KR20170097415A - Membrane electrode assembly, fuel cell comprising the same and method for preparing thereof - Google Patents

Abstract

The present invention relates to a membrane electrode assembly, comprising a cathode and an anode having a gas diffusion layer and a catalyst layer, and an electrolyte membrane arranged between the anode and the cathode, a fuel cell comprising the same, and a method for manufacturing the same. The membrane electrode assembly comprises a hydrocarbon-based electrolyte membrane; a first protective film; an anode catalyst layer and a cathode catalyst layer which are arranged on both sides of the hydrocarbon-based electrolyte membrane having the first protective film; and a second protective film having the first protective film and a second through-hole. According to an embodiment of the present invention, durability of the membrane electrode assembly is increased.

Description

TECHNICAL FIELD [0001] The present invention relates to a membrane electrode assembly, a membrane electrode assembly, a fuel cell including the membrane electrode assembly, and a method of manufacturing the same. BACKGROUND ART [0002] Membrane Electrode Assemblies

The present invention relates to a cathode and an anode comprising a gas diffusion layer and a catalyst layer; And an electrolyte membrane provided between the anode and the cathode, a fuel cell including the membrane electrode assembly, and a method of manufacturing the same.

Recently, as the exhaustion 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 energies, fuel cells have attracted particular attention due to their advantages such as high efficiency, no emission of pollutants such as NOx and SOx, and abundant fuel.

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

BACKGROUND ART Fuel cells include a polymer electrolyte fuel cell (PEMFC), a direct methanol fuel cell (DMFC), a phosphoric acid fuel cell (PAFC), an alkaline fuel cell (AFC), a molten carbonate fuel cell (MCFC) And a battery (SOFC). Among them, polymer electrolyte fuel cells have been actively studied because they have high energy density and high output. Such a polymer electrolyte fuel cell differs from other fuel cells in that it uses a solid polymer electrolyte membrane instead of a liquid electrolyte.

Korean Patent Publication No. 2003-0076057

The present specification is intended to provide a membrane electrode assembly, a fuel cell including the same, and a method of manufacturing the same.

The present invention relates to a hydrocarbon-based electrolyte membrane; A first protective film provided on both surfaces of the hydrocarbon-based electrolyte membrane and having first through-holes penetrating in the thickness direction; An anode catalyst layer and a cathode catalyst layer provided on both surfaces of a hydrocarbon-based electrolyte membrane provided with the first protective film so as not to overlap with the first protective film; And a second passivation film provided on the other surface of the first protective film and the anode catalyst layer and on the other surface of the first protective film and the cathode catalyst layer to cover a part of the anode catalyst layer or the cathode catalyst layer, And a second protective film having a hole.

Further, the present specification provides a fuel cell including the membrane electrode assembly.

The present invention also relates to a method of manufacturing a fuel cell, comprising the steps of: laminating a first protective film having a first through hole penetrating in a thickness direction on both surfaces of a hydrocarbon-based electrolyte membrane; Stacking an anode catalyst layer and a cathode catalyst layer on both sides of a hydrocarbon-based electrolyte membrane provided with the first protective film so as not to overlap with the first protective film; And a second through hole penetrating in the thickness direction so as to cover a part of the anode catalyst layer or the cathode catalyst layer on one surface provided with the first protective film and the anode catalyst layer and on the other surface provided with the first protective film and the cathode catalyst layer And a step of laminating a second protective film on the surface of the membrane electrode assembly.

The membrane electrode assembly according to one embodiment of the present invention has an advantage of improving durability.

The membrane electrode assembly according to one embodiment of the present disclosure can prevent the electrolyte membrane from being directly exposed to fuel or air.

