KR20200013993A - Membrane electrode assembly, fuel cell comprising the same and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a membrane-electrode assembly, a fuel cell and a manufacturing method of the membrane-electrode assembly. The membrane-electrode assembly comprises an anode catalyst layer; a cathode catalyst layer; and a polymer electrolyte membrane. The durability of battery performance can be increased under low-humidity conditions and high-humidity conditions.

Description

Method for manufacturing membrane-electrode assembly, fuel cell and membrane-electrode assembly {MEMBRANE ELECTRODE ASSEMBLY, FUEL CELL COMPRISING THE SAME AND MANUFACTURING METHOD THEREOF}

The present specification relates to a method of manufacturing a membrane-electrode assembly, a fuel cell and a membrane-electrode assembly.

Recently, as the depletion of existing energy resources such as oil and coal is predicted, interest in energy that can replace them is increasing. As one of such alternative energy, fuel cells have been particularly noticed for their advantages such as high efficiency, no pollutants such as NOx and SOx, and abundant fuel used.

A fuel cell is a power generation system that converts chemical reaction energy of fuel and oxidant into electrical energy. Hydrogen, hydrocarbons such as methanol, butane, and the like are typically used as fuel, and oxygen is used as the oxidant.

Fuel cells include polymer electrolyte fuel cells (PEMFC), direct methanol fuel cells (DMFC), phosphoric acid fuel cells (PAFC), alkaline fuel cells (AFC), molten carbonate fuel cells (MCFC), and solid oxide fuels. Batteries (SOFC) and the like.

The polymer electrolyte fuel cell has high hydrogen ion conductivity at high humidity and high performance, but has low performance at low humidity. This occurs because the membrane's hydrogen ion conductivity is reduced and water management in the membrane-electrode assembly is poor.

In particular, the use of hydrocarbon-based membranes increases the performance difference between high humidification and low-humidity rather than fluorine-based membranes. This is because hydrogen ion transport channels of hydrocarbon membranes are not developed continuously in low humidity compared with fluorine series.

In order to solve this problem, there are technologies in which polyvinyl alcohol, zirconia, silica, hydrogel, etc. are mixed in the membrane or electrode, but these techniques improve the low-humidity performance but have the problem of lowering the high-humidity performance .

Republic of Korea Patent Publication No. 2003-0045324 (2003.06.11 published)

The present specification is to provide a method for manufacturing a membrane-electrode assembly, a fuel cell and a membrane-electrode assembly.

The present specification is an anode catalyst layer;

A cathode catalyst layer comprising functional particles having an average diameter of at least 1 nm and at most 1,000 nm; And

It provides a membrane-electrode assembly comprising a polymer electrolyte membrane provided between the cathode catalyst layer and the anode catalyst layer.

In addition, the present disclosure provides a fuel cell including the membrane-electrode assembly.

In addition, the present specification comprises the steps of preparing an anode catalyst layer;

Forming a cathode catalyst layer using a catalyst ink comprising functional particles; And

It provides a method for producing the membrane-electrode assembly comprising the step of providing a polymer electrolyte membrane between the anode catalyst layer and the cathode catalyst layer.

The membrane-electrode assembly according to the present specification has an advantage of increasing durability of battery performance under low humidity conditions and high humidity conditions.

1 is a schematic diagram showing the principle of electricity generation of a fuel cell.
2 is a view schematically showing the structure of a membrane-electrode assembly.
3 is a view schematically showing an embodiment of a fuel cell.
4 is a view showing the performance in the constant current driving of the comparative example and the embodiment of the invention.

Hereinafter, this specification is demonstrated in detail.

In this specification, "or" means the meaning of "and / or" when it includes any or all of them listed, unless otherwise defined.

In the present specification, "layer" means covering 70% or more of the area in which the layer exists. It means preferably covering at least 75%, more preferably at least 80%.

The present specification is an anode catalyst layer;

A cathode catalyst layer comprising functional particles having an average diameter of at least 1 nm and at most 1,000 nm; And

It provides a membrane-electrode assembly comprising a polymer electrolyte membrane provided between the cathode catalyst layer and the anode catalyst layer.

