WO2017116041A1

WO2017116041A1 - Electrolyte membrane for fuel cell, electrode for fuel cell, and membrane-electrode assembly and fuel cell using same

Info

Publication number: WO2017116041A1
Application number: PCT/KR2016/014540
Authority: WO
Inventors: 임정혁; 김상욱; 양은준; 이주호
Original assignee: 주식회사 동진쎄미켐
Priority date: 2015-12-29
Filing date: 2016-12-12
Publication date: 2017-07-06

Abstract

The present invention relates to: an electrolyte membrane for a fuel cell, having excellent durability by effectively removing radicals generated when the cell is driven; an electrode for a fuel cell, and a membrane-electrode assembly and a fuel cell capable of implementing stable performance by using the electrolyte membrane or the electrode for a fuel cell.

Description

【Specification】

[Name of invention]

Electrolyte membrane for fuel cell, electrode for fuel cell, membrane-electrode assembly and fuel cell using same

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0188627 of December 29, 2015 and Korean Patent Application No. 10-2015-0188629 of December 29, 2015. All contents disclosed in these documents are included as part of this specification.

The present invention relates to an electrolyte membrane for a fuel cell, an electrode for a fuel cell, a membrane-electrode assembly using the same, and a fuel cell. More specifically, a membrane-electrode assembly capable of effectively removing radicals generated when the battery is driven to realize stable performance using a fuel cell electrolyte membrane having excellent durability, a fuel cell electrode, the electrolyte membrane or a fuel cell electrode, and Relates to a fuel cell.

[Technique to become background of invention]

Polymer electrolyte fuel cell (PEFC) is a fuel cell using polymer membrane with hydrogen ion exchange characteristics as electrolyte, solid polymer electrolyte fuel cell (SPEFC), Hydrogen is called by various names such as proton exchange membrane fuel cells (PEMFC). Compared to other fuel cells, the polymer electrolyte membrane fuel cell (PEMFC) has a low operating temperature of 8 (rc), high efficiency, high current density and power density, short start-up time, and fast response to load changes. In particular, the polymer membrane is used as the electrolyte, which eliminates the need for corrosion and electrolyte control, and is less sensitive to changes in the pressure of the reaction vessel, and because of its simplicity of design, ease of manufacture, and the ability to produce a wide range of outputs. In addition, the polymer electrolyte fuel cell (PEFC) has the advantage that can be used in a wide variety of fields, such as the power source of pollution-free vehicles, local installation power generation, mobile power, military power. The characteristics of hydrogen ion exchange membrane in polymer electrolyte fuel cell (PEFC) are mainly expressed by ion exchange capacity (IEC) or equivalent weight (EW) and used as electrolyte membrane for fuel cell. Hydrogen exchange membranes should have high hydrogen ion conductivity, mechanical strength, low gas permeability and water transport. When dehydration, the conductivity of hydrogen ions drops rapidly, so it must be resistant to dehydration. It must have a high resistance to oxidation and reduction reactions, hydrolysis, etc., which are directly experienced by the electrolyte membrane, have a positive cationic binding force, and require homogeneity. And these properties must be maintained for some time. In addition to satisfying all of these conditions, linking with commercialization requires the development of cheap and environmentally friendly manufacturing techniques.

The polymer electrolyte membrane may be classified into a perfluorine system, a partial fluorine system, and a hydrocarbon system. Perfluoro-based electrolyte membranes are suitable for high mechanical strength, physical and chemical stability, and high cationic conductivity, including Naf i on® from Dufont, Ac ipl ex® from Asahi Chemi Cal, and Flemi on® from Asahi Gl ass. Although commercialized, the hydrogen ion permeability is high and the Cell performance is deteriorated due to decreased physical and chemical stability. On the other hand, in the fluorine-based and hydrocarbon-based electrolyte membranes, the electrolyte membrane is destroyed by radicals generated during fuel cell operation, and the membrane-electrode assembly is typically formed by impregnating a radical scavenger such as Ce02 into the porous support together with the electrolyte membrane. Improves the radical resistance.

However, in the prior art, when the catalyst of the radical protective layer on the surface of the electrolyte membrane and the electrode layer are in electrical contact with each other, there is a limit in that the radical removal effect is decreased and the permeability is increased, thereby degrading the MEA performance.

Accordingly, there is a need to develop an electrolyte membrane or a polymer electrolyte fuel cell electrode for a polymer electrolyte fuel cell that can realize stable performance when applied to a battery while maximizing radical removal effect.

[Content of invention]

Problem to be solved

The present invention effectively removes radicals generated during battery operation It is to provide an electrolyte membrane for a fuel cell or an electrode for a fuel cell having a durability.

In addition, the present invention is to provide a membrane-electrode assembly and a fuel cell that can implement a stable performance using the electrolyte membrane or the electrode. [Measures of problem]

In the present specification, the conductive film; A radical protective layer formed on at least one surface of the ion conductive membrane and including at least one metal and an ion conductive polymer; And an insulating layer formed on the radical protective layer, the insulating layer including an ion conductive polymer, wherein the metal included in the radical protective layer is formed in a state in which the conductive polymer is brought into contact with a surface thereof _. An electrolyte membrane for an acid fuel cell is provided.

In the present specification, the electrode catalyst layer; An insulating layer formed on at least one surface of the electrode catalyst layer, the conductive layer including a conductive polymer; And a radical protective layer formed on the insulating layer, the radical protective layer including at least one metal and an ion conductive polymer, wherein the metal included in the radical protective layer is dispersed in contact with a conductive polymer subsequent to the surface thereof. An electrode is provided.

In the present specification, there is also provided a fuel cell membrane-electrode assembly including an electrolyte membrane and an electrode catalyst layer provided on both surfaces of the electrolyte membrane.

In the present specification, there is provided a fuel cell membrane-electrode assembly including an electrolyte membrane and two electrodes provided on both sides of the electrolyte membrane, and at least one of the two electrodes includes the fuel cell electrode. Also provided herein is a fuel cell comprising the membrane-electrode assembly.

Hereinafter, a fuel cell electrolyte membrane, a fuel cell electrode, a membrane-electrode assembly using the same, and a fuel cell according to specific embodiments of the present invention will be described in detail. According to one embodiment of the invention, the ion conductive membrane; A radical protective layer formed on at least one surface of the ion conductive membrane and including at least one metal and an ion conductive polymer; And formed on the radical protective layer, and ion conductive An insulating layer including a polymer; and the metal included in the radical protection layer may be provided with an electrolyte membrane for a fuel cell in which the conductive polymer is dispersed in contact with a surface thereof.