1 is a schematic view showing an electricity generation principle of a fuel cell.
2 is a schematic view showing the structure of a membrane electrode assembly for a fuel cell.
3 is a schematic view showing one embodiment of a fuel cell.
4 is a graph of RH cycle test results of Example 1-2 and Comparative Example 1. Fig.
FIG. 5 shows a case where cracks are generated at edges of the electrolyte membrane and the protective film in the case of Comparative Example 1. FIG.
6 is a vertical sectional view of the membrane electrode assembly of the first embodiment according to the present invention.
7 is a vertical sectional view of the membrane electrode assembly of the second embodiment according to the present specification.
8 is a vertical cross-sectional view of the membrane electrode assembly of the third embodiment according to the present invention.
9 is a vertical cross-sectional view of the membrane electrode assembly of the fourth embodiment according to the present specification.
10 is a vertical cross-sectional view of the membrane electrode assembly of the fifth embodiment according to the present specification.
11 is a vertical sectional view of the membrane electrode assembly of the sixth embodiment according to the present invention.
12 is a flowchart of a method of manufacturing a membrane electrode assembly according to a second embodiment of the present invention.
13 is a flowchart of a method of manufacturing a membrane electrode assembly according to a sixth embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a cathode and an anode comprising a gas diffusion layer and a catalyst layer; And an electrolyte membrane provided between the anode and the cathode.

FIG. 1 schematically shows an electricity generating principle of a fuel cell. In a fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which includes an electrolyte membrane M and an electrolyte membrane M, And an anode (A) and a cathode (C) formed on both sides of the cathode (C). Referring to Fig. Showing the electricity generating principle of a fuel cell 1, an anode (A) in the hydrogen or methanol, butane and the oxidation of the fuel (F) of the hydrocarbon and so on up the hydrogen ions (H ⁺⁾ and electron (e ^-), such as And the hydrogen ions move to the cathode C through the electrolyte membrane M. In the cathode (C), the hydrogen ions transferred through the electrolyte membrane (M) react with the oxidizing agent (O) such as oxygen, and water (W) is produced. This reaction causes electrons to migrate to the external circuit.

2 schematically shows the structure of a membrane electrode assembly for a fuel cell. The membrane electrode assembly for a fuel cell includes an electrolyte membrane 10, a cathode 50 positioned opposite to the electrolyte membrane 10, And an anode 51 may be provided. The cathode includes a cathode catalyst layer 20 and a cathode gas diffusion layer 40 sequentially from an electrolyte membrane 10. The anode includes an anode catalyst layer 21 and an anode gas diffusion layer 41 successively from the electrolyte membrane 10, .

The present invention relates to a hydrocarbon-based electrolyte membrane; A first protective film provided on both surfaces of the hydrocarbon-based electrolyte membrane and having first through-holes penetrating in the thickness direction; An anode catalyst layer and a cathode catalyst layer provided on both surfaces of a hydrocarbon-based electrolyte membrane provided with the first protective film so as not to overlap with the first protective film; And a second passivation film provided on the other surface of the first protective film and the anode catalyst layer and on the other surface of the first protective film and the cathode catalyst layer to cover a part of the anode catalyst layer or the cathode catalyst layer, And a second protective film having a hole.

The membrane electrode assembly of the present invention includes a hydrocarbon-based electrolyte membrane provided between the cathode and the anode. Specifically, a hydrocarbon-based electrolyte membrane is provided between the catalyst layer of the cathode and the catalyst layer of the anode.

The hydrocarbon-based electrolyte membrane of the membrane electrode assembly serves as a medium through which protons pass and serves as a separation membrane of air and hydrogen gas. The higher the proton mobility of the hydrocarbon-based electrolyte membrane, the higher the performance of the membrane electrode assembly. At this time, the proton mobility of the hydrocarbon-based electrolyte membrane is affected by humidity, and the higher the humidity, the more easily the proton can move.

In one embodiment of the present invention, the polymer electrolyte composition forming the polymer electrolyte membrane may include a solvent and a polymer.

The polymer may be at least one hydrocarbon polymer, and conventional materials known in the art may be used.

For example, the polymer may be selected from the group consisting of sulfonated polyetheretherketone, sulfonated polyketone, sulfonated poly (phenylene oxide), sulfonated poly (phenylene sulfide), sulfonated polysulfone, (Phosphonite) polyphosphazene, and a sulfonated polybenzimidazole, and at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of at least one selected from the group consisting of poly (vinylidene fluoride), polycarbonate, sulfonated polystyrene, sulfonated polyimide, sulfonated polyquinoxaline, .