The cathode catalyst layer of the membrane-electrode assembly includes functional particles having a specific range of average diameters, thereby increasing durability of battery performance under low humidity conditions and high humidity conditions. In addition, the above-described effects can be increased by changing the type of the functional particles or by surface treating the surface of the functional particles. Comparing Comparative Example 1 and Examples 1 and 2, the moisture-containing retention ability of the functional particles in the case of containing the functional particles (Examples 1 and 2) compared to the case of not containing the functional particles (Comparative Example 1). The excellent performance of the membrane electrode assembly (membrane electrode assembly (MEA)) can be confirmed.

In the present specification, the functional particles may be referred to as "moisture particles" having a moisture function.

In one embodiment of the present specification, the anode catalyst layer and the cathode catalyst layer may each include a catalyst and an ionomer.

In one embodiment of the present specification, the catalyst is not limited in kind as long as it can serve as a catalyst in a fuel cell, but may include one of platinum, transition metal and platinum-transition metal alloy.

Here, the transition metal is a group 3 to 11 elements in the periodic table, and may be, for example, any one of ruthenium, osmium, palladium, molybdenum and rhodium.

Specifically, the catalyst may be used selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-molybdenum alloy and platinum-rhodium alloy, but is not limited thereto. Does not.

The catalysts can be used on their own as well as supported on a carbon-based carrier.

Examples of the carbon-based carrier include graphite (graphite), carbon black, acetylene black, denka black, canyon black, activated carbon, mesoporous carbon, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon nanorings, carbon nanowires, One or a mixture of two or more selected from the group consisting of fullerene (C60) and Super P black may be a preferred example.

The ionomer plays a role of providing a passage for ions generated by the reaction between a fuel such as hydrogen or methanol and a catalyst to the electrolyte membrane.

The ionomer may be a polymer having a cation exchange group selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof in the side chain.

The ionomer may be a hydrocarbon-based polymer, a partially fluorine-based polymer or a fluorine-based polymer.

The ionomer may be a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a polyether ketone polymer, a polyether It may include one or more hydrogen ion conductive polymer selected from ether ketone-based polymer, or polyphenylquinoxaline-based polymer.

The average thickness of the anode catalyst layer and the cathode catalyst layer may be each independently 5㎛ 15㎛. If the thickness exceeds 15 μm, gas permeation may be a problem, and performance may be degraded. If the thickness is less than 5 μm, the gas may directly contact the electrolyte membrane, causing short-circuit. That is, when the numerical range is satisfied, the gas permeability may be improved, and a short circuit phenomenon may be prevented.

In one embodiment of the present specification, the cathode catalyst layer includes functional particles having an average diameter of 1 nm or more and 1,000 nm or less.

In one embodiment of the present specification, the average diameter of the functional particles may be 1 nm or more and 1,000 nm or less, preferably 10 nm or more and 800 nm or less, more preferably 10 nm or more and 500 nm or less. When the numerical range is satisfied, the dispersibility of the functional particles is improved, and the functional particles catch the water generated at the cathode so as not to be discharged to the outside. The performance is improved.

The average diameter of the functional particles can be measured by a method generally used in the art, for example, by the Dynamic Light Scattering (DLS) method.

The "average diameter" of the functional particles may be a value derived by dividing a value of measuring the diameter of any one functional particle by two or more times. Alternatively, after deriving the average diameter of the two or more functional particles, respectively, it may be a final derived value divided by the number of functional particles.

The average diameter of the functional particles can be changed by changing the type of dispersant for surface treatment of the functional particles or by adjusting the surface treatment time, dispersant concentration during surface treatment, microwave treatment, and the like, which will be described later.

Since the proton ion conductivity of the electrolyte membrane is an important factor in the performance of the membrane-electrode assembly, and it is greatly influenced by the relative humidity, the relative humidity changes in the electrolyte membrane proton ion conductivity when measuring the electrolyte membrane proton ion conductivity according to the relative humidity. Based on this large interval.

Specifically, in the low humidity conditions, the humidity condition means a relative humidity measured at a battery temperature of 70 ° C., in the present specification, the low humidity conditions are more than 40% and 65% or less, and the ultra low humidity conditions are relative humidity. It means the case of 0% or more and 40% or less. In Experimental Example 1 described later, the relative humidity of the low-humidity condition was set to 50%, and the relative humidity of the ultra-low humidification condition was set to 32%.