The present inventors further introduce an insulating layer containing an ion conductive polymer onto the radical protective layer by using the above-described specific fuel cell electrolyte membrane, thereby separating the radical protective layer and the electrode layer and the electrode layer when the membrane-electrode assembly is bonded. It was confirmed that the electrical protection of the radical protecting insects with the catalyst can be blocked. Accordingly, by fully exhibiting the radical removal effect by the radical protective layer, it was confirmed through experiments that an electrolyte membrane structure having physically and chemically excellent durability was confirmed and completed the invention.

In particular, since the radical protective layer can secure insulation by a separate insulating layer, it is not necessary to use a separate carbon support as in the prior art, and the ion conductive polymer directly contacts the metal surface in the radical protective layer. Can be dispersed in a state, it is possible to maximize the radical removal efficiency.

In addition, the insulating layer contains a conductive polymer, which not only blocks the electrical contact between the electrode charge and the catalyst of the radical protective layer when the membrane-electrode assembly is bonded, but also provides excellent electrical properties even when applied and driven in a fuel cell. As a result, the improved performance can be realized.

The electrolyte membrane for a fuel cell of one embodiment described above can be used in all energy storage and production devices such as solar cells, secondary cells, supercapacitors and the like. It can also be used in organic electroluminescent devices.

Specifically, the ion conductive membrane, the radical protective layer, and the insulating layer included in the electrolyte membrane for a fuel cell of the embodiment are as follows. Ion conductive membrane

The ion conductive membrane is a polymer membrane having electrical insulation and subsequent conductivity, and may include a conductive polymer. The ion conductive polymer refers to a polymer having a property of transporting charges by ions, and the ion conductive polymer may include a fluorine-based polymer or a hydrocarbon-based polymer. Specific examples of the fluorine-based polymer are not particularly limited, and examples For example, a perfluorinated sulfonic acid group-containing polymer or a perfluoro-based proton conductive polymer can be used.

In addition, specific examples of the hydrocarbon-based polymer are not particularly limited, for example, sulfonated polysulfone copolymer, sulfonated poly (ether-ketone) -based polymer, sulfonated polyether ether ketone-based polymer, polyimide-based polymer Polystyrene-based polymers, polysulfone-based polymers, clay-sulfonated polysulfone nanocomposites or mixtures of two or more thereof may be used.

More specific examples include Aquivion® membranes. Radical protection layer

The radical protective layer included in the electrolyte membrane for the fuel cell may be formed on at least one surface of the ion conductive membrane and include at least one metal and an ion conductive polymer.

At least one surface of the conductive film on which the radical protective layer is formed may mean one surface of the upper surface or the lower surface of the ion conductive film, or may include both the upper surface and the lower surface. Specifically, through the following Figure 1, for example, a radical protective layer 3 may be formed on the upper surface of the ion conductive membrane (4).

The radical protection layer may include at least one metal to effectively remove radicals generated during operation of the fuel cell. The at least one metal is a catalyst for promoting oxidation of hydrogen and reduction of oxygen, and may serve to remove radicals by decomposing peroxy radicals and hydroperoxy radicals into water and oxygen.

The at least one metal may include at least one metal selected from the group consisting of metal elements belonging to groups 3 to 13 of the periodic table. That is, the additive metal may include a transition metal belonging to Groups 3 to 12 of the Periodic Table or a post-transition metal belonging to Group 13 of the Periodic Table.

More specifically, the at least one metal is palladium (Pal ladium, Pd) or alloys including palladium. The alloy containing palladium may include at least one metal selected from the group consisting of palladium and metal elements belonging to Groups 3 to 13 of the Periodic Table.

As the palladium metal has a higher hydrogen bonding energy than other metals, the palladium metal may exhibit better selectivity for radicals or ions. Accordingly, when the palladium metal is used as the radical protection layer, the generation of hydrogen peroxide and radicals generated during fuel cell operation is suppressed. The effect of removing the generated radicals can be maximized, thereby improving the durability while reducing the gas permeability of the electrolyte membrane.

Examples of metals other than palladium added in the alloy including the palladium are not particularly limited. For example, platinum (Pt), gold (Au), silver (Ag), gallium (Ga), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), molybdenum (Mo), zinc (Zn) or two kinds thereof The above mixture can be used. More specifically, examples of the alloy containing palladium include palladium-cobalt alloy, palladium-titanium alloy, palladium-manganese alloy, palladium-platinum alloy, palladium-nickel alloy or a combination thereof.

The radical protective layer may include a conductive polymer. The conductive polymer may serve as a binder in which the radical protective layer including the metal may be more stably laminated. Accordingly, in the radical protective layer, at least one metal may be dispersed in the ion conductive polymer.

Specifically, the metal may be dispersed in a state in which the ion conductive polymer is in contact with the surface. This is because the metal is directly used without being supported on a carrier such as a carbon support. As the metal is used directly without being supported on the carrier, the active surface area of the metal is increased, and the radical removal efficiency by the radical protection layer can be maximized.

More specifically, the total surface area of the metal contained in the radical protective layer

50% or more, or 50% to 100% may be in contact with the ion conductive polymer. On the surface of the metal in contact with the ion conductive polymer, hydrogen peroxide and radical scavenging action by the metal may exhibit activity. Therefore metal full table When more than 50% of the area is in contact with the ion conductive polymer, the active surface area of the metal may increase to 5 or more of the total surface area.

On the other hand, as in the conventional technique in which the metal is supported on a carrier, when less than 50% of the total surface area of the metal is in contact with the ion conductive polymer, as the active surface area of the metal decreases to less than 50%, There is a limit to decrease the hydrogen peroxide and radical removal efficiency.

The ion conductive polymer refers to a polymer having a property of transporting charges by silver, and the ion conductive polymer may include a fluorine-based polymer or a hydrocarbon-based polymer.

Specific examples of the fluorine-based polymer are not particularly limited. For example, a perfluorinated sulfonic acid group-containing polymer or a perfluoro-based proton conductive polymer may be used.

In addition, specific examples of the hydrocarbon-based polymer are not particularly limited. For example, sulfonated polysulfone copolymer, sulfonated poly (ether-ketone) polymer, sulfonated polyether ether ketone polymer, polyimide polymer , Polystyrene-based polymers, polysulfene-based polymers, clay-sulfonated polysulfone nanocomposites or two or more kinds thereof may be used.

The silver conductive polymer included in the radical protective layer and the ion conductive polymer included in the silver conductive film described above may be the same material or different materials.

The radical protective layer is 1 part by weight to 20 parts by weight, or 3 parts by weight to 10 parts by weight, or 5 parts by weight to 10 parts by weight, or 5.5 parts by weight based on ₁₀₀ parts by weight of the ion conductive polymer. It may contain up to 10 parts by weight. When too much metal is added to the ion conductive polymer in the radical protective layer, the coating composition for reducing the stability and uniformity of the coating composition for forming the radical protective layer may be reduced.