The content of the polymer can be adjusted according to the appropriate IEC (ion exchange capacity) value required for the electrolyte membrane for a fuel cell to be applied. In the case of polymer synthesis for membrane separation for fuel cells, the polymer can be designed by calculating the ion exchange capacity (IEC) meq./g = mmol / g. The polymer content can be selected so as to be within the range of 0.5 < = IEC <

The polymer may have a weight average molecular weight ranging from tens of thousands to millions. Specifically, the weight average molecular weight of the polymer may be selected within the range of 10,000 to 1,000,000.

The solvent is not particularly limited as long as it is a substance capable of reacting with the polymer to dissolve the polymer, and conventional materials known in the art can be used.

The hydrocarbon electrolyte membrane may be formed using the polymer electrolyte composition by a conventional method known in the art. For example, an electrolyte membrane may be formed by casting using the polymer electrolyte composition, May be impregnated with a polymer electrolyte composition to form an electrolyte membrane.

In order to realize the ion conductivity and the performance of a unit cell at the same level as that of the fluorine-based electrolyte membrane, the polymer is polymerized to have a higher IEC value than the fluorine-based electrolyte membrane in general in the case of the hydrocarbon-based electrolyte membrane. However, since the water absorption rate is increased by the increased IEC value, the dimensional stability of the hydrocarbon electrolyte membrane is increased due to the humidification situation, and the dimensional stability is decreased.

When a protective film is attached to the boundary between the hydrocarbon-based electrolyte membrane and the electrode after transferring the electrode to the hydrocarbon-based electrolyte membrane, the hydrocarbon-based electrolyte membrane having a sensitive dimensional change due to the humidifying state has a problem that the electrodes are not transferred on the surface of the hydrocarbon- There is a problem that the surface is not smooth and is overlapped or wrinkled.

Since the hydrocarbon-based electrolyte membrane has a warpage or a dimensional change of the membrane in a humidifying state, it is preferable to adhere the electrode to the electrolyte membrane to prevent warping or dimensional change of the membrane so as to maintain the shape of the surface of the hydrocarbon- First, the protective film is attached first and the electrode is attached. However, in such a case, the electrolyte membrane may be exposed between the electrode and the protective film.

Meanwhile, the membrane electrode assembly according to one embodiment of the present disclosure can prevent the electrolyte membrane from being directly exposed to fuel or air.

In addition, the membrane electrode assembly according to one embodiment of the present invention has an advantage of improving durability.

The first protective film may have first through holes provided on both surfaces of the hydrocarbon-based electrolyte membrane and penetrated in the thickness direction.

The first protective film may not overlap with the anode catalyst layer and the cathode catalyst layer provided on both surfaces of the hydrocarbon-based electrolyte membrane.

The cross-sectional area in the plane direction of the first through-hole may be equal to or wider than the cross-sectional area in the plane direction of the anode catalyst layer.

The cross-sectional area in the plane direction of the first through-hole may be the same as the cross-sectional area in the plane direction of the anode catalyst layer.

The cross-sectional area in the plane direction of the first through-hole may be wider than the cross-sectional area in the plane direction of the anode catalyst layer.

The cross-sectional area in the plane direction of the first through-hole may be equal to or larger than the cross-sectional area in the plane direction of the cathode catalyst layer.

The cross-sectional area in the plane direction of the first through-hole may be the same as the cross-sectional area in the plane direction of the cathode catalyst layer.

The cross-sectional area in the plane direction of the first through-hole may be wider than the cross-sectional area in the plane direction of the cathode catalyst layer.

Sectional area of the first through-hole may be the same as the cross-sectional area in the plane direction of the anode catalyst layer and the cross-sectional area in the plane direction of the cathode catalyst layer.

Sectional area of the first through-hole may be larger than a cross-sectional area in the plane direction of the anode catalyst layer and a cross-sectional area in the plane direction of the cathode catalyst layer.

Sectional area of the first through-hole may be the same as the cross-sectional area in the plane direction of the anode catalyst layer and wider than the cross-sectional area in the plane direction of the cathode catalyst layer.

Sectional area of the first through-hole may be the same as the cross-sectional area in the plane direction of the cathode catalyst layer and wider than the cross-sectional area in the plane direction of the anode catalyst layer.

When the cross-sectional area in the plane direction of the first through-hole is wider than the cross-sectional area in the plane direction of the anode catalyst layer, the distance between the first through-hole and the anode catalyst layer may be 0.1 mm or more and 100 mm or less.