The reactant gas of the fuel cell passes through a bubbler that heats a metal container containing water, so that the temperature of the gas line is about 10 ° C. to 30 ° C. above the setting temperature of the humidifier so that the unit cell does not condense in the gas line. Adjust it high. In this case, the relative humidity of the unit cell is calculated according to the relative humidity conversion equation based on the temperature of the water in the humidifier through which the reactant gas, that is, the dew point temperature, is measured.

In one embodiment of the present specification, the functional particles are 1 or selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), gibbsite (Al (OH) ₃ ), and boehmite (γ-AlO (OH)). It may be two or more. It may preferably comprise boehmite particles. The boehmite particles may use the Sasol DISPAL series.

In one embodiment of the present specification, the functional particles are surface treated with one or two or more dispersants selected from the group consisting of an aqueous dispersant, an organic dispersant, an anionic dispersant, a cationic dispersant, an amphoteric dispersant, and a block copolymer on the particle surface. It may comprise a surface treatment layer.

In an exemplary embodiment of the present specification, a kind of the dispersant includes BYKJET 9151, DISPERBYK 182, DISPERBYK 190, DISPERBYK194, DISPERBYK 2012, Pluronic P123, Pluronic F127, Pluronic F68, or Pluronic L92, and preferably Pluronic L92 may be used. Can be.

In the case of the surface treatment, the size of the functional particles when the surface treatment is sufficiently small, so that the hydroxyl group (-OH) groups on the surface of the functional particles catch the water generated in the cathode from being discharged to the outside, Under the conditions, the moisture concentration in the unit cell can be increased.

In one embodiment of the present specification, the thickness of the surface treatment layer may be 1 nm or more and 200 nm or less, 10 nm or more and 180 nm or less, preferably 20 nm or more and 160 nm or less. When the numerical range is satisfied, the surface treatment layer sufficiently covers the surface of the functional particles, whereby the effect of improving the performance in the low-humidity conditions described above can be increased.

In one embodiment of the present specification, the cathode catalyst layer includes a catalyst, and the content of the functional particles is 0.01 wt% or more and 7 wt% or less, 0.01 wt% or more and 5 wt% or less, based on the total weight of the catalyst, 1 wt% or more and 3 wt% or less, or 2 wt% or more and 3 wt% or less. When the numerical range is satisfied, the content of the functional particles in the catalyst layer is sufficiently secured, so that a high current density can be obtained even under low humidity conditions.

In one embodiment of the present specification, the volume of the functional particles may be 0.1 vol% or more and 10 vol% or less, 0.2 vol% or more and 5 vol%, or 0.3 vol% or more and 3 vol% or less based on the volume of the cathode catalyst layer. have. When the numerical range is satisfied, the content of the functional particles in the catalyst layer is sufficiently secured, so that a high current density can be obtained even under low humidity conditions.

In one embodiment of the present specification, the average diameter of the functional particles may have a profile in the thickness direction of the cathode catalyst layer.

In one embodiment of the present specification, the membrane-electrode assembly includes a cathode gas diffusion layer provided on an opposite surface of the cathode catalyst layer on which the polymer electrolyte membrane is provided; And an anode gas diffusion layer provided on an opposite side of the surface of the anode catalyst layer on which the polymer electrolyte membrane is provided.

In the present specification, the gas diffusion layer may mean the cathode gas diffusion layer and the anode gas diffusion layer.

In an exemplary embodiment of the present specification, the anode gas diffusion layer and the cathode gas diffusion layer are provided on one surface of the catalyst layer, respectively, and serve as a current conductor, and become a passage for the reaction gas and water, and have a porous structure. Therefore, the gas diffusion layer may include a conductive substrate.

In one embodiment of the present specification, the conductive substrate may be a conventional material known in the art, for example, carbon paper, carbon cloth, or carbon felt. ) May be preferably used, but is not limited thereto.

In one embodiment of the present specification, the average thickness of the gas diffusion layer may be 100 μm or more and 500 μm or less. In this case, there is an advantage of minimizing the reactant gas transfer resistance through the gas diffusion layer and an optimum state in view of the proper moisture content in the gas diffusion layer.

In one embodiment of the present specification, the polymer electrolyte membrane is provided between the cathode catalyst layer and the anode catalyst layer, the polymer included in the polymer electrolyte membrane may be an ion conductive polymer.

