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WO2025230090A1 - Ensemble membrane-électrode pour pile à combustible, son procédé de fabrication et pile à combustible comprenant un ensemble membrane-électrode - Google Patents

Ensemble membrane-électrode pour pile à combustible, son procédé de fabrication et pile à combustible comprenant un ensemble membrane-électrode

Info

Publication number
WO2025230090A1
WO2025230090A1 PCT/KR2024/097043 KR2024097043W WO2025230090A1 WO 2025230090 A1 WO2025230090 A1 WO 2025230090A1 KR 2024097043 W KR2024097043 W KR 2024097043W WO 2025230090 A1 WO2025230090 A1 WO 2025230090A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
membrane
fuel cell
electrode assembly
polymer electrolyte
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/KR2024/097043
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 KR1020240186427A external-priority patent/KR20250157936A/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Publication of WO2025230090A1 publication Critical patent/WO2025230090A1/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
    • H01M4/88—Processes of manufacture
    • 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
    • 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 membrane-electrode assembly for a fuel cell, a method for manufacturing the same, and a fuel cell including the membrane-electrode assembly.
  • a fuel cell is a power generation system that directly converts the chemical reaction energy of hydrogen and oxygen contained in hydrocarbons such as methanol, ethanol, and natural gas into electrical energy.
  • hydrocarbons such as methanol, ethanol, and natural gas
  • a representative example of this type of fuel cell is the polymer electrolyte membrane fuel cell (PEMFC). Due to its advantages, such as low operating temperature (below 100°C), fast start-up and response characteristics, and excellent durability, the PEMFC is attracting attention as a power source for portable, automotive, and home use.
  • the membrane electrode assembly that actually generates electricity has a structure in which an anode electrode (called a fuel electrode or oxidation electrode) and a cathode electrode (called an air electrode or reduction electrode) are positioned with an electrolyte membrane in between.
  • anode electrode called a fuel electrode or oxidation electrode
  • a cathode electrode called an air electrode or reduction electrode
  • One of the key variables determining the efficiency of these fuel cells is the efficiency of the hydrogen ion reduction reaction. Specifically, this depends on how efficiently the hydrogen ions formed by the oxidation reaction at the anode move through the electrolyte and then undergo a reduction reaction with oxygen at the cathode. This requires smooth hydrogen ion movement not only within the polymer electrolyte membrane but also between the anode and cathode, which are in contact with the polymer electrolyte membrane. Furthermore, one of the challenges hindering the commercialization of fuel cells is the deterioration of electrode durability during operation. Therefore, continued research on durable electrodes is essential to extend the service life of fuel cells.
  • An object of the present invention is to provide a membrane-electrode assembly for a fuel cell that can improve the performance and durability of the fuel cell.
  • Another object of the present invention is to provide a method for manufacturing the membrane-electrode assembly for the fuel cell.
  • Another object of the present invention is to provide a fuel cell including the membrane-electrode assembly.
  • the present invention provides a membrane-electrode assembly for a fuel cell, comprising: a polymer electrolyte membrane; a first layer formed on a predetermined area of one side of the polymer electrolyte membrane; and a second layer formed to cover an outer surface of the first layer and an area of the one side of the polymer electrolyte membrane on which the first layer is not formed; wherein the first layer includes platelet carbon nanofibers, and the second layer includes a catalyst carrier, a catalyst supported on the catalyst carrier, and an ionomer.
  • the side of the nanofiber may be in contact with one side of the polymer electrolyte membrane.
  • the above platelet carbon nanofibers can be randomly arranged on the surface of a polymer electrolyte membrane.
  • the above platelet carbon nanofibers may have a width of 5 to 100 nm and a length of 100 to 10,000 nm.
  • the polymer electrolyte membrane may have a first layer formed thereon and may include a rough structure on a predetermined area of one side of the polymer electrolyte membrane.
  • a portion of the second layer may cover the outer surface of the uneven structure formed on the polymer electrolyte membrane.
  • One surface area of the polymer electrolyte membrane covered by the second layer, where the first layer is not formed, may include the catalyst carrier of the second layer, the catalyst supported on the catalyst carrier, and the ionomer.
  • the above platelet carbon nanofibers may be electrically conductive carbon nanofibers that do not support a catalyst.
  • the first layer further comprises a first ionomer, and the first ionomer may be applied by mixing with the platelet carbon nanofibers or may be included in a form coated on the platelet carbon nanofibers.