When the cross-sectional area in the plane direction of the first through-hole is larger than the cross-sectional area in the plane direction of the cathode catalyst layer, the distance between the first through-hole and the cathode catalyst layer may be 0.1 mm or more and 50 mm or less.

The first protective film may have a first through hole. The one first through-hole may be located at the center in the plane direction of the first protective film.

The cross-sectional shape of the first through-hole may be selected depending on the planar shape of the membrane electrode assembly or the fuel cell, and may be, for example, a square or a circle.

The material of the first protective film may include at least one of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide.

The thickness of the first protective film may be 5 占 퐉 or more and 100 占 퐉 or less.

Plane direction cross-sectional area of the first through-hole can be selected according to the film plane direction, the cross-sectional area of the electrode assembly or fuel cell, for example, 5cm ² or more may be less than 500cm ^2.

The catalyst layer of the anode may be a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum- Can be used.

The catalyst layer of the cathode is where the reduction reaction of the oxidizing agent occurs, and platinum or a platinum-transition metal alloy can be preferably used as a catalyst.

In one embodiment of the present invention, the thickness of the catalyst layer may be 3 탆 or more and 30 탆 or less, respectively. At this time, the thickness of the catalyst layer of the anode and the thickness of the catalyst layer of the cathode may be the same or different from each other.

The catalysts can be used not only by themselves but also by being supported on a carbon-based carrier.

Examples of the carbon-based material include graphite, carbon black, acetylene black, denka black, cacao black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, , Carbon nanowire, fullerene (C60), and super P black (a mixture of two or more) may be preferable examples.

The catalyst layer may be introduced by a conventional method known in the art. For example, the catalyst composition may be directly coated on the electrolyte membrane, or a catalyst layer may be formed on a separate substrate, followed by thermocompression bonding to the electrolyte membrane It may be formed by removing a separate substrate. Here, the method of coating the catalyst composition is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used. The catalyst composition typically comprises a catalyst, a polymer ionomer and a solvent.

As the polymer ionomer, a sulfonated polymer such as a Nafion ionomer or a sulfonated polytrifluorostyrene may be used.

The solvent contained in the catalyst composition may be any one or a mixture of two or more selected from the group consisting of water, butanol, isopropanol, methanol, ethanol, n-propanol, n-butyl acetate, glycerol and ethylene glycol Can be preferably used.

The gas diffusion layer serves as a current conductor and serves as a passage for reacting gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive base material.

As the conductive base material, any conventional materials known in the art can be used. For example, carbon paper, carbon cloth or carbon felt can be preferably used. It does not.

In one embodiment of the present invention, the thickness of the gas diffusion layer may be 200 占 퐉 or more and 500 占 퐉 or less.

The membrane electrode assembly may be produced by a conventional method known in the art, in which the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane.

The second protective film may be provided on one surface of the first protective film and the anode catalyst layer, and on the other surface of the first protective film and the cathode catalyst layer.

The second protective film has a second through-hole penetrating in the thickness direction, and may be provided to cover only a part of the anode catalyst layer or the cathode catalyst layer.

Sectional area of the second through-hole may be smaller than that of the anode catalyst layer, and the cross-sectional area of the second through-hole may be smaller than the cross-sectional area of the cathode catalyst layer in the plane direction.

The separation distance between the second through-hole and the anode catalyst layer may be -100 mm (minus 100 mm) or more and 1 mm or less based on the plan view of the membrane electrode assembly. At this time, the separation distance may be a negative distance from the end of the anode catalyst layer to the second through hole because the second through-hole is smaller in cross-sectional area than the anode catalyst layer.

The distance between the second through-hole and the cathode catalyst layer may be -100 mm (minus 100 mm) or more and 1 mm or less with reference to the plan view of the membrane electrode assembly.

The second protective film may have one second through hole. And the one second through-hole may be located at the center in the plane direction of the second protective film.

The anode catalyst layer and the cathode catalyst layer covered with the second protective film are sealed and the anode catalyst layer and the cathode catalyst layer not covered with the second protection film by the second through holes of the second protective film are in contact with the gas diffusion layer, Is an active area that reacts with the fuel or oxidant supplied through the diffusion layer.

The cross-sectional shape of the second through-hole may be selected according to the planar shape of the membrane electrode assembly or the fuel cell, and may be, for example, rectangular or circular.