The radical protective layer may have a thickness of 10 inn to 2000 nm, or 50 ran to 1500 nm. When the thickness of the radical protective layer is too thick, exceeding 2000 ran, the performance of the membrane-electrode assembly may be degraded, and it may be difficult to manufacture a thin electrolyte membrane having a thin thickness. Insulation layer

The insulating layer included in the electrolyte membrane for the fuel cell is formed on the radical protective layer, and may include an ion conductive polymer.

The insulating layer may be formed on the radical protective layer and stacked for the purpose of separating the radical protective layer from the electrode catalyst layer. Specifically. The insulating layer may be formed on the other side of the radical protection insect that does not contact the aion conductive film. That is, an ion conductive film may be formed on one surface of the radical protection layer, and an insulating layer may be formed on the other surface.

More specifically, as shown in FIG. 1, the electrolyte membrane on which the insulating layer is formed may have a three-layer structure in which the conductive membrane 4, the radical protective layer 3, and the insulating layer 2 are laminated in this order. .

The insulating layer may include an ion conductive polymer. The ion conductive polymer refers to a polymer having a property of transporting charges by ions, and the silver conductive polymer may include a fluorine-based polymer or a hydrocarbon-based polymer.

In addition, specific examples of the hydrocarbon-based polymer are not particularly limited. For example, sulfonated polysulfone copolymer, sulfonated poly (ether-ketone) polymer, sulfonated polyether ether ketone polymer, polyimide polymer , Polystyrene-based polymers, polysulfone-based polymers, clay-sulfonated polysulfone nanocomposites or two or more kinds thereof can be used.

The silver conductive polymer included in the insulating layer and the silver conductive polymer included in the radical protective layer or the ion conductive membrane described above may be the same material or different materials.

The content of the ion conductive polymer included in the insulating layer may be 300 parts by weight to 500 parts by weight, or 350 parts by weight to 400 parts by weight with respect to 100 parts by weight of the ion conductive polymer included in the radical protecting insect. The thickness of the insulating layer may be 10 nm to 2000 ran, or 50 nm to 1500 inn. If the thickness of the insulating layer is too thick, more than 2000 nm, the performance of the membrane-electrode assembly may be degraded, it may be difficult to manufacture a thin electrolyte membrane of a thin thickness.

More specifically, the ratio of the radical protective layer thickness to the thickness of the insulating layer may be 1 to 10, or 1.1 to 5, or 1.2 to 3. The radical protective layer thickness ratio with respect to the insulation layer thickness means a value obtained by dividing the thickness of the radical protective layer by the thickness of the insulating layer. Manufacturing method of electrolyte membrane for fuel cell

The method of manufacturing an electrolyte membrane for a fuel cell includes coating a first coating composition including at least one metal and a conductive polymer on at least one surface of an ion conductive membrane to form a radical protective layer; And forming an insulating layer by coating a second coating composition including an ion conductive polymer on the radical protection layer.

Coating the first coating composition including the at least one metal and the ion conductive polymer on at least one surface of a subsequent conductive film to form a radical protective layer, wherein the first coating composition is a composition for forming a radical protective layer, at least It may include one or more metal and ion conductive polymers. Details of the metal ion conductive polymer, the ion conductive membrane, and the radical protective layer may include the above-described details in the embodiment.

The first coating composition may further include a solvent. The solvent may include an aqueous solvent or an organic solvent, a water-based or organic solvent that is commonly used without limitation, and may be the same as the solvent used in the preparation of the electrode catalyst layer composition to be described later.

An example of a method of preparing the first coating composition is not particularly limited. For example, a method of dispersing the at least one metal or ion conductive polymer in an organic solvent or an aqueous solvent may be used.

Examples of the method of coating the first coating composition are also not limited in scope, for example, spraying, screen printing, inkjet printing, dipping, bar Coating, cap coating, knife coating, slot die coating, gravure coating and the like can be carried out through a variety of known methods.

After forming the radical protective layer by coating the first coating composition including the at least one metal and the ion conductive polymer on at least one surface of the ion conductive membrane, the method may further include drying the coated radical protective layer. . After the coating layer of the first coating composition and the coating layer of the second coating composition are sequentially formed on the conductive film, these coating layers may be dried together, and the respective coating layers may be separately formed and dried. have.

Examples of the drying step are not particularly limited, for example, a first heat treatment process performed for 1 to 24 hours at 20 to 100 ^° C, and a second performed for 0.5 to 10 minutes under 120 to 250 ^° C. Heat treatment processes may be included. Residual solvent included in the coating layer may be sufficiently removed through the first and second heat treatment processes, and the radical protective layer may be more stably laminated on the ion conductive membrane. In addition, when an ion conductive polymer is used, the thermal curing may be performed through the plurality of heat treatment processes.

In the step of forming an insulating layer by coating a second coating composition including an ion conductive polymer on the radical protective layer, the second coating composition may further include a solvent. Information on the ion conductive polymer may include the above-described information in the embodiment. The solvent may include an aqueous solvent or an organic solvent, a water-based or organic solvent that is commonly used without limitation, may be used in the same manner as the solvent used in the preparation of the electrocatalyst layer composition to be described later.

An example of a method of preparing the second coating composition is not particularly limited. For example, a method of dispersing the ion conductive polymer in an organic solvent or an aqueous solvent may be used.

Examples of the method of coating the second coating composition are also not limited thereto, and for example, spraying, screen printing, inkjet printing, dipping, bar coating, cap coating, knife coating, slurry die coating, and gravure Known coatings This can be done through various methods.

After coating the second coating composition including the ion conductive polymer on the radical protective layer to form an insulating layer, the method may further include drying the coated insulating worm. After the coating layer of the first coating composition and the coating layer of the second coating composition are sequentially formed on the ion conductive membrane, these coating layers may be dried together, or the coating layers may be formed and dried separately. have.

Examples of the drying step are not particularly limited, for example, the first heat treatment process is performed for 1 to 24 hours at 20 to 100 ^° C, and the second is performed for 0.5 to 10 minutes under 120 to 250 ° C. Heat treatment processes may be included. Through the first and second heat treatment processes, the residual solvent included in the coating layer may be sufficiently removed, and the insulating layer may be more stably stacked. In addition, _{when the} ion conductive polymer is used, the thermal curing may be performed through the plurality of heat treatment processes. On the other hand, according to another embodiment of the invention, the electrode catalyst layer; An insulating layer formed on at least one surface of the electrode catalyst layer and including an ion conductive polymer; And a radical protective layer formed on the insulating layer and including at least one metal and an ion conductive polymer, wherein the metal included in the radical protective layer is dispersed in a state in which the ion conductive polymer is in contact with the surface. An electrode for a fuel cell may be provided.