  • the first ionomer or ionomers may be at least one selected from the group consisting of cation conductors having at least one cation exchange group selected from the group consisting of a sulfonic acid group, a carboxyl group, a boronic acid group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a sulfonic acid fluoride group, and combinations thereof.
  • the first layer may have a thickness of 30 to 2,000 nm, and the second layer may have a thickness equal to or thicker than the first layer.
  • the catalyst carrier may be a spherical or plate-shaped carbon-based carrier.
  • the catalyst carrier may be at least one selected from the group consisting of graphite, graphene, fullerene, super P, carbon black, Ketjen Black, Denka black, acetylene black, carbon sphere, activated carbon, carbon nanoball, carbon nanohorn, carbon nanocage, and carbon nanoring.
  • the first layer may occupy an area of 5 to 65% of the total surface of the polymer electrolyte membrane.
  • the present invention provides a method for manufacturing a membrane-electrode assembly for a fuel cell, comprising: forming a first layer including platelet carbon nanofibers on a predetermined area of one surface of a polymer electrolyte membrane; and applying a slurry including a catalyst carrier, a catalyst supported on the catalyst carrier, and an ionomer on the polymer electrolyte membrane on which the first layer is formed, to form a second layer so as to cover the outer surface of the first layer and an area of one surface of the polymer electrolyte membrane on which the first layer is not formed.
  • the formation of the first layer can be performed by applying a composition including the platelet carbon nanofibers and the first ionomer onto the polymer electrolyte membrane.
  • the platelet carbon nanofibers and the first ionomer may be included in a weight ratio of 1.0:0.1 to 1.0:0.5.
  • the formation of the first layer can be performed by applying platelet carbon nanofibers coated with a first ionomer onto the polymer electrolyte membrane.
  • the first ionomer may be coated on the platelet carbon nanofibers at a weight ratio of 1.0:0.1 to 1.0:0.5 or a thickness of 2 to 10 nm.
  • the present invention provides a fuel cell including the membrane-electrode assembly.
  • the membrane electrode assembly for a fuel cell of the present invention has the effect of improving durability without deteriorating the performance of the fuel cell by disposing a catalyst layer with superior durability on the outer peripheral surface of the electrode and disposing a catalyst layer with superior electrochemical performance, such as electrical conductivity, on the inside of the electrode.
  • the membrane-electrode assembly for a fuel cell according to the present invention has the effect of reducing the cost of using a fuel cell including the same due to improved electrochemical performance and durability.
  • FIG. 1 is a cross-sectional view schematically showing a membrane-electrode assembly according to one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically illustrating an example of an electrode for a fuel cell according to one embodiment of the present invention.
  • FIG. 3 is a SEM image of a first layer formed on a polymer electrolyte membrane manufactured according to one embodiment of the present invention, and an enlarged image of the first layer in FIG. 3 is a TEM image.
  • Figure 4 schematically illustrates a method for manufacturing a membrane-electrode assembly according to one embodiment of the present invention.
  • Figure 5 is a schematic diagram showing the overall configuration of a fuel cell according to one embodiment of the present invention.
  • Figure 6 is a schematic diagram showing the structure of platelet carbon nanofibers.
  • Fig. 1 is a cross-sectional view schematically illustrating a membrane-electrode assembly (100) according to one embodiment of the present invention
  • Fig. 2 is a cross-sectional view schematically illustrating an example of an electrode (120) for a fuel cell according to one embodiment of the present invention.
  • the electrode (120) may be an anode electrode, a cathode electrode, or both.
  • a membrane-electrode assembly (100) includes a polymer electrolyte membrane (110); a first layer (121) formed on a predetermined area of one surface of the polymer electrolyte membrane (110); and a second layer (122) formed to cover an outer surface of the first layer (121) and an area of the one surface of the polymer electrolyte membrane where the first layer (121) is not formed; wherein the first layer (121) includes platelet carbon nanofibers, and the second layer includes a catalyst carrier, a catalyst supported on the catalyst carrier, and an ionomer.
  • a side of the nanofiber can be in contact with one surface of the polymer electrolyte membrane based on the long axis direction of the platelet carbon nanofiber.
  • the above-mentioned major axis direction may refer to the direction having the longest length of the platelet carbon nanofibers. Specifically, it may be the longitudinal direction of the platelet carbon nanofibers.