The material of the second protective film may include at least one of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide.

The thickness of the second protective film may be 5 占 퐉 or more and 100 占 퐉 or less.

Plane direction cross-sectional area and the second through-hole may be a film selected in accordance with the plane cross section of the electrode assembly or fuel cell, for example, 5cm ² or more may be less than 500cm ^2.

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

Another embodiment of the present disclosure relates to a stack comprising two or more membrane electrode assemblies according to the present disclosure and a separator provided between the membrane electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply part for supplying the oxidant to the stack.

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

The stack 60 includes one or more of the membrane electrode assemblies described above and includes a separator interposed therebetween when two or more membrane electrode assemblies are included. The separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer the fuel and oxidant supplied from the outside to the membrane electrode assembly.

The oxidant supply part 70 serves to supply the oxidant to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air can be injected into the pump 70 and used.

The fuel supply unit 80 serves to supply the fuel to the stack 60 and includes a fuel tank 81 for storing the fuel and a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 Lt; / RTI > As the fuel, gas or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

The present invention relates to a method of manufacturing a fuel cell, comprising: laminating a first protective film having a first through hole penetrating in a thickness direction on both surfaces of a hydrocarbon-based electrolyte membrane; Depositing an anode and a cathode on both sides of a hydrocarbon-based electrolyte membrane provided with the first protective film so as not to overlap with the first protective film; And a second protective film having a second through hole penetrated in the thickness direction so as to cover a part of the anode or the cathode on one surface of the first protective film and the anode, And a step of laminating the membrane electrode assembly.

The above-described method for producing the membrane electrode assembly can be referred to the above for the membrane electrode assembly and the fuel cell.

In the step of laminating the first protective film on both surfaces of the hydrocarbon-based electrolyte membrane, the first protective film may be positioned on both surfaces of the hydrocarbon-based electrolyte membrane and thermally compressed.

The step of laminating the anode catalyst layer and the cathode catalyst layer on both sides of the hydrocarbon-based electrolyte membrane having the first protective film may include forming an anode catalyst layer and a cathode catalyst layer on both surfaces of the hydrocarbon- The cathode catalyst layer can be respectively positioned and thermocompression bonded.

The step of laminating the second protective film may include a step of laminating the first protective film and the anode catalyst layer on one side and the second protective film and the cathode catalyst layer on the other side, The films can be positioned and thermocompressed, respectively.

The method and conditions for thermocompression may be selected from conventional methods and conditions known in the art, and the method, temperature, force for pressing, and compression time may be selected depending on the material to be compressed.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following embodiments are intended to illustrate the present disclosure and are not intended to limit the present disclosure.

[Example]

[Production Example 1]

Hydrocarbon-based Sulfonation  Block copolymer formation

Hydroquinonesulfonic acid potassium salt (0.9 eq.) And 4,4'-difluorobenzophenone (4, 4'-difluorobenzophenone) were added to a 1 L round bottom flask equipped with a Dean-Stark trap and a condenser. (4-fluorobenzoyl) phenyl (4-fluorophenyl) methanone was prepared by reacting 4'-difluorobenzophenone (0.97 eq.) And 3,5- methanone (0.02 eq.) were placed in a nitrogen atmosphere using dimethylsulfoxide (DMSO) as a catalyst and potassium carbonate as a catalyst in benzene solvent. The reaction mixture was then stirred for 4 hours in an oil bath at a temperature of 140 ° C to remove the azeotropic mixture by adsorption on molecular sieves of the Dean-Stark apparatus while the benzene was refluxing, The temperature was raised to 180 DEG C and condensation polymerization was carried out for 20 hours. After the completion of the reaction, the temperature of the reactant was reduced to 60 ° C, 4,4'-Difluorobenzophenone (0.2275 eq.), 9,9-bis (3-fluorobenzyl) phenyl (4-fluorophenyl) methanone (0.005 eq.) Was added The reaction was resumed using DMSO and benzene as catalysts in a nitrogen atmosphere with potassium carbonate. The reaction mixture was then stirred again in an oil bath for 4 hours at a temperature of 140 ° C to adsorb and remove the azeotropic mixture into the molecular sieves of the Dean-Stark apparatus while the benzene was refluxing, Was heated to 180 DEG C and condensation polymerization was carried out for 20 hours. Then, the temperature of the reaction was reduced to room temperature, and further DMSO was added to dilute the product. The diluted product was poured into an excess amount of methanol to separate the copolymer from the solvent. Thereafter, the excess potassium carbonate was removed by using water, and the resulting copolymer was dried in a vacuum oven at 80 DEG C for 12 hours or more to obtain a branched sulfonated multi-block type membrane in which hydrophobic blocks and hydrophilic blocks were alternately chemically bonded To prepare a copolymer.

