a plate-like structure similar to graphite, and thus may have excellent thermal conductivity, insulation, and chemical stability at high temperatures.
  • the above carbon nanoparticles may be, for example, at least one selected from the group consisting of carbon nanofibers, carbon black, acetylene black, carbon nanotubes (CNTs), carbon spheres, carbon ribbons, fullerenes, graphene, and activated carbon.
  • the above hygroscopic nanoparticles may be nanoparticles that effectively absorb moisture generated during fuel cell operation.
  • the hygroscopic nanoparticles may include, for example, any one selected from the group consisting of porous silica, zeolite, and polyacrylonitrile (PAN).
  • a crack repair electrode slurry may further include a binder dispersion to bind the catalyst nanoparticles together.
  • the binder dispersion may be a mixture of a dispersion medium and a binder (ion conductor).
  • the dispersion medium may be appropriately modified depending on the type of the ion conductor.
  • the content of the binder dispersion may be 20 to 30 wt%, 21 to 29 wt%, 22 to 28 wt%, 23 to 27 wt%, 24 to 26 wt%, or 25 to 26 wt% based on the total weight of the electrode slurry for crack repair. According to some embodiments of the present invention, when the content of the binder dispersion satisfies the numerical range, the effect of binding functional nanoparticles to each other can be better implemented.
  • the content of the binder may be 5 to 25 wt%, 6 to 24 wt%, 7 to 23 wt%, 8 to 22 wt%, 10 to 20 wt%, 15 to 20 wt%, or 16 to 20 wt% based on the total weight of the binder dispersion.
  • the binder may mean the total solid content of the binder dispersion. According to some embodiments of the present invention, when the content of the binder satisfies the numerical range, the performance and physical durability of an electrode manufactured with the electrode slurry for crack repair can be further improved.
  • the above binder may be, for example, any one selected from the group consisting of fluorine-based ion conductors, hydrocarbon-based ion conductors, and mixtures thereof.
  • the fluorine-based ion conductor may be any one selected from the group consisting of poly(perfluorosulfonic acid), poly(perfluorocarboxylic acid), a copolymer of tetrafluoroethylene and fluorovinyl ether containing a sulfonic acid group, a polystyrene-graft-ethylenetetrafluoroethylene copolymer, a polystyrene-graft-polytetrafluoroethylene copolymer, and mixtures thereof.
  • the hydrocarbon-based ion conductor may be sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (S-PAES), sulfonated polyetheretherketone (S-PEEK), sulfonated polybenzimidazole (S-PBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyethersulfone, sulfonated It may be any one selected from the group consisting of sulfonated polyether ketone, sulfonated polyphenylene sulfone, sulfonated polyphenylene sulfide, sulfonated polyphenylene sulfulf
  • the crack repair electrode slurry according to the present invention can be coated using any one method selected from the group consisting of slot-die coating, comma coating, spray coating, brushing, and doctor blade coating, for example. Since the crack repair electrode slurry can be applied using various coating methods, it can have the advantage of being easily applicable in industry.
  • a catalyst layer for a fuel cell repaired with the above-described crack repair electrode slurry and a membrane-electrode assembly including the same are provided.
  • FIG. 1a is a cross-sectional view of a catalyst layer for a fuel cell with a crack repaired according to one embodiment of the present invention.
  • a catalyst layer (20) for a fuel cell may be disposed on at least one surface of a polymer electrolyte membrane (10).
  • the catalyst layer (20) for a fuel cell may include a first catalyst layer (21) and a second catalyst layer (23) disposed on the first catalyst layer (21).
  • the first catalyst layer (21) may be an electrode in which a crack is formed due to shrinkage or expansion of the polymer electrolyte membrane (10)
  • the second catalyst layer (23) may be an electrode formed with the electrode slurry for crack repair.
  • the first catalyst layer (21) may include a crack region (CR) in which a crack is formed and a peripheral region (PR) of the crack region (CR).