The present inventors further introduce an insulating layer containing an ion conductive polymer together with a radical protective layer by using the above-described specific fuel cell electrode, thereby separating the radical protective layer and the electrode catalyst layer and included in the electrode and the radical protective layer, respectively. It was confirmed that the electrical contact of the catalyst can be blocked. Accordingly, by fully exhibiting the radical removal effect by the radical protective layer, it was confirmed through experiments that an electric structure having excellent physical and chemical durability was formed through experiments and completed the invention.

In particular, since the radical protective layer can ensure insulation by a separate insulating layer, it is not necessary to use a separate carbon support as in the prior art. Accordingly, the ion conductive polymer may be dispersed in a directly contacted state on the metal surface in the radical protection layer, thereby maximizing radical removal efficiency.

In addition, the insulating layer includes an ion conductive polymer, and not only blocks electrical contact between the electrode catalyst layer and the catalyst of the radical protective layer, but also provides excellent electrical properties when driven and applied to a fuel cell. Improved performance can be achieved.

The fuel cell electrode of one embodiment described above may be used in all energy storage and production devices such as solar cells, secondary cells, supercapacitors, and the like. It can also be used in organic electroluminescent devices.

Specifically, looking at the electrode for a fuel cell of the embodiment as follows. Electrocatalyst layer

The electrode catalyst layer may comprise conventional metals known to promote oxidation of hydrogen and reduction of oxygen. For example, the electrode catalyst layer may comprise a platinum group metal (platinum, para, rhodium, ruthenium, iridium, and osmium), gold, silver, or an alloy thereof, and the metals and base metal (gallium) , Titanium vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and the like.

The metal may be used in an unsupported state or a supported state. When the metal is supported, it may be used in a state supported on an inorganic carrier such as acetylene black or carbon-based carrier such as graphite, alumina or silica. When used in a supported state of the metal, in order to express an appropriate catalytic effect, the carrier has a specific surface area of at least 150 m '/ g or 500 to 1200 m7 g and an average particle diameter of 10 to 300 nm or 20 to 100 nm. It is preferable to have.

An example of a method of manufacturing the electrode catalyst layer is not particularly limited, but for example, the metal, the binder, and the solvent may be mixed to prepare a catalyst slurry, and may be prepared by a method of applying the catalyst slurry. The insulation worm included in the electrode for the fuel cell is formed on at least one surface of the electrode catalyst layer, and may include an ion conductive polymer.

The insulating layer may be formed on at least one surface of the electrode catalyst layer and stacked for the purpose of separating the radical protective layer from the electrode catalyst layer.

At least one surface of the electrode catalyst layer on which the insulating layer is formed may mean one surface of an upper surface or a lower surface of the electrode catalyst layer, or may include both an upper surface and a lower surface. In detail, for example, the insulating layer 4 may be formed on the upper surface of the electrode catalyst layer 5 through FIG. 1.

The insulating layer may include a conductive polymer. The ion conductive polymer refers to a polymer having a property of transporting charges by silver, and the silver conductive polymer may include a fluorine-based polymer or a hydrocarbon-based polymer.

Specific examples of the fluorine-based polymer are not particularly limited, and for example, a perfluorinated sulfonic acid group-containing polymer or a perfluoro-based proton conductive polymer may be used.

In addition, specific examples of the hydrocarbon-based polymer are not particularly limited, but for example, sulfonated pulleysulphene copolymer, sulfonated pulley (ether-kerone) -based polymer, sulfonated polyether ether ketone polymer, polyimide polymer , Polystyrene-based polymers, polysulfone-based polymers, clay-sulfonated polysulfone nanocomposites or two or more kinds thereof can be used.

The content of the ion conductive polymer included in the insulating layer may be 300 parts by weight to 500 parts by weight, or 350 parts by weight to 400 parts by weight with respect to 100 parts by weight of the ion conductive polymer included in the radical protective layer.

The thickness of the insulating layer may be 10 i to 2000 ran, or 50 ran to 1500 iim. If the thickness of the insulating layer is too thick, exceeding 2000 ran, the performance of the film-electrode assembly may be degraded, and it may be difficult to manufacture a thin electrode having a thin thickness.

More specifically, the ratio of the radical protective layer thickness to the thickness of the insulating layer may be 1 to 10, or 1.1 to 5, or 1.2 to 3. The radical protective layer thickness ratio to the insulating layer thickness is the radical protective layer It means the value obtained by dividing the thickness by the insulation layer thickness. Radical protection layer

The radical protective layer included in the fuel cell electrode may be formed on the insulating layer and include at least one metal and an ion conductive polymer. Specifically, the radical protective layer may be formed on the other surface of the insulating layer that is not in contact with the electrode catalyst layer. That is, an electrode catalyst layer is formed on one surface of the insulating layer, and a radical protection layer may be formed on the other surface.

More specifically, the electrode on which the radical protective layer is formed may have a three-layer structure stacked in the order shown in FIG. 3, the electrode catalyst layer 5, the insulating layer 2, and the radical protective layer 3. have.

The radical protective layer may include at least one metal to effectively remove radicals generated during operation of the fuel cell. The at least one metal is a catalyst for promoting the oxidation of hydrogen and the reaction of oxygen reduction, and may serve to remove radicals by decomposing peroxy radicals and hydroperoxy radicals into water and oxygen.

The at least one metal may include at least one metal selected from the group consisting of metal elements belonging to groups 3 to 13 of the periodic table. That is, the metal may include a transition metal belonging to group 3 to 12 of the periodic table or a post-transit ion metal belonging to group 13 of the periodic table.

More specifically, the at least one metal may include palladium (Pal) or an alloy including palladium. The alloy containing palladium may include one or more metals selected from the group consisting of metal elements belonging to the group 3 to 13 of the periodic table.

As the palladium metal has a higher hydrogen bonding energy than other metals, the palladium metal may exhibit better selectivity for radicals or ions. Accordingly, when palladium metal is used as the radical protecting insect, generation of hydrogen peroxide and radicals generated during fuel cell operation is suppressed. Generated radicals Removal effect can be maximized, thereby improving the durability while reducing the gas permeability of the electrode.

Examples of metals other than palladium added in the alloy containing palladium are not particularly limited. For example, platinum (Pt), gold (Au), silver (Ag), gallium (Ga), titanium (Ti), Vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), molybdenum (Mo), zinc (Zn) or two of these Mixtures of more than one species can be used. More specifically, examples of the alloy containing palladium include a palladium-cobalt alloy, a palladium-titanium alloy, a palladium-manganese alloy, a palladium-platinum alloy, a palladium-nickel alloy, or a combination thereof.

The radical protective layer may include an ion conductive polymer. The ion conductive polymer may serve as a binder to allow the radical protective layer including the metal to be more stably laminated. Accordingly, in the radical protective layer, at least one metal may be dispersed in the silver conductive polymer.