[Production Example 2]

Preparation of Polymer Electrolyte Composition

38 g of dimethyl sulfoxide as a first solvent and 2 g of water as a second solvent were prepared, mixed and stirred for 2 hours to prepare a different solvent. Then, 10 g of the hydrocarbon-based sulfonated block copolymer prepared in Preparation Example 1 was dissolved in the above-mentioned different solvent and filtered through a BORU glass filter (pore size 3) to remove dust and the like, and then a polymer electrolyte composition solution was prepared

[Production Example 3]

Electrolyte membrane fabrication

The solution prepared in Preparation Example 2 was cast on a horizontal plate of a film applicator in a clean bench using a doctor blade and maintained at a temperature of 50 ° C for 2 hours to obtain a soft Soft bake. Thereafter, the polymer electrolyte membrane was placed in an oven set at 100 ° C and dried for 24 hours to form an electrolyte membrane containing the polymer electrolyte composition prepared in Preparation Example 2.

[Example 1]

Membrane electrode  Fabrication of the bonded body

Using the electrolyte membrane of Preparation Example 3, a cross-sectional area of the primary protective film through-hole of 9 cm x 9 cm in outer diameter was prepared to be 5.5 cm x 5.5 cm, and the electrolyte membrane was thermocompression-bonded at 100 ° C for 10 seconds to produce an electrolyte membrane having a protective film on both sides . Thereafter, an electrode having a surface area of 5.3 cm < 5 > and 5.3 cm was prepared. An electrolyte membrane having a protective film attached therebetween was placed thereon and hot pressed at 140 DEG C for 5 minutes using a hot press machine. To prepare an electrolyte membrane.

Thereafter, a secondary protective film for covering the electrolyte membrane exposed between the primary protective film and the electrode is prepared. The total area of the secondary protective film was 5.5 cm x 5.5 cm. The cross-sectional area of the through holes of the secondary protective film was 5 cm x 5 cm, which was smaller than the area of the electrode, and thermocompression was performed at 100 ° C for 10 seconds. .

[Example 2]

Using the electrolyte membrane of Preparative Example 3, the cross-sectional area of the primary protective film through-hole having an outer size of 9 cm x 9 cm was prepared to be 5.3 cm x 5.3 cm, and the electrolyte membrane was thermocompression-bonded at 100 ° C for 10 seconds to produce an electrolyte membrane having a protective film on both sides . Thereafter, an electrode having a surface area of 5.3 cm < 5 > and 5.3 cm was prepared. An electrolyte membrane having a protective film attached therebetween was placed thereon and hot pressed at 140 DEG C for 5 minutes using a hot press machine. To prepare an electrolyte membrane.

Thereafter, the total area of the secondary protective film is 9 cm x 9 cm, the cross-sectional area of the secondary protective film is 5 cm x 5 cm, which is smaller than the area of the electrode, thermocompression at 100 ° C for 10 seconds, .

[Comparative Example 1]

Using the electrolyte membrane of Preparation Example 3, a cross-sectional area of 5 cm x 5 cm of the primary protective film through-hole having an outer size of 9 cm x 9 cm was prepared, and the electrolyte membrane was thermocompression-bonded at 100 ° C for 10 seconds to prepare an electrolyte membrane having a protective film on both sides. Thereafter, an electrode having a 5 cm × 5 cm area was prepared, and an electrolyte membrane having a protective film between the electrodes was placed. The electrolyte membrane was thermally compressed at 140 ° C. for 5 minutes using a hot press machine, .

[Experimental Example 1]

RH cycle test

The RH cycle means to measure the durability in the fuel cell cell fastening state after manufacturing the electrolyte membrane with an MEA (Membrane Electrode Assembly).