  • the side of the above nanofiber may mean a side surface, including an edge, of the long axis of the platelet carbon nanofiber.
  • the platelet carbon nanofiber may mean a structure in which a plurality of carbon hexagonal network planes are arranged at right angles to the long axis direction of the nanofiber.
  • the side of the nanofiber with respect to the long axis direction of the platelet carbon nanofiber comes into contact with one surface of the polymer electrolyte membrane (110), so that the side of the plurality of carbon hexagonal network planes within the platelet carbon nanofiber has an arrangement that is approximately perpendicular to the surface of the polymer electrolyte membrane (110) (see FIG. 3).
  • a space is created between the plurality of carbon hexagonal network planes arranged approximately perpendicularly in this way, and this space can serve as an electron path.
  • the membrane-electrode assembly (100) of the present invention can improve durability by preventing performance degradation and improving heat dissipation function utilizing the electron path due to the formation of a shorter electron movement path.
  • the platelet carbon nanofibers do not necessarily need to be arranged in one direction on the polymer electrolyte membrane (110) and may be arranged randomly.
  • the platelet carbon nanofibers may overlap each other and be laminated on the polymer electrolyte membrane (110). Accordingly, some of the carbon hexagonal network planes may not necessarily be perpendicular to the plane of the polymer electrolyte membrane (110) and may be inclined.
  • the first layer for example, platelet carbon nanofibers
  • the first layer may cover an area of 5 to 65%, 7 to 64%, 9 to 63%, 11 to 62%, 13 to 61%, 17 to 60%, 20 to 59%, 24 to 58%, 27 to 57%, 30 to 56%, 34 to 55%, 37 to 54%, 40 to 53%, 43 to 52%, 45 to 51% or 50% of the entire surface of the polymer electrolyte membrane (110), but is not limited thereto.
  • the platelet carbon nanofibers cover an area of the polymer electrolyte membrane beyond the above-described range, the effect of the addition of the platelet carbon nanofibers may not be exerted, and the catalytically active area may be insufficient or water discharge may not be smooth.
  • the platelet carbon nanofibers may have a width of, but is not limited to, 5 to 100 nm, 8 to 95 nm, 12 to 90 nm, 16 to 85 nm, 20 to 80 nm, 24 to 75 nm, 28 to 70 nm, 32 to 65 nm, 36 to 60 nm, 40 to 55 nm, 44 to 53 nm, or 50 nm.
  • the above platelet carbon nanofibers may have a length of 100 to 10,000 nm, 120 to 8,000 nm, 140 to 6,000 nm, 160 to 4,000 nm, 180 to 2,000 nm, 200 to 1,000 nm, 220 to 900 nm, 240 to 800 nm, 260 to 700 nm, 280 to 600 nm, 300 to 500 nm, 350 to 450 nm or 400 nm, but is not limited thereto.
  • the platelet carbon nanofibers may have a ratio of fiber length to fiber width of 20 or more, and an interplanar distance of carbon hexagonal mesh planes may be less than 3.9 ⁇ .
  • Carbonaceous materials such as carbon nanotubes can be used as catalyst carriers that are electrically conductive and also support catalysts.
  • the platelet carbon nanofibers may be electrically conductive carbon nanofibers that do not essentially support a catalyst.
  • the platelet carbon nanofibers may be mixed with a first ionomer for hydrogen ion transport, or the first ionomer may be coated on the platelet carbon nanofibers.
  • the first layer (121) may additionally include a first ionomer.
  • the first ionomer may be the same as or different from the ionomer of the second layer, and any ionomer that can be used as an ionomer in the field of fuel cell technology may be used without limitation.
  • the first ionomer or ionomers are for hydrogen ion transport and may also function as a binder.
  • the first ionomer or ionomers may be at least one selected from the group consisting of cation conductors having at least one proton exchange group selected from the group consisting of a sulfonic acid group, a carboxyl group, a boronic acid group, a phosphoric acid group, an imide group, a sulfonimide group, a sulfonamide group, a sulfonic acid fluoride group, and combinations thereof.
  • both the first layer and the second layer contain an ionomer, low-humidification performance and durability can be excellent.
  • the first ionomer or ionomers may be a fluorine-based cation conductor, a hydrocarbon-based cation conductor, or a mixture thereof.
  • the first ionomer or ionomers may be a fluorine-based cation conductor having a sulfonic acid group and/or a carboxyl group, a hydrocarbon-based cation conductor having a sulfonic acid group and/or a carboxyl group, or a mixture thereof.