Specifically, the metal may be dispersed in a state in which the ion conductive polymer is in contact with the surface. This is because the metal is directly used without being supported on a carrier such as a carbon support. As such, as the metal is directly used without being supported on the carrier, the active surface area of the metal is increased, thereby maximizing radical removal efficiency by the radical protection layer.

50% or more, or 50% to 100% may be in contact with the ion conductive polymer. The hydrogen peroxide and radical scavenging action by the metal may be active on the surface of the metal in contact with the conductive polymer. Therefore, when more than 50¾> of the total surface area of the metal is in contact with the ion conductive polymer, the active surface area of the metal may increase to more than 50% of the total surface area.

On the other hand, as in the conventional technique in which the metal is supported on a carrier, when less than 50% of the total surface area of the metal is in contact with the ion conductive polymer, the active surface area of the metal is reduced to less than 50%, and thus, the radical protective layer There is a limit to decrease the hydrogen peroxide and radical removal efficiency.

The ion conductive polymer has a property of carrying charges by silver It means a polymer having, the ion conductive polymer may include a fluorine-based polymer or a hydrocarbon-based polymer.

The silver conductive polymer included in the radical protecting insect and the ion conductive polymer included in the insulating layer described above may be the same material or different materials.

The radical protective layer is 1 part by weight to 20 parts by weight, or 3 parts by weight to 10 parts by weight, or 5 parts by weight to 10 parts by weight, or 5.5 parts by weight to at least one metal based on 100 parts by weight of the ion conductive polymer. It can be included in 10 increments. When too much metal is added to the ion conductive polymer in the radical protective layer, coating stability may be reduced by decreasing the stability and uniformity of the coating composition for forming the radical protective layer.

The radical protective layer may have a thickness of 10 ran to 2000 nm, or 50 ran to 1500 nm. When the thickness of the radical protective layer is too thick, exceeding 2000 ran, the performance of the membrane-electrode assembly may be degraded, and it may be difficult to manufacture a thin electrode having a thin thickness. Manufacturing method of electrode for fuel cell

The method for manufacturing an electrode for a fuel cell may include forming an insulating worm by coating a first coating composition including an ion conductive polymer on at least one surface of an electrode catalyst layer; And coating a second coating composition comprising at least one metal and an ion conductive polymer on the insulating layer to form a radical protective layer. It may include. In the step of forming an insulating layer by coating the first coating composition comprising the conductive polymer on at least one surface of the electrode catalyst layer, the first coating composition is a composition for forming the insulating layer, it may include a conductive polymer have.

The first coating composition may further include a solvent. The solvent may include an aqueous solvent or an organic solvent, a conventionally widely used aqueous or organic solvent may be used without limitation, and specifically, the same solvent as that used in the preparation of the electrolytic membrane described below may be used.

An example of a method of preparing the first coating composition is not particularly limited. For example, a method of dispersing the ion conductive polymer in an organic solvent or an aqueous solvent may be used.

Examples of the method of coating the first coating composition are also not limited to, for example, spraying, screen printing, inkjet printing, dipping, bar coating, cap coating, knife coating, slot die coating, gravure coating It may be carried out through various known methods such as.

After the coating of the first coating composition including the conductive polymer on at least one surface of the electrode catalyst layer to form an insulating layer, the method may further include drying the coated insulating charge. After the coating layer of the first coating composition and the coating layer of the second coating composition are sequentially formed on the electrode catalyst layer, the coating layers may be dried together, or the coating layers may be formed and dried separately. .

Examples of the drying step are not particularly limited, for example, the first heat treatment process performed for 1 to 24 hours under 20 to 100 t, and the second heat treatment carried out for 0.5 to 10 minutes under 120 to 250 ^° C. This may include the process. Residual solvents included in the coating layer may be removed through the first and second heat treatment processes, and the insulating layer may be more stably stacked on the electrode catalyst layer. In addition, when an ion conductive polymer is used, the thermal curing may be performed through the plurality of heat treatment processes.

Coating the second coating composition including at least one metal and an ion conductive polymer on the insulating layer to form a radical protective layer; The second coating composition may further comprise a solvent. The metal, ion conductive polymer, the electrode catalyst layer, the radical protective layer may include the above-described details in one embodiment.

The solvent may include an aqueous solvent or an organic solvent, an aqueous or organic solvent which is generally widely used may be used without limitation, and specifically, the same solvent as that used in the preparation of the electrolyte membrane described later may be used.

An example of a method of preparing the second coating composition is not particularly limited. For example, a method of dispersing the at least one metal or ion conductive polymer in an organic solvent or an aqueous solvent may be used.

Examples of the method of coating the second coating composition are also not limited thereto, for example, spraying, screen printing, inkjet printing, dipping, bar coating, cap coating, knife coating, slot die coating, gravure coating It can be carried out through various known methods such as.

After forming the radical protective layer by coating the second coating composition including the at least one metal and the conductive polymer on the insulating layer, the method may further include drying the coated radical protective layer. After the coating layer of the first coating composition and the coating layer of the second coating composition are sequentially formed on the electrode catalyst layer, these coating layers may be dried together, or the formation and drying of each coating layer may be performed separately. have.

A second heat treatment but is not an example of the drying step greatly restricted, for example, performed during the first heat treatment step, a 0.5 to 10 minutes at from 120 to 250 t is performed for 1 to 24 hours under 20 within the support 100 ^° C This may include the process. Through the first and second heat treatment processes, the residual solvent included in the coating may be removed in layers, and the radical protective layer may be more stably laminated. In addition, when an ion conductive polymer is used, the thermal curing may be performed through the plurality of heat treatment processes. On the other hand, according to another embodiment of the invention, the fuel cell electrolyte membrane and the electrode catalyst layer provided on both sides of the electrolyte membrane of the embodiment Membrane-electrode assemblies for fuel cells can be provided.

The content of the electrolyte membrane for the fuel cell includes the content described above with respect to the embodiment.

In addition, the electrode catalyst layers provided on both surfaces of the electrolyte membrane may include a conventional metal known to promote oxidation of hydrogen and reduction of oxygen. For example, the electrode catalyst layer may include platinum group metals (platinum, palladium, rhodium, ruthenium, iridium, and osmium), gold, silver, or alloys thereof, and the metals and base metals (gallium, titanium) Alloys of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, and the like.

The metal may be used in an unsupported state or a supported state. When the metal is supported, it may be used in a state supported on an inorganic carrier such as acetylene black, graphite and ground carbon-based carrier, alumina or silica. When used in a supported state of the metal, in order to express an appropriate catalytic effect, the carrier has a specific surface area of 150 mVg or more or 500 to 1200 mVg and an average particle diameter of 10 to 300 ran or 20 to 100 nm. desirable.