  • the electrode slurry for crack repair according to the present invention can effectively repair cracks that have occurred in the electrode by filling both the crack region (CR) and the peripheral region (PR) of the first catalyst layer (21), and at the same time, provide a catalyst layer (20) for a fuel cell having a uniform thickness.
  • the polymer electrolyte membrane (10) according to the present invention is not particularly limited, but may be, for example, a single membrane or a reinforced composite membrane in the relevant technical field.
  • the reinforced composite membrane may be a composite membrane in which an ionomer is impregnated into a porous support to form an ionomer layer on the surface to enhance durability.
  • the ionomer may be the same as or different from the ion conductor.
  • a catalyst layer for a fuel cell comprising: a first catalyst layer including a crack region; and a second catalyst layer on the first catalyst layer, wherein a portion of the second catalyst layer corresponding to the crack region extends along the crack surface and includes a first region including a first binder and a second region different from the first region and including a second binder, wherein a content of the first binder per unit volume of the first region is higher than a content of the second binder per unit volume of the second region.
  • Figure 1b is an enlarged view of a portion of the second catalyst layer positioned at a position corresponding to the crack area of Figure 1a.
  • a portion (CR') of the second catalyst layer corresponding to the crack region (CR) according to the present invention includes a first region (CR1) and a second region (CR2).
  • the first region (CR1) may be different from the second region (CR2).
  • the first region (CR1) may overlap the second region (CR2) in a direction intersecting the direction in which the crack surface (22) extends.
  • the first region (CR1) may be interposed between the second region (CR2) and the crack surface (22).
  • the content of binder (ionomer) per unit volume is distributed higher than in the second region (CR2), so that not only can the ion conductivity due to the ion channel be further increased, but also the binding force between catalyst particles can be further increased, thereby increasing the durability of the catalyst layer.
  • the height (h) of the first region (CR1) may be greater than 0 ⁇ m and less than or equal to 2 ⁇ m, and may be from 0.1 ⁇ m to 1.8 ⁇ m in a direction intersecting the direction in which the crack surface (22) extends.
  • the direction intersecting the direction in which the crack surface (22) extends may be a direction toward the inside or center of a portion (CR') of the second catalyst layer, and specifically, may be a direction perpendicular to the direction in which the crack surface (22) extends (e.g., a direction of a normal vector of the crack surface).
  • the direction in which the crack surface (22) extends may be any one of several directions that the crack surface can define.
  • the shape of the crack surface (22) is not particularly limited, but may specifically be V-shaped in cross-section. In some other examples, the crack surface (22) may be formed irregularly or randomly as an interface where the first and second catalyst layers (21, 23) come into contact.
  • the first region (CR1) according to the present invention comprises a first binder.
  • the first binder can improve the adhesion between catalyst particles included in the first region and provide an ion path.
  • the first binder may be any one selected from the group consisting of the above-described fluorine-based ion conductor, hydrocarbon-based ion conductor, and mixtures thereof.
  • the second region (CR2) according to the present invention comprises a second binder.
  • the second binder can improve the adhesion between catalyst particles included in the second region and simultaneously provide an ion path.
  • the second binder may be any one selected from the group consisting of the above-described fluorine-based ion conductor, hydrocarbon-based ion conductor, and mixtures thereof.
  • the first and second binders may be the same or different from each other.
  • being the same or different from each other may mean that the types and properties of the binders are both the same or different.
  • the content of the first binder per unit volume of the first region (CR1) according to the present invention is higher than the content of the second binder per unit volume of the second region (CR2). Specifically, by adjusting the content of the first binder per unit volume of the first region to be higher than the content of the second binder per unit volume of the second region, not only can the ionic conductivity of the membrane-electrode assembly be further increased, but also the binding force between catalyst particles can be further increased, thereby increasing the durability of the catalyst layer.
  • the concentration of the binder per unit volume contained in the portion (CR') of the second catalyst layer corresponding to the crack area may increase from the inside of the portion (CR') of the second catalyst layer toward the crack surface. According to some embodiments of the present invention, since the concentration of the binder per unit volume increases from the inside of the portion (CR') of the second catalyst layer toward the crack surface, not only can the ionic conductivity of the membrane-electrode assembly be further increased, but also the bonding force between catalyst particles can be further increased, thereby increasing the durability of the catalyst layer.