  • fluorine-based cation conductor examples include Nafion, Asiplex, Flemion, polyvinylidene fluoride, hexafluoropropylene, trifluoroethylene, polytetrafluoroethylene or copolymers thereof.
  • hydrocarbon-based cation conductor examples include hydrocarbon-based polymers having the cation exchange group in the side chain, for example, sulfonated polyimide (S-PI), sulfonated polyarylethersulfone (SPAES), sulfonated polyetheretherketone (SPEEK), sulfonated polybenzimidazole (SPBI), sulfonated polysulfone (S-PSU), sulfonated polystyrene (S-PS), sulfonated polyphosphazene, sulfonated polyquinoxaline, sulfonated polyketone, sulfonated polyphenylene oxide, sulfonated polyethersulfone, sulfonated polyetherketone, sulfonated polyphenylenesulfone, sulfonated polyphenylenesulfide, sulfonated polyphenylenesulfidesulfone, It may be s
  • the first ionomer or ionomer may have an equivalent weight (EW) of 600 to 1,200.
  • EW equivalent weight
  • the first ionomer may be applied by mixing with the platelet carbon nanofibers, or may be included in a form of coating on the platelet carbon nanofibers.
  • the first layer (121) may be composed of platelet carbon nanofibers alone, platelet carbon nanofibers coated with an ionomer alone, or a mixture of platelet carbon nanofibers and ionomer.
  • the polymer electrolyte membrane may have a first layer formed thereon and may include a roughened structure on a predetermined area of one side of the polymer electrolyte membrane.
  • the first layer may have a rough structure on the surface of the polymer electrolyte membrane (110) due to the platelet carbon nanofibers (see FIGS. 2 and 3).
  • a portion of the second layer (122) may cover the outer surface of the uneven structure formed on the polymer electrolyte membrane.
  • a portion of the second layer (122) may cover the remaining area of the polymer electrolyte membrane where no uneven structures are formed on the polymer electrolyte membrane. That is, the second layer (122) may fill the spaces between the convex portions of the uneven structure formed on the polymer electrolyte membrane, the concave portions, and/or the spaces within the uneven structure.
  • a portion of the second layer (122) may cover an area of one surface of the polymer electrolyte membrane where the first layer (121) is not formed, and at least a portion of the components of the second layer (122), for example, a catalyst, a catalyst carrier, or an ionomer, may be included in the first layer (121).
  • the first layer (121) may include platelet carbon nanofibers that do not essentially support a catalyst, platelet carbon nanofibers coated with a first ionomer and that do not essentially support a catalyst, or a catalyst carrier that supports a catalyst.
  • the first layer (121) may have a thickness of 30 to 2,000 nm, 60 to 1,900 nm, 100 to 1,800 nm, 130 to 1,700 nm, 170 to 1,600 nm, 200 to 1,500 nm, 250 to 1,500 nm, 300 to 1,400 nm, 370 to 1,400 nm, 450 to 1,200 nm, 530 to 1,100 nm, or 600 to 1,000 nm, but is not limited thereto. If the thickness of the first layer is outside the above-described range, it is difficult to effectively exert the effect of adding platelet carbon nanofibers, and the movement distance of ions and electrons may increase, thereby increasing resistance.
  • the second layer (122) includes a catalyst carrier, a catalyst supported on the catalyst carrier, and an ionomer.
  • the catalyst carrier, catalyst, and ionomer may be any of those commonly used in the field of fuel cell technology and are not particularly limited.
  • the catalyst may be any metal catalyst that can participate in the reaction of a fuel cell and be used as a catalyst.
  • the catalysts may each independently be a platinum-based catalyst.
  • the platinum-based catalyst any one metal particle selected from the group consisting of platinum, ruthenium, osmium, a platinum-M alloy (wherein M is any one transition metal selected from the group consisting of Pd, Ir, Os, Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Mo, W, Rh, Ru, and alloys thereof), and mixtures thereof may be used.