The membrane-electrode assembly may further include a gas diffusion layer. The gas diffusion layer serves to support the electrode catalyst layer and to improve reaction efficiency by diffusing the reaction gas into the electrode catalyst layer. As an example of the gas diffusion layer, carbon paper or carbon cloth may be used. Preferably, a water repellent treatment of carbon paper or carbon cloth with a fluorine resin such as polytetrafluoroethylene may be used. The water diffusion treated gas diffusion layer may prevent the performance of the gas diffusion layer from being deteriorated by water generated when the fuel cell is driven.

In addition, a microporous layer (mi croporous layer) may be further included between the electrode catalyst layer and the gas diffusion layer to further increase the diffusion effect of the gas. The microporous layer may be prepared by coating a composition including a carbon powder, a carbon block, an activated carbon, a conductive material such as acetylene black, a binder such as polytetrafluororoethylene, and a conductive polymer.

In addition, the membrane-electrode assembly may further include a sub-gasket. The sub gasket protects the electrode catalyst layer and the electrolyte membrane, and assembles the fuel cell. In order to ensure ease of handling in the case, it may be bonded to both edge regions of the electrode catalyst layer or the electrolyte membrane. Although the specific example of the said sub-gasket is not restrict | limited greatly, For example, polymer films, such as polyethylene (PE) and polyethylene naphthalate (PEN), can be used.

An example of a method of manufacturing the electrode catalyst layer is not particularly limited. For example, the metal, binder, and solvent may be mixed to prepare a catalyst slurry, and the method may be prepared by applying the catalyst slurry to a gas diffusion layer. All. ᅳ

Meanwhile, an example of a method of manufacturing the membrane-electrode assembly is not particularly limited. For example, an electrolyte membrane for a fuel cell of the embodiment is inserted between the prepared electrode catalyst layers (anode and cathode), and press or hot The method of pressing by the crimping method can be used. In this case, the press compression method may be performed under a pressure of 0 to 2000 psi, a silver content of 50 to 300 ° C, and an isotropic speed of 0.1 to 3 m / min. In addition, the hot pressing may be performed under a pressure of 500 to 2000 psi, a silver of 50 to 300 ^° C., and a pressing time of 1 to 60 minutes. On the other hand, according to another embodiment of the invention, an electrolyte membrane and two electrodes provided on both sides of the electrolyte membrane, at least one or more of the two electrodes includes a fuel cell electrode of the embodiment Membrane-electrode assemblies can be provided

The electrolyte membrane may include a conductive polymer, which is a polymer membrane having electrical insulation and subsequent conductivity. The ion conductive polymer refers to a polymer having a property of transporting charges by ions, and the ion conductive polymer may include a fluorine-based polymer or a hydrocarbon-based polymer. Specific examples of the fluorine-based polymer are not particularly limited, but for example, a perfluorinated sulfonic acid group-containing polymer or a perfluoro-based proton conductive polymer may be used.

In addition, specific examples of the hydrocarbon-based polymer are not particularly limited, for example, sulfonated polysulfone copolymer, sulfonated poly (ether-ketone) Type polymer, sulfonated polyether ether ketone type polymer, polyimide type polymer, polystyrene type polymer, polysulfone type polymer, clay-sulfonated polysulfone nanocomposite or two or more kinds thereof can be used.

The silver conductive polymer included in the electrolyte membrane and the ion conductive polymer included in the radical protective layer or the insulating layer of the embodiment may be the same material or different materials.

More specific examples include Aquivion® membranes.

Two electrodes may be included on both surfaces of the electrolyte membrane. The two electrodes (anode and cathode) may be formed on both surfaces of the electrolyte membrane, respectively, and serve as a hydrogen electrode or an air electrode. At least one of the two electrodes may include the fuel cell electrode of the embodiment. That is, only one of the two electrodes may be the fuel cell electrode of the embodiment, or both electrodes may be the fuel cell electrode of the embodiment.

Specifically, in the case of using the fuel cell electrode of the embodiment, as shown in FIG. 4, an insulating layer 2 and a radical protective layer 3 are disposed between the electrode catalyst charge 5 and the electrolyte membrane 4. It is desirable to position.

The membrane-electrode assembly may further include a gas diffusion layer. The gas diffusion layer serves to support the electrode catalyst layer included in the electrode and to improve reaction efficiency by diffusing the reaction gas into the electrode catalyst layer. Examples of the gas diffusion layer may include carbon paper or carbon cloth, and preferably water repellent treated carbon paper or carbon cloth with a fluorine resin such as polytetrafluoroethylene. The water diffusion treated gas diffusion layer can prevent the performance of the gas diffusion layer from being deteriorated by water generated when the fuel cell is driven.

In addition, a microporous layer may be further included between the electrode catalyst layer and the gas diffusion layer to further increase the diffusion effect of the gas. The microporous layer may be prepared by coating a composition containing a conductive material such as carbon powder, carbon black, activated carbon, acetylene black, a binder such as polytetrafluorofluoroethylene, and an ion conductive polymer. In addition, the membrane-electrode assembly may further include a sub-gasket. The sub-gasket protects the electrode and the electrolyte membrane and ensures easy handling on assembly of the fuel cell, and may be bonded to both edge regions of the electrode or the electrolyte membrane. Although the specific example of the said sub-gasket is not largely limited, For example, polymeric films, such as polyethylene (PE) and polyethylene naphthalate (PEN), can be used.

Meanwhile, an example of a method of manufacturing the membrane-electrode assembly is not particularly limited. For example, a method of inserting an electrolyte membrane between two electrodes (the anode and the cathode) and pressing the electrode by pressing or hot pressing may be used. have. At this time, the press compression method may be performed under a pressure of 0 to 2000 psi, a temperature of 50 to 300 ^° C, and a moving speed of 0.1 to 3 m / min. The hot pressing may be performed at a pressure of 500 to 2000 psi, a temperature of 50 to 300 ^° C., and a pressurization time of 1 to 60 minutes. On the other hand, according to another embodiment of the invention, a fuel cell comprising the fuel cell membrane-electrode assembly is provided.

Specifically, the fuel cell may include a fuel cell membrane-electrode assembly. The number of the membrane-electrode assemblies is not limited, and may include a single or a plurality.

In addition, the fuel cell may include a power generation unit in which a separator is added to both surfaces of the membrane-electrode assembly. The separator is attached to both sides of the membrane-electrode assembly, and the separator attached to the anode is called an anode separator and the separator attached to the cathode is called a cathode separator. The anode separator has a flow path for supplying fuel to the anode, and serves as an electron conductor for transferring electrons generated from the anode to an external circuit or an adjacent unit cell. The cathode separator has a flow path for supplying an oxidant to the cathode, and serves as an electron conductor for transferring electrons supplied from an external circuit or an adjacent unit cell to the cathode.