  • a method for manufacturing a catalyst layer for a fuel cell comprising the steps of: (S1) preparing an electrode having a crack formed therein; (S2) applying an electrode slurry for crack repair of some embodiments onto one surface of the electrode having the crack formed therein; and (S3) drying the resultant of step (S2).
  • the electrode having the crack formed therein may be a first catalyst layer.
  • Figure 2 is a schematic diagram illustrating a fuel cell according to one embodiment of the present invention.
  • a fuel cell including the membrane-electrode assembly is provided.
  • a fuel cell (200) may include a fuel supply unit (210) that supplies a mixed fuel in which fuel and water are mixed, a reforming unit (220) that reforms the mixed fuel to generate a reformed gas containing hydrogen gas, a stack (230) that generates electrical energy by causing an electrochemical reaction between the reformed gas containing hydrogen gas supplied from the reforming unit (220) and an oxidizer, and an oxidizer supply unit (240) that supplies an oxidizer to the reforming unit (220) and the stack (230).
  • a fuel supply unit (210) that supplies a mixed fuel in which fuel and water are mixed
  • a reforming unit (220) that reforms the mixed fuel to generate a reformed gas containing hydrogen gas
  • a stack (230) that generates electrical energy by causing an electrochemical reaction between the reformed gas containing hydrogen gas supplied from the reforming unit (220) and an oxidizer
  • an oxidizer supply unit (240) that supplies an oxidizer to the reforming unit (220) and the stack (230
  • the above stack (230) may be equipped with a plurality of unit cells that generate electrical energy by inducing an oxidation/reduction reaction of a reforming gas containing hydrogen gas supplied from the reforming unit (220) and an oxidizing agent supplied from the oxidizing agent supply unit (240).
  • Each unit cell refers to a unit cell that generates electricity, and may include the membrane-electrode assembly that oxidizes/reduces oxygen in a reforming gas containing hydrogen gas and an oxidizing agent, and a separator (also called a bipolar plate, hereinafter referred to as a "separator") for supplying the reforming gas containing hydrogen gas and the oxidizing agent to the membrane-electrode assembly.
  • the separator is positioned on both sides of the membrane-electrode assembly with the membrane-electrode assembly at the center. At this time, the separator plates each positioned at the outermost side of the stack are specifically referred to as end plates.
  • the end plate may be provided with a first supply pipe (231) in the shape of a pipe for injecting reformed gas containing hydrogen gas supplied from the reforming unit (220), and a second supply pipe (232) in the shape of a pipe for injecting oxygen gas, and the other end plate may be provided with a first discharge pipe (233) for discharging reformed gas containing hydrogen gas that is ultimately unreacted and remains in a plurality of unit cells to the outside, and a second discharge pipe (234) for discharging oxidant that is ultimately unreacted and remains in the unit cells to the outside.
  • a first supply pipe (231) in the shape of a pipe for injecting reformed gas containing hydrogen gas supplied from the reforming unit (220)
  • a second supply pipe (232) in the shape of a pipe for injecting oxygen gas
  • the other end plate may be provided with a first discharge pipe (233) for discharging reformed gas containing hydrogen gas that is ultimately unreacted and remains in a plurality of unit cells to the outside,
  • the separator, fuel supply unit, and oxidizer supply unit constituting the electricity generation unit are used in a typical fuel cell, and therefore, a detailed description thereof is omitted in this specification.
  • the current density measured using a fuel cell unit cell evaluation device may be 2500 mA/cm 2 or more.
  • the hydrogen crossover current density of the fuel cell may be 15 mA/cm 2 or less, 14 mA/cm 2 or less, 13 mA/cm 2 or less, 12 mA/cm 2 or less, 11 mA/cm 2 or less, or 10 mA/cm 2 or less.