  • the platinum-based catalyst is Pt, Pt-Pd, Pt-Mn, Pt-Sn, Pt-Mo, Pt-Cr, Pt-W, Pt-Ru, Pt-Ni, Pt-Co, Pt-Y, Pt-Ru-W, Pt-Ru-Ir, Pt-Ru-Ni, Pt-Ru-Mo, Pt-Ru-Rh-Ni, Pt-Ru-Sn-W, Pt-Ru-Ir-Ni, Pt-Ru-Ir-Y, Pt-Co-Mn, Pt-Co-Ni, Pt-Co-Fe, Pt-Co-Ir, Pt-Co-S, Pt-Co-P, Pt-Fe, Pt-Fe-Ir, Pt-Fe-Ir, Pt-Fe-S, Pt-Fe-P, Pt-Au-Co, Pt-Au-Fe, Pt-Au-Ni, Pt-N
  • the catalyst may have a particle diameter in the range of 2 to 20 nm. Since larger particle diameters result in greater durability but lower performance, by maintaining the particle diameter within the above range, the durability and performance of the catalyst can be maintained within an appropriate range.
  • the above catalyst carrier can be used as long as it can be used as a carrier in the field of catalyst technology for fuel cells.
  • any carrier other than platelet carbon nanofibers can be used as the catalyst carrier.
  • the catalyst carrier can be selected from, for example, a spherical or plate-shaped carbon-based carrier, a porous inorganic oxide carrier such as zirconia, alumina, titania, silica, and ceria, and a zeolite carrier.
  • a spherical or plate-shaped carbon-based carrier can be used as the catalyst carrier, and the spherical or plate-shaped carbon-based carrier can be at least one selected from the group consisting of graphite, graphene, fullerene, super P, carbon black, Ketjen Black, Denka black, acetylene black, carbon sphere, activated carbon, carbon nanoball, carbon nanohorn, carbon nanocage, and carbon nanoring.
  • the catalyst carrier may have a diameter of 15 to 100 nm and a pore size of 0.1 to 15 nm or 1 to 10 nm.
  • the above ionomer may be the same as or different from the first ionomer that may be included in the first layer (121).
  • the second layer (122) may have a thickness of, for example, 3 to 20 ⁇ m, and the thickness of the second layer (122) may be the same as or thicker than the thickness of the first layer (121). If the second layer (122) is thinner than the first layer (121), catalytic activity, etc. may not be sufficient.
  • the second layer (122) may be formed as a plurality of layers, i.e., at least one second layer (122), on the first layer (121).
  • the above polymer electrolyte membrane (110) is a solid polymer electrolyte having a thickness of 5 to 200 ⁇ m and has an ion exchange function that moves hydrogen ions generated at the anode electrode (120) to the cathode electrode (120).
  • the above polymer electrolyte membrane (110) may use a hydrocarbon-based polymer electrolyte membrane, a fluorine-based polymer electrolyte membrane, or a mixture or copolymer of one or more thereof.
  • the above hydrocarbon polymer electrolyte membrane may include a hydrocarbon polymer, and the polymer may be selected from styrene, imide, sulfone, phosphazene, ether ether ketone, ethylene oxide, polyphenylene sulfide, or an aromatic group homopolymer or copolymer and derivatives thereof, and these polymers may be used alone or in combination.
  • Manufacturing an electrolyte membrane using a hydrocarbon polymer is cheaper, easier to manufacture, and exhibits higher ionic conductivity than using a fluorinated polymer.
  • the above fluorinated polymer electrolyte membrane can be used without any particular restrictions as long as it has mechanical strength and high electrochemical stability sufficient to form a film as an ion-conducting membrane.
  • Specific examples of the fluorinated polymer electrolyte membrane include perfluorosulfonic acid resins and copolymers of tetrafluoroethylene and fluorovinyl ether.
  • the fluorovinyl ether moiety has the function of conducting hydrogen ions.
  • the copolymer is commercially available and sold under the trade name Nafion by DuPont.
  • the membrane-electrode assembly (100) may additionally be bonded to a gas diffusion layer (130) (see FIG. 1).
  • the above gas diffusion layer (130) is disposed between the membrane-electrode assembly (100) and the separator of the fuel cell, and any gas diffusion layer used in the art can be used without limitation.
  • the gas diffusion layer (130) may be formed by including a conductive substrate selected from the group consisting of carbon paper, carbon cloth, and carbon felt.
  • the gas diffusion layer may further be formed by including a microporous layer formed on one surface of the conductive substrate, and the microporous layer may be formed by including a carbon-based material such as carbon black or carbon nanotubes, and a fluorine-based resin such as polytetrafluoroethylene or polyvinylidene fluoride (PVdF).