The ion conductive polymer may be a hydrocarbon-based polymer, a partial fluorine-based polymer or a fluorine-based polymer. Specifically, the polymer electrolyte membrane may be a hydrocarbon-based polymer electrolyte membrane or a fluorine-based polymer electrolyte membrane, preferably, the electrolyte membrane may be a hydrocarbon-based polymer electrolyte membrane.

The hydrocarbon-based polymer may be a hydrocarbon-based sulfonated polymer without a fluorine group, on the contrary, the fluorine-based polymer may be a sulfonated polymer saturated with a fluorine group, and the partial fluorine-based polymer may not be saturated with a fluorine group. Sulfonated polymer.

The ion conductive polymer may be a perfluorosulfonic acid polymer, a hydrocarbon polymer, an aromatic sulfone polymer, an aromatic ketone polymer, a polybenzimidazole polymer, a polystyrene polymer, a polyester polymer, a polyimide polymer, polyvinylidene fluoride Ride type polymer, polyether sulfone type polymer, polyphenylene sulfide type polymer, polyphenylene oxide type polymer, polyphosphazene type polymer, polyethylene naphthalate type polymer, polyester type polymer, doped polybenzimidazole type polymer, It may be one or two or more polymers selected from the group consisting of a polyether ketone polymer, a polyether ether ketone polymer, a polyphenylquinoxaline polymer, a polysulfone polymer, a polypyrrole polymer and a polyaniline polymer. The polymer may be used by sulfonated and may be a single copolymer, an alternating copolymer, a random copolymer, a block copolymer, a multiblock copolymer or a graft copolymer, but is not limited thereto.

In one embodiment of the present specification, the polymer electrolyte membrane is preferably a hydrocarbon-based polymer, and may be a hydrocarbon-based polymer that is a block copolymer including the hydrophilic block and the hydrophobic block.

In one embodiment of the present specification, the average thickness of the polymer electrolyte membrane may be 1 μm or more and 100 μm or less.

The present specification provides a fuel cell including the membrane-electrode assembly.

FIG. 1 schematically illustrates the principle of electricity generation of a fuel cell. In the fuel cell, the most basic unit for generating electricity is a membrane-electrode assembly (MEA), which is an electrolyte membrane (M) and the electrolyte membrane (M). It is composed of an anode (A) and a cathode (C) formed on both sides of. Referring to FIG. 1, which illustrates the electricity generation principle of a fuel cell, in the anode A, an oxidation reaction of a fuel F such as hydrogen or a hydrocarbon such as methanol and butane occurs to generate hydrogen ions (H ⁺ ) and electrons (e ⁻ ). Is generated, and hydrogen ions move to the cathode C through the electrolyte membrane M. The cathode C reacts with hydrogen ions transferred through the electrolyte membrane M, an oxidizing agent O such as oxygen, and electrons to generate water W. This reaction causes the movement of electrons in the external circuit.

As shown in FIG. 2, the membrane-electrode assembly may include an electrolyte membrane 10 and a cathode 50 and an anode 51 positioned to face each other with the electrolyte membrane 10 interposed therebetween. In detail, the cathode includes a cathode catalyst layer 20 and a cathode gas diffusion layer 30 sequentially provided from the electrolyte membrane 10, and the anode includes an anode catalyst layer 21 and an anode sequentially provided from the electrolyte membrane 10. It may include a gas diffusion layer (31).

3 schematically illustrates the structure of a fuel cell, in which the fuel cell includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80.

The fuel cell stack 60 includes one or two or more membrane-electrode assemblies described above, and includes two or more separators interposed therebetween when two or more membrane-electrode assemblies are included. The separator prevents the membrane-electrode assemblies from being electrically connected and delivers fuel and oxidant supplied from the outside to the membrane-electrode assembly.

The oxidant supply unit 70 serves to supply the oxidant to the fuel cell stack 60. Oxygen is typically used as the oxidizing agent, and may be used by injecting oxygen or air into a pump.