In addition, the fuel cell may further include at least one selected from the group consisting of a reformer, a fuel tank, and a fuel pump. The reformer, fuel tank, lead Fuel pumps can be used without limitation as are well known in the fuel cell art.

The fuel cell may be a direct methanol fuel cell. In addition, the configuration and output of the fuel cell may be designed according to the purpose thereof. Specifically, for example, the fuel cell may be a vehicle fuel cell. The vehicle may include a vehicle for all purposes, such as a vehicle for transportation such as an automobile, a truck, a vehicle for other uses such as an excavator, a forklift, and the like. More specifically, it can be used in fuel cell systems in an environment where repetitive residuals are required to be changed in a short time, such as on / off or sudden start of an automobile.

【Effects of the Invention】

According to the present invention, a membrane-electrode assembly and a fuel cell capable of achieving stable performance by using a fuel cell electrolyte membrane, a fuel cell electrode, the electrolyte membrane or an electrode having excellent durability by effectively removing radicals generated by a battery driver. May be provided.

[Brief Description of Drawings]

FIG. 1 schematically shows the structure of an electrolyte membrane for a fuel cell prepared in Example 1. FIG.

FIG. 2 schematically shows the structure of a membrane-electrode composite for a fuel cell prepared in Example 1. FIG.

3 schematically shows the structure of an electrode for a fuel cell prepared in Example 2. FIG.

Figure 4 schematically shows the structure of the membrane-electrode composite for a fuel cell prepared in Example 2.

[Specific contents for carrying out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

EXAMPLES Preparation of Membrane-Electrode Composites

Example 1 a) Preparation of radical protective layer coating solution

Distilled water, isopropyl alcohol and 1-propyl alcohol were added to a 3.25 g (5% dispersion) Aquivion® ionomer di spersion solution containing 0.195 g of Palarch Black in a volume ratio of 1: 1. Ultrasonic vibration agitation was performed to prepare a radical protective layer coating solution.

b) Preparation of insulating layer coating solution

Distilled water, isopropyl alcohol, and 1-propyl alcohol were added to a 12.6 g (24% aqueous solution) of Aquivion® ionomer di spersion solution in a volume ratio of 1: 1: 1, followed by ultrasonic vibration agitation to insulate the ionomer. The solution was prepared. c) production of radical protective layers and insulating layers

After fixing the fluorine-based reinforcing membrane (Aquivion® membrane) to a 60 ^° C dry plate, the radical protective layer was coated by spraying the radical protective layer coating solution on the fluorine-based reinforcing film using a compression spray.

In addition, an insulating layer was prepared by spraying the insulating layer coating solution on the radical protective layer using a compression spray. Thereafter, the resultant was dried for 12 hours in an oven at 80 ^° C., and heat-treated at 180 ^° C. to obtain a radical protective layer having a thickness of 1000 nm and a fluorine-based reinforcement layer coated with an insulating insect having a thickness of 800 nm.

d) preparation of membrane-electrode complexes;

After cutting two sheets of an electrode catalyst layer coated film into 25αιί, and inserting a fluorine-based reinforcing layer coated with a radical protective layer and an insulating layer therebetween, the films were thermally compressed using a press. Subsequently, 25 αιί sized sub-gaskets were overlaid and a membrane-electrode composite was prepared by thermal compression using a press. Conduct female 12

a) Preparation of Radial Protective Layer Coating Solution

Distilled water, isopropyl alcohol and 1-propyl alcohol in a volume ratio of 1: 25: 1 in a solution of 3.25 g (5% dispersion) of Aquivion® ionomer di spersion D83-24B containing 0.19 palladium black After the addition, ultrasonic wave stirring was performed to prepare a radical protective layer coating solution. b) Preparation of insulating layer coating solution

Distilled water, isopropyl alcohol, and 1-propyl alcohol were added to a solution of 12.6 g (24% aqueous solution of aqueous solution) Aquivion® ionomer di spersion D83-24B in a volume ratio of 1: 1: 1, followed by ultrasonic vibration agitation. A layer ionomer coating solution was prepared.

c) production of radical protective layers and insulating layers

After fixing the electrode to a 60 ^° C dry tube, the insulating layer coating solution was sprayed on the electrode by using a compression spray to coat the insulating layer.

In addition, by spraying the radical protective layer coating solution using a compression spray on the insulating worms to prepare a radical protective layer. Thereafter, the resultant was dried for 12 hours in an oven at 80 ° C. and heat-treated in an oven at 180 ^° C. to obtain an electrode coated with an insulating layer having a thickness of 800 nm and a radical protective layer having a thickness of 1000 nm.

d) Preparation of membrane-electrode composite

After inserting a fluorine-based reinforcing layer (Aquivion® membrane) between the electrode and the other electrode is coated with the radical protective layer and the insulating layer, was pressed by using a press. At this time, the fluorine-based reinforcing film was inserted at a position between the radical protective layer and the other electrode of the electrode coated with the radical protective layer and the insulating layer. The 25-ciif-sized sub-gaskets were overlaid and the membrane-electrode composite was prepared by thermal compression using a press.

Comparative Example: Fabrication of Membrane Electrode Composite

compare

The film coated with the electrode catalyst layer was 25αη ^! After cutting two sheets with a fluorine-based reinforcing film (Aquivion® membrane) in which no radical protective layer and insulating layer were formed therebetween, and thermally crimped by using a press, the above Example In the same manner as in 1, a membrane-electrode composite was prepared. Comparative Example 2

After cutting two sheets of a film coated with an electrode catalyst layer to 25 cm ', only a radical protective layer is formed between them, and a fluorine-based reinforcing film having no insulating layer formed thereon (Aquivion® membrane) was inserted, and a membrane-electrode composite was prepared in the same manner as in Example 1, except that was pressed by using a press. Comparison ^ 13

A membrane-electrode composite was prepared in the same manner as in Example 2, except that an electrode without a radical protective layer and an insulating layer was used. Compare ^] 4

A membrane-electrode composite was prepared in the same manner as in Example 2, except that only a radical protective layer was formed and an electrode without an insulating layer was used.

<Experimental example: Performance measurement of the membrane-electrode composite obtained by the Example and the comparative example Experimental example 1: Durability evaluation of battery

In order to test the performance of the unit cell including the membrane-electrode composite obtained in Examples and Comparative Examples, the unit cells were disposed by arranging gas diffusion charges (SGL 10BB, SGL Carbon Group) adjacent to both sides of the membrane-electrode composite. It was assembled.