  • PVdF polytetrafluoroethylene or polyvinylidene fluoride
  • a membrane-electrode assembly for a fuel cell according to one embodiment of the present invention can be manufactured as follows.
  • a method for manufacturing a membrane-electrode assembly for a fuel cell including: forming a first layer including platelet carbon nanofibers on a predetermined area of one surface of a polymer electrolyte membrane; applying a slurry including a catalyst carrier, a catalyst supported on the catalyst carrier, and an ionomer onto the polymer electrolyte membrane on which the first layer is formed, to form a second layer so as to cover an outer surface of the first layer and an area of one surface of the polymer electrolyte membrane on which the first layer is not formed.
  • FIG. 4 schematically illustrates a method for manufacturing a membrane-electrode assembly according to one embodiment of the present invention.
  • FIG. 4 (a) is a schematic diagram illustrating a process of forming a first layer including platelet carbon nanofibers on a polymer electrolyte membrane
  • FIG. 4 (b) is a schematic diagram illustrating a process of forming a first layer including platelet carbon nanofibers coated with an ionomer on a polymer electrolyte membrane.
  • a method for manufacturing a membrane-electrode assembly for a fuel cell including: forming a second layer by applying a slurry including a catalyst carrier, a catalyst supported on the catalyst carrier, and an ionomer on a transfer substrate; forming a first layer including platelet carbon nanofibers on the second layer; and bonding the first layer to at least one surface of a polymer electrolyte membrane.
  • the step of forming the first layer can be performed by laminating the platelet carbon nanofibers on the surface of the polymer electrolyte membrane or the second layer.
  • the platelet carbon nanofibers can be laminated alone or, if necessary, together with an appropriate solvent, as illustrated in (a) of Fig. 4.
  • the solvent can be any one selected from the group consisting of water, methanol, ethanol, butanol, n-propanol, isopropanol, n-butyl acetate, ethylene glycol, dipropylene glycol, glycerol, and combinations thereof, and is not limited to the type thereof as long as it can well disperse the carbon nanofibers.
  • the step of forming the first layer may be performed by applying a composition mixed with the platelet carbon nanofibers and the first ionomer onto the surface of the polymer electrolyte membrane or the second layer.
  • the platelet carbon nanofibers and the first ionomer may be included in a weight ratio of 1:0.1 to 1:0.5.
  • the method for manufacturing the membrane-electrode assembly of the present invention further comprises a step of coating the platelet carbon nanofibers with a first ionomer, and the step of forming the first layer may be performed by applying the platelet carbon nanofibers coated with the first ionomer onto the polymer electrolyte membrane, as illustrated in FIG. 4 (b).
  • the coating of the first ionomer may be performed, for example, by heat treatment, specifically, heat treatment at 100 to 160°C.
  • the first ionomer may be coated at a weight ratio of 1:0.1 to 1:0.5 or a thickness of 2 to 10 nm with respect to the platelet carbon nanofibers.
  • the platelet carbon nanofibers When the ionomer is coated at the weight ratio or thickness, the platelet carbon nanofibers can be easily coated and aggregation of the carbon nanofibers can be reduced.
  • the platelet carbon nanofibers coated with the first ionomer may be applied together with an appropriate solvent as needed.
  • the first layer and the second layer can be formed by any method known in the art, such as spray coating, inkjet printing, roll-to-roll printing, screen printing, etc. Specific manufacturing conditions, such as spray atomization pressure, drying temperature, drying time, etc., can be appropriately selected and performed by those skilled in the art.
  • a fuel cell according to one embodiment of the present invention includes the membrane-electrode assembly and may be, for example, a fuel cell that uses hydrogen gas as fuel.
  • Figure 5 is a schematic diagram showing the overall configuration of a fuel cell according to one embodiment of the present invention.
  • the fuel cell (200) includes 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) has 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 includes 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 is 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
  • the other end plate is provided with a first discharge pipe (233) for discharging reformed gas containing hydrogen gas that is ultimately unreacted and remaining in a plurality of unit cells to the outside, and a second discharge pipe (234) for discharging oxidant that is ultimately unreacted and remaining in the unit cells to the outside.
  • Fe 3 O 4 nanoparticle catalyst was reduced by reacting it at 600°C for 3 hours under a mixture of hydrogen (5%) and argon (95%), and then reacted at 600°C for 24 hours under a mixture of argon (80%), CO (15%), and hydrogen (5%) to produce platelet carbon nanofibers with a length of 400 nm and a width of 50 nm.