  • a lower hydrogen crossover current density of the fuel cell may mean a better crack repair effect.
  • Pt/C As a catalytic nanoparticle, Pt/C was used in which platinum particles having an average size (D 50 ) of about 3 to 4 nm were supported on carbon particles having an average size (D 50 ) of about 30 to 40 nm. Ethanol was used as a solvent having a surface tension of less than 40 mN/m at 20°C, and water was used as a solvent having a surface tension of more than 40 mN/m at 20°C.
  • CeO 2 having an average particle size of 15 nm was used as a radical scavenger
  • IrO 2 having an average particle size (D 50 ) of 30 nm was used as an OER catalytic nanoparticle
  • h-BN having an average particle size of 150 nm was used as a heat-radiating nanoparticle
  • porous silica (aerogel) having an average particle size of 50 nm was used as a hygroscopic nanoparticle
  • PFSA perfluorosulfonic acid
  • a commercial Nafion D2020 dispersion (20 wt% PFSA) mixed with propanol (dispersing medium) was used.
  • An electrode slurry was prepared consisting of 70 wt% of a solvent (water) having a surface tension exceeding 40 mN/m at 20°C, 5 wt% of a catalyst nanoparticle (Pt/C), and 25 wt% of a binder (Nafion solid content 20 wt%).
  • An electrode slurry was prepared by comprising 50 wt% of a solvent (ethanol) having a surface tension of 40 mN/m or less at 20°C, 8 wt% of a solvent (water) having a surface tension of more than 40 mN/m at 20°C, 7 wt% of a catalyst nanoparticle (Pt/C), and 35 wt% of a binder (Nafion solid content 20 wt%).
  • a crack repair electrode slurry was prepared, comprising 65 wt% of a first solvent (ethanol) having a surface tension of 40 mN/m or less at 20°C, 5 wt% of a second solvent (water) having a surface tension of more than 40 mN/m at 20°C, 5 wt% of a catalyst nanoparticle (Pt/C), and 25 wt% of a binder (Nafion solid content 20 wt%).
  • a first solvent ethanol
  • water water
  • Pt/C catalyst nanoparticle
  • An electrode slurry for crack repair was prepared in the same manner as in Example 1, except that 4.9 wt% of catalyst nanoparticles (Pt/C) and 0.1 wt% of radical scavenger (CeO 2 ) were used instead of 5 wt% of catalyst nanoparticles (Pt/C) in Example 1.
  • An electrode slurry for crack repair was prepared in the same manner as in Example 1, except that 4.9 wt% of catalytic nanoparticles (Pt/C) and 0.1 wt% of heat-dissipating nanoparticles (h-BN) were used instead of 5 wt% of catalytic nanoparticles (Pt/C) in Example 1.
  • An electrode slurry for crack repair was prepared in the same manner as in Example 1, except that 4.9 wt% of catalytic nanoparticles (Pt/C) and 0.1 wt% of hygroscopic nanoparticles (porous silica having a BET specific surface area of about 640 m 2 /g) were used instead of 5 wt% of catalytic nanoparticles (Pt/C) in Example 1.
  • Pt/C catalytic nanoparticles
  • hygroscopic nanoparticles porous silica having a BET specific surface area of about 640 m 2 /g
  • An electrode slurry for crack repair was prepared in the same manner as in Example 1, except that 4.9 wt% of catalyst nanoparticles (Pt/C) and 0.1 wt% of OER catalyst nanoparticles (IrO 2 ) were used instead of 5 wt% of catalyst nanoparticles (Pt/C) in Example 1.
  • the viscosity of the above crack repair electrode slurry was measured using a Brookfield viscosity measuring device at 20°C.
  • the surface tension of the electrode slurry for crack repair was measured at 20°C using a surface tension measuring device (Kruss K20) based on the De Nouy ring method.
  • the electrode slurry for crack repair was sufficiently dried at a temperature of 100°C or higher until the solvent and dispersion medium completely evaporated.
  • the total solids content was measured based on the total weight of the electrode slurry for crack repair, and the total solids content ratio was calculated.