The cell temperature is 80 ^° C, the relative humidity of the hydrogen electrode and the air electrode is 50%, the atmospheric pressure and the pressure difference are maintained at 0 psig, and the flow rate is 0.11 L / min, 0.34 L / min at the hydrogen electrode and the air electrode, respectively, and the open circuit voltage The change of (Open Circuit Voltage, 0CV) was measured for 300 hours in real time. And after 150 hours, the cell temperature is 65 ^° C, 100% relative humidity after the activation for 3 hours to evaluate the current-voltage and 0CV, the performance reduction rate was confirmed, the results are shown in Table 1 below.

Table 1

Evaluation of Battery Durability Using Membrane-electrode Composites of Examples and Comparative Examples

Category Initial IV 0CV Initial IV Performance IV 0CV Reduction Rate Performance Reduction Rate

(V) (mA / cii) (uV / h) (uV / h @ 1.2A / cm ') Example 1 1.013 1200 32 51 Example 2 1.005 1210 41 53 Comparative Example 1 0.975 1250 143 183 Comparative Example 2 0.992 1220 92 103 Comparative Example 3 0.975 1250 143 187 Comparative Example 4 0.993 1200 95 100

As shown in Table 1, the 0CV reduction rate of Example 1 in which both the radical protective layer and the insulating layer were secured was 32 uV / h, and 143 uV / h of Comparative Example 1 in which neither the radical protective layer nor the insulating layer was secured. And it can be seen that very low compared to 92 uV / h of Comparative Example 2 secured only a radical protective layer.

In addition, the 0CV reduction rate of Example 2 in which both the radical protective layer and the insulating layer were secured was 41 uV / h. It can be seen that it is very low compared with 95 uV / h of Comparative Example 4 secured.

The membrane-electrode composite with the insulating layer secured 0CV durability as it can exert the maximum radical removal effect by blocking the electrical contact between the catalyst of the electrode layer and the protective layer when compared with the membrane-electrode composite without the insulating layer. It was confirmed that this could be improved.

In addition, in Table 1, the performance reduction rate of Example 1 in which both the radical protective layer and the insulating layer are secured is 51 uV / h @ 1.2 A / cuf, and in Comparative Example 1 in which neither the radical protective layer nor the insulating layer is secured. 183 uV / h @ 1.2A / ciu ^! And it can be seen that very low compared to 103 uV / h @ 1.2A / cuf of Comparative Example 2 secured only a radical protective layer. In addition, the performance reduction rate of Example 2 in which both the radical protective layer and the insulating layer were secured was 53 uV / h @ 1.2 A / cuf, and 187 uV / h of Comparative Example 3 in which neither the radical protective layer nor the insulating layer was secured. @ 1.2 A / aif and the radical protective layer only 100 uV / h @ 1.2 A / cuf of Comparative Example 4 can be confirmed that the very low.

In the film-electrode composites of Comparative Examples 1 and 3 in which the radical protective layer does not exist, it was confirmed that the reduction rate of 0CV performance was greatly increased due to the increase of the film-electrode composite resistance caused by radicals.

This ensures that both the radical protector and the insulation layer are expanded in a dry / humidified environment. The membrane-electrode complexes were found to increase the physical and chemical radical resistance of the electrolyte membranes compared to the conventional membrane-electrode complexes, thereby improving 0CV performance and durability.

[Explanation of code]

1-Electrocatalyst layer

2-insulation layer

3-radical protection layer

4-ion conductive membrane

5-Electrocatalyst layer

Claims

[Claim]

[Claim 1]

Ion conductive membranes;

A radical protective layer formed on at least one surface of the ion conductive membrane and including at least one metal and an ion conductive polymer; And

Is formed on the radical protective layer, the insulating layer containing an ion conductive polymer; including,

The metal contained in the radical protective layer is dispersed in a state in which the ion conductive polymer in contact with the surface, the electrolyte membrane for a fuel cell.

[Claim 2]

The method of claim 1,

The metal contained in the radical protection layer is in contact with the ion conductive polymer 50% or more of the total surface area, the fuel cell electrolyte membrane.

[Claim 3]

The method of claim 1,

1 to 20 parts by weight of at least one metal based on 100 parts by weight of the ion conductive polymer in the radical protection layer.

[Claim 4]

The method of claim 1,

Wherein said at least one metal comprises a parallax or an alloy comprising a parallax.

[Claim 5]

The method of claim 4,

The alloy containing palladium includes one or more metals selected from the group consisting of palladium and metal elements belonging to Groups 3 to 13 of the periodic table, Electrolyte membrane for fuel cell.

[Claim 6]

The method of claim 1,

The ratio of the radical protective layer thickness to the thickness of the insulating layer is 1 to 10, the electrolyte membrane for a fuel cell.

[Claim 7]

The method of claim 1,

The conductive polymer contained in the insulating charge includes a fluorine-based polymer or a hydrocarbon-based polymer, an electrolyte membrane for a fuel cell.

[Claim 8]

The method of claim 1

The ion conductive membrane comprises a conductive polymer, the electrolyte membrane for a fuel cell.

[Claim 9]

An electrode catalyst layer;

An insulating layer formed on at least one surface of the electrode catalyst charge and including a conductive polymer; And

A radical protective layer formed on the insulating layer and comprising at least one metal and an ion conductive polymer;

The metal contained in the radical protective layer is dispersed in a state in which the ion conductive polymer in contact with the surface, the fuel cell electrode.

[Claim 10]

The method of claim 9,

The metal contained in the radical protective layer is in contact with a conductive polymer followed by more than 50% of the total surface area, the fuel cell electrode. [Claim 111]

The method of claim 9,

1 to 20 parts by weight of at least one metal based on 100 parts by weight of the ion conductive polymer in the radical protection layer, the fuel cell electrode.

[Claim 12]

The method according to claim 9,

Wherein said at least one metal comprises palladium or an alloy comprising a palladium.

[Claim 13]

The method of claim 12,

The alloy including the parallax comprises at least one metal selected from the group consisting of palladium and metal elements belonging to Groups 3 to 13 of the periodic table, the electrode for fuel cells.

[Claim 14]

The method of claim 9,

The ratio of the radical protective layer thickness to the insulating layer thickness is 1 to 10, the fuel cell electrode.

[Claim 15]

The method of claim 9,

The conductive polymer contained in the insulating layer includes a fluorine-based polymer or a hydrocarbon-based polymer, an electrode for a fuel cell.

[Claim 16]

An electrolyte membrane for a fuel cell of claim 1; And the electrolyte membrane for the fuel cell Membrane-electrode assembly for fuel cell, comprising an electrode catalyst layer provided on both sides.

[Claim 17]

An electrolyte membrane and two electrodes provided on both sides of the electrolyte membrane;

At least one of the two electrodes comprises the fuel cell electrode of claim 9, wherein the membrane-electrode assembly for fuel cell.

[Claim 18]

A fuel cell comprising the fuel cell membrane-electrode assembly of claim 16 or 17.