  • the platelet carbon nanofibers, 400 nm in length and 50 nm in width, manufactured in the above Manufacturing Example 1 were mixed with the first ionomer, Nafion, in a weight ratio of 1:0.3, coated on a polymer electrolyte membrane (DuPont product; Nafion 212 Membrane) using a bar coater method, and then dried to form a first layer on the polymer electrolyte membrane.
  • the first layer was formed so that the platelet carbon nanofibers occupied 50% of the surface area of the polymer electrolyte membrane, and it was confirmed by a scanning electron microscope that the surface of the first layer formed on the polymer electrolyte membrane had an uneven structure.
  • the results are shown in Fig. 3.
  • the platelet carbon nanofibers coated with the first ionomer were dispersed in water to a solid content of 20%, and then coated on a polymer electrolyte membrane (DuPont product; Nafion 212 Membrane) using a bar coater method, followed by drying to produce a first layer.
  • the platelet carbon nanofibers formed the first layer so that they occupy 50% of the surface area of the polymer electrolyte membrane, and it was confirmed by scanning electron microscopy that the surface of the first layer formed on the polymer electrolyte membrane had an uneven structure (not shown).
  • a catalyst slurry for an electrode was prepared by mixing 5 g of a commercial Pt/carbon catalyst (Tanaka) and 25 g of Nafion (D2020), and the catalyst slurry for an electrode was coated on the first layer in the same manner as the first layer and dried to form a second layer, thereby preparing an electrode.
  • Example 2 a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that 2 g of platelet carbon nanofibers coated with the first ionomer were dispersed in water so that the solid content was 5% instead of 20%, and the first layer was formed so that the platelet carbon nanofibers occupied 8% of the surface area of the polymer electrolyte membrane.
  • Example 2 a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that 2 g of platelet carbon nanofibers coated with the first ionomer were dispersed in water so that the solid content was 30% instead of 20%, and the first layer was formed so that the platelet carbon nanofibers occupied 65% of the surface area of the polymer electrolyte membrane.
  • Example 1 a membrane-electrode assembly was manufactured in the same manner as in Example 1, except that only 1 g of platelet carbon nanofibers was used instead of mixing the platelet carbon nanofibers with the first ionomer, Nafion, in a weight ratio of 1:0.3.
  • a catalyst slurry for an electrode was prepared by mixing 5 g of a commercial Pt/carbon catalyst (Tanaka) and 25 g of Nafion, and then bar-coated on a fluorinated ethylene propylene release film, dried, and heat-treated to prepare an electrode.
  • the above dried electrode was cut to the required size, aligned so that the electrode surface and the electrolyte membrane were in contact with each other on both sides of a polymer electrolyte membrane (DuPont product; Nafion 212 Membrane), pressed under heating and pressure, and then transferred by hot pressing by maintaining it at room temperature for a predetermined period of time, and the release film was peeled off to manufacture a membrane-electrode assembly.
  • a polymer electrolyte membrane DuPont product; Nafion 212 Membrane
  • Example 2 a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that 1 g of carbon nanofibers in the form of a general layer (Sigma aldrich.) was used instead of 1 g of platelet carbon nanofibers.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that 1 g of spherical carbon black (Cabot/Vulcan XC-72) was used instead of 1 g of platelet carbon nanofibers.
  • a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that the catalyst layer was manufactured using only the first layer on the polymer electrolyte membrane in the same manner as in Example 2.
  • Example 2 a membrane-electrode assembly was manufactured in the same manner as in Example 2, except that the thickness of the first layer was manufactured to be 2,100 nm.
  • each membrane-electrode assembly was evaluated based on the durability assessment protocol of the U.S. Department of Energy (DOE). Specifically, to evaluate the physical durability of the membrane-electrode assembly, H2 crossover was measured after 20,000 wet/dry cycles, and the measured values are shown in Table 1 below.
  • the output performance of the membrane-electrode assembly manufactured in the examples and comparative examples was evaluated through I (current) - V (voltage) measurements. Specifically, in order to confirm the output performance under actual fuel cell operating conditions, the membrane-electrode assembly was supplied with hydrogen (100 %RH) and air (100 %RH) to the anode and cathode, respectively, in amounts corresponding to the stoichiometry of 1.2/2.0 under 65°C conditions using a fuel cell unit cell evaluation device (Scribner 850 fuel cell test system). The current density was measured when the voltage was 0.6 V, and a higher value indicated better output performance.