  • FIG. 3 is an optical microscope photograph of catalyst layers for fuel cells to which electrode slurry for crack repair is applied according to Example 1 and Comparative Example 1. Referring to Fig. 3, it can be confirmed that cracks formed on the surface of the catalyst layer for fuel cells repaired with the electrode slurry for crack repair according to Example 1 are significantly less than those in Comparative Example 1.
  • Each of the electrode slurries for crack repair according to Manufacturing Example 1 was slot die-coated with a wet thickness of 100 ⁇ m on a catalyst layer having a crack formed inside and disposed on one side of a polymer electrolyte membrane, and then dried at 90°C for 10 minutes to manufacture a membrane-electrode assembly including a catalyst layer for a fuel cell with the crack repaired.
  • the performance was evaluated by measuring the voltage according to the current density for the membrane-electrode assembly according to Manufacturing Example 2 using Scitech's fuel cell unit cell evaluation equipment under conditions of 80 o C, 100% RH, and atmospheric pressure.
  • Figure 4 is a graph showing the performance of membrane-electrode assemblies according to Comparative Examples 1 and 2 and Example 1.
  • Example 1 in which the crack was repaired, exhibited a higher current density at the same voltage compared to Comparative Examples 1 and 2, in which the crack was repaired.
  • Second catalyst layer CR Crack region

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Abstract

L'invention concerne une suspension d'électrode qui permet de réparer des fissures dans une électrode. Selon un aspect de la présente invention, la suspension d'électrode comprend au moins 60 % en poids d'un premier solvant qui a une tension superficielle inférieure ou égale à 40 mN/m à 20 oC, la suspension d'électrode ayant une tension superficielle inférieure ou égale à 65 mN/m à 20 °C, une viscosité inférieure ou égale à 100 cP à 20 °C, et une teneur totale en solides inférieure ou égale à 12 % en poids.
PCT/KR2024/009439 2024-02-29 2024-07-04 Suspension d'électrode pour la réparation de fissures, couche de catalyseur pour pile à combustible, ensemble membrane-électrode et pile à combustible Pending WO2025183275A1 (fr)

Applications Claiming Priority (4)

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KR20240029388 2024-02-29
KR10-2024-0029388 2024-02-29
KR10-2024-0087823 2024-07-03
KR1020240087823A KR20250133120A (ko) 2024-02-29 2024-07-03 크랙 보수용 전극 슬러리, 연료전지용 촉매층, 막-전극 어셈블리 및 연료전지

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WO2025183275A1 true WO2025183275A1 (fr) 2025-09-04

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009048936A (ja) * 2007-08-22 2009-03-05 Dainippon Printing Co Ltd 触媒層付電解質膜の補修方法及び補修用転写フィルム
KR20090117370A (ko) * 2008-05-09 2009-11-12 주식회사 에이디피엔지니어링 수소 분리막 보수 방법
JP2015035355A (ja) * 2013-08-09 2015-02-19 トヨタ自動車株式会社 電極膜の補修方法及び補修装置
JP2016066446A (ja) * 2014-09-24 2016-04-28 本田技研工業株式会社 燃料電池
KR20170050929A (ko) * 2015-11-02 2017-05-11 주식회사 엘지화학 연료전지 스택의 실링 보수 장치 및 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009048936A (ja) * 2007-08-22 2009-03-05 Dainippon Printing Co Ltd 触媒層付電解質膜の補修方法及び補修用転写フィルム
KR20090117370A (ko) * 2008-05-09 2009-11-12 주식회사 에이디피엔지니어링 수소 분리막 보수 방법
JP2015035355A (ja) * 2013-08-09 2015-02-19 トヨタ自動車株式会社 電極膜の補修方法及び補修装置
JP2016066446A (ja) * 2014-09-24 2016-04-28 本田技研工業株式会社 燃料電池
KR20170050929A (ko) * 2015-11-02 2017-05-11 주식회사 엘지화학 연료전지 스택의 실링 보수 장치 및 방법

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