The fuel supply unit 80 supplies fuel to the fuel cell stack 60, and a fuel tank 81 storing fuel and a pump 82 supplying fuel stored in the fuel tank 81 to the stack 60. It can be composed of). As fuel, hydrogen or hydrocarbon fuel in gas or liquid state may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

The present specification comprises the steps of preparing an anode catalyst layer;

Forming a cathode catalyst layer using a catalyst ink comprising functional particles; And

It provides a method for producing a membrane-electrode assembly comprising the step of providing a polymer electrolyte membrane between the anode catalyst layer and the cathode catalyst layer.

In one embodiment of the present specification, providing a polymer electrolyte membrane between the anode catalyst layer and the cathode catalyst layer comprises: forming a cathode catalyst layer on one surface of the polymer electrolyte membrane; And forming an anode catalyst layer on the other surface of the polymer electrolyte membrane.

In one embodiment of the present specification, the polymer electrolyte membrane is a polymer electrolyte membrane composition for forming a pure membrane, or impregnated with a polymer electrolyte membrane composition on a porous substrate to form a reinforcing membrane, or a composite comprising at least one pure membrane and at least one reinforcing membrane A film can be formed.

In one embodiment of the present specification, the step of providing a polymer electrolyte membrane between the anode catalyst layer and the cathode catalyst layer is directly coated on the polymer electrolyte membrane, or a catalyst layer formed on a releasable substrate, and then heat on the polymer electrolyte membrane. The catalyst layer may be introduced by forming the catalyst layer by compressing and removing the releasable substrate or by coating the gas diffusion layer to form a catalyst layer and the gas diffusion layer having the catalyst layer and the polymer electrolyte membrane.

At this time, the coating method of the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, inkjet coating, die coating or spin coating may be used.

In an exemplary embodiment of the present specification, the surface of the functional particles is selected from the group consisting of an aqueous dispersant, an organic dispersant, an anionic dispersant, a cationic dispersant, an amphoteric dispersant and a block copolymer before the forming of the cathode catalyst layer. Or surface treatment with two or more dispersants. The description of the dispersant is as described above.

Surface treatment of the functional particles may include dispersing the functional particles in a solvent; Surface treating the surface of the functional particles with a dispersant; Washing the surface treated functional particles; And drying.

Surface treatment of the surface of the functional particles with a dispersant may be a reaction of the -OH functional group of the functional particles with the hydrophilic portion and the functional group of the dispersant. For example, the molecular formula of Pluronic used as a dispersant is shown in Formula 1.

[Formula 1]

There are several types depending on molecular weight and chain length. In the case of P123, x = 20, y = 70, x = 20, and in the case of L92, x = 15, y = 37, x = 15 and the molecular weight is smaller than P123.

Polyethylene groups on either side of the formula are hydrophilic blocks, and polypropylene groups in the middle are hydrophobic blocks. When the dispersant and the functional particles are mixed, the polyethylene portion, which is the hydrophilic portion of the dispersant, is dispersed while adsorbing with the -OH group of the functional particles. The particle size may vary depending on the type and concentration of the dispersant.

In one embodiment of the present specification, the surface treatment of the functional particles may be performed for 10 minutes to 2 hours, preferably 30 minutes to 2 hours.

In one embodiment of the present specification, the content of the dispersant is 15 wt% to 300 wt%, preferably 20 wt% to 250 wt%, more preferably 30 wt% to 200 wt%, based on the total weight of the catalyst. Can be. When the numerical range is satisfied, the dispersibility of the functional particles is improved.

In one embodiment of the present specification, surface treating the functional particles may further include microwave treating.

Hereinafter, the present specification will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the present specification, but not to limit the present specification.

EXAMPLE

Example 1

3M 825 fluorine ionomer was mixed with 1-propanol and glycerol. Thereafter, boehmite (1 wt% of the total weight of the catalyst) surface-treated with Pluronic L92 was added to the mixed solution, followed by ultrasonic dispersion for 1 hour. After keeping at low temperature at 2 ° C. for 30 minutes, the catalyst (Pt 10V50E Tanaka Co., Ltd.) supported by platinum (Pt) on carbon black was added to the solution. The mass ratio (I / C) of ionomer (I, Ionomer) and carbon (C, Carbon) ) Was added at 0.6. The electrode slurry was completed after ultrasonic dispersion for 1 hour. The prepared electrode slurry was cast on a PTFE (Polytetrafluoroethylene) film using a doctor blade, and then dried at 35 ° C. for 30 minutes and at 140 ° C. for 30 minutes to finally prepare a catalyst layer.