  • the membrane-electrode assemblies manufactured in the examples and comparative examples were examined using a scanning electron microscope (SEM) to determine the thickness of the first layer and the area occupied by the first layer among the entire surface of the polymer electrolyte membrane. The results are shown in Table 3 below.
  • Thickness of the first catalyst layer (nm) Area ratio occupied by the first catalyst layer (%)
  • the durability of the fuel cell was excellent without any degradation in performance.
  • the first layer was formed with a thickness of 30 to 2,000 on the polymer electrolyte membrane, the durability and cell performance of the fuel cell were excellent.
  • the plate carbon nanofibers occupy an area of 5 to 65% of the total surface of the polymer electrolyte membrane, the durability and cell performance of the fuel cell were excellent, and in particular, when the plate carbon nanofibers occupy an area of 10 to 60% of the total surface of the polymer electrolyte membrane, the durability and cell performance of the fuel cell were confirmed to be even better.
  • Second layer Second catalyst layer
  • Fuel supply section 220 Reforming section
  • Second supply pipe 233 First discharge pipe
  • Second discharge pipe 240 Oxidizer supply section

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

Abstract

La présente invention concerne un ensemble membrane-électrode pour une pile à combustible, son procédé de fabrication, et une pile à combustible comprenant l'ensemble membrane-électrode, l'ensemble membrane-électrode comprenant : une membrane électrolytique polymère ; une première couche formée sur une région prédéterminée d'une surface quelconque de la membrane électrolytique polymère ; et une seconde couche destinée à recouvrir la surface externe de la première couche et la région d'une surface de la membrane électrolytique polymère dépourvue de la première couche, la première couche comprenant des nanofibres de carbone plaquettaire, et la seconde couche comprenant un support de catalyseur, un catalyseur supporté sur le support de catalyseur et un ionomère. Selon la présente invention, les performances et la durabilité peuvent être améliorées grâce à la première couche.
PCT/KR2024/097043 2024-04-29 2024-12-17 Ensemble membrane-électrode pour pile à combustible, son procédé de fabrication et pile à combustible comprenant un ensemble membrane-électrode Pending WO2025230090A1 (fr)

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KR20240056924 2024-04-29
KR10-2024-0056924 2024-04-29
KR1020240186427A KR20250157936A (ko) 2024-04-29 2024-12-13 연료전지용 막-전극 어셈블리, 이의 제조방법 및 막-전극 어셈블리를 포함하는 연료전지
KR10-2024-0186427 2024-12-13

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006253030A (ja) * 2005-03-11 2006-09-21 Toshiba Corp 液体燃料型固体高分子燃料電池用カソード電極及び液体燃料型固体高分子燃料電池
KR20070106303A (ko) * 2006-04-28 2007-11-01 삼성에스디아이 주식회사 연료전지용 막-전극 어셈블리, 및 이를 포함하는 연료전지시스템
JP2017525103A (ja) * 2014-07-08 2017-08-31 ビーディーエフ アイピー ホールディングス リミテッド 電気化学的電池のためのカソード設計
KR20230171817A (ko) * 2022-06-14 2023-12-21 코오롱인더스트리 주식회사 막-전극 어셈블리 및 이를 포함하는 연료전지
KR20240011562A (ko) * 2022-07-19 2024-01-26 코오롱인더스트리 주식회사 막-전극 어셈블리 및 이를 포함하는 연료전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006253030A (ja) * 2005-03-11 2006-09-21 Toshiba Corp 液体燃料型固体高分子燃料電池用カソード電極及び液体燃料型固体高分子燃料電池
KR20070106303A (ko) * 2006-04-28 2007-11-01 삼성에스디아이 주식회사 연료전지용 막-전극 어셈블리, 및 이를 포함하는 연료전지시스템
JP2017525103A (ja) * 2014-07-08 2017-08-31 ビーディーエフ アイピー ホールディングス リミテッド 電気化学的電池のためのカソード設計
KR20230171817A (ko) * 2022-06-14 2023-12-21 코오롱인더스트리 주식회사 막-전극 어셈블리 및 이를 포함하는 연료전지
KR20240011562A (ko) * 2022-07-19 2024-01-26 코오롱인더스트리 주식회사 막-전극 어셈블리 및 이를 포함하는 연료전지

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