Example 2

An electrode catalyst layer was prepared in the same manner as in Example 1 except that the content of boehmite was added at 3 wt% based on the catalyst.

Comparative Example 1

Except not adding boehmite, an electrode catalyst layer was prepared in the same manner as in Example 1.

Experimental Example 1

In order to manufacture a membrane-electrode assembly (MEA), a sulfonated polyarylene ether ketone copolymer polymer membrane was used as the ion conductive polymer membrane and a Pt / C catalyst layer having no boehmite mixed as the anode. The catalyst layers of Examples 1, 2 and Comparative Example 1 were used as cathodes, and the membrane-electrode assembly was prepared by thermally compressing the sulfonated polyarylene ether ketone membrane between the anodes.

The performance of the unit cells of Examples 1, 2 and Comparative Example 1 was used with Nara Cell's PEMFC station equipment and IV performance was measured in the constant current mode. Specifically, the 0 to 1,500 mA / cm ² was measured by scanning the range to 100 mA / cm ² steps, compared the performance of mA / cm ² in value of 0.6V. The unit cell temperature was measured at 70 ° C., relative humidity at 50% and 32% RH. The results are shown in Table 1 below.

In addition, 800 mA / cm while injecting fuel at 100% RH anode and 0% RH cathode to investigate the effect of boehmite moisture infiltration capacity on low-humidity conditions for unit cells of Examples 1, 2 and Comparative Example 1 The voltage change of the unit cell was observed under the constant current condition of ² , and the results are shown in FIG. 4.

As shown in Table 1 below, it can be seen that the moisture retention characteristics of Examples 1 and 2 were higher than those of Comparative Example 1, and among them, the MEA performance prepared in Example 2 was maintained for the longest time.

MEA Humidity conditions Performance (@ 0.6V) (mA / cm ² ) Comparative Example 1 50% 915.8 32% 531.2 Example 1 50% 930.7 32% 585.8 Example 2 50% 1042.3 32% 637.6

10: electrolyte membrane
20: cathode catalyst layer
21: anode catalyst layer
30: cathode gas diffusion layer
31: anode gas diffusion layer
50: cathode
51: anode
60: stack
70: oxidant supply
80: fuel supply
81: fuel tank
82: pump

Claims (9)

Anode catalyst layer;
A cathode catalyst layer comprising functional particles having an average diameter of at least 1 nm and at most 1,000 nm; And
Membrane-electrode assembly comprising a polymer electrolyte membrane provided between the cathode catalyst layer and the anode catalyst layer. The method according to claim 1, wherein the functional particles are one or two or more selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), Gibbsite (Al (OH) ₃ ) and boehmite (γ-AlO (OH)). Membrane-electrode assembly. The surface treatment layer of claim 1, wherein the functional particles are surface-treated with one or two or more dispersants selected from the group consisting of an aqueous dispersant, an organic dispersant, an anionic dispersant, a cationic dispersant, an amphoteric dispersant, and a block copolymer on the surface of the particle. Membrane-electrode assembly comprising a. The film-electrode assembly according to claim 3, wherein the thickness of the surface treatment layer is 1 nm or more and 200 nm or less. The membrane-electrode assembly of claim 1, wherein the cathode catalyst layer comprises a catalyst, and the content of the functional particles is 0.01 wt% or more and 7 wt% or less based on the total weight of the catalyst. The membrane-electrode assembly according to claim 1, wherein the volume ratio of the functional particles is 0.1 vol% or more and 10 vol% or less based on the volume of the cathode catalyst layer. A fuel cell comprising the membrane-electrode assembly of claim 1. Preparing an anode catalyst layer;
Forming a cathode catalyst layer using a catalyst ink comprising functional particles; And
The method of manufacturing a membrane-electrode assembly according to any one of claims 1 to 6, comprising providing a polymer electrolyte membrane between the anode catalyst layer and the cathode catalyst layer. The method of claim 8, wherein the surface of the functional particles before the step of forming the cathode catalyst layer is one or two or more dispersants selected from the group consisting of an aqueous dispersant, an organic dispersant, an anionic dispersant, a cationic dispersant, an amphoteric dispersant and a block copolymer The method of manufacturing a membrane-electrode assembly further comprising the step of surface treatment.

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