Specifically, in the RH cycle of the present specification, nitrogen was injected into the anode at a flow rate of 0.95 slm (standard liter per minute) at a temperature of 80 캜, nitrogen was injected into the cathode at a flow rate of 1.0 slm, RH 150% % Of non-wetting was switched every 2 minutes.

In this specification, LSV (linear sweep voltametry) was used to measure the damage of the electrolyte membrane during the RH cycle. Specifically, the LSV means to measure the crossover of hydrogen at 0.1 to 0.4 V (2 mV / s) by injecting hydrogen into the anode at a flow rate of 0.2 slm and injecting nitrogen at a rate of 0.2 slm into the cathode . That is, when the crossover value of hydrogen rises during the RH cycle, it can be considered that the electrolyte membrane is damaged, and the degree of damage of the electrolyte membrane can be judged according to the degree of increase of the crossover value of hydrogen.

A graph of the results of RH cycles and hydrogen crossover values for Examples 1 and 2 and Comparative Example 1 is shown in Fig. At this time, the higher the RH cycle, the higher the durability of the electrolyte membrane.

Comparative Example 1 In some cases, the failure of the electrolyte membrane in the active area of the actual electrolyte membrane occured, but cracks as shown in FIG. 5 occurred at the edges of the electrolyte membrane and the protective film, cycle values.

10: electrolyte membrane
20, 21: catalyst layer
40, 41: gas diffusion layer
50: cathode
51: anode
60: Stack
70: oxidant supplier
80: fuel supply unit
81: Fuel tank
82: Pump
100: hydrocarbon-based electrolyte membrane
200: first protective film 250: first through hole
300: catalyst layer
400: second protective film 450: second through hole

Claims (14)

A hydrocarbon-based electrolyte membrane;
A first protective film provided on both surfaces of the hydrocarbon-based electrolyte membrane and having first through-holes penetrating in the thickness direction;
An anode catalyst layer and a cathode catalyst layer provided on both surfaces of a hydrocarbon-based electrolyte membrane provided with the first protective film so as not to overlap with the first protective film; And
A first through-hole, a second through-hole, and a second through-hole, the first through-hole extending through the first through-hole, the first through-hole, and the second through- And a second protective film formed on the first protective film. The membrane-electrode assembly according to claim 1, wherein the cross-sectional area in the plane direction of the first through-hole is equal to or wider than the cross-sectional area in the plane direction of the anode catalyst layer. The membrane-electrode assembly according to claim 1, wherein the cross-sectional area in the plane direction of the first through-hole is equal to or wider than the cross-sectional area in the plane direction of the cathode catalyst layer. 3. The fuel cell system according to claim 1, wherein the cross-sectional area in the plane direction of the second through-hole is smaller than the cross-sectional area in the plane direction of the anode catalyst layer,
Sectional area of the second through-hole is smaller than a cross-sectional area in the plane direction of the cathode catalyst layer. The membrane electrode assembly of claim 1, wherein the first protective film has one first through-hole. The membrane electrode assembly of claim 1, wherein the second protective film has one second through-hole. The membrane electrode assembly of claim 1, wherein the cross-sectional shape of the first through-hole and the second through-hole is rectangular or circular. The membrane electrode assembly according to claim 1, wherein the first protective film has a thickness of 5 占 퐉 or more and 100 占 퐉 or less. The membrane electrode assembly according to claim 1, wherein the thickness of the second protective film is 5 占 퐉 or more and 100 占 퐉 or less. A fuel cell comprising the membrane electrode assembly according to any one of claims 1 to 9. Depositing a first protective film having a first through hole penetrating in a thickness direction on both surfaces of a hydrocarbon-based electrolyte membrane;
Stacking an anode catalyst layer and a cathode catalyst layer on both sides of a hydrocarbon-based electrolyte membrane provided with the first protective film so as not to overlap with the first protective film; And
A second protective film and a cathode catalyst layer are formed on one surface of the first protective film and the anode catalyst layer and on the other surface of the second protective film and the cathode catalyst layer, 2 < / RTI > protective film. 12. The method of manufacturing a membrane-electrode assembly according to claim 11, wherein the step of laminating the first protective film on both surfaces of the hydrocarbon-based electrolyte membrane comprises positioning the first protective film on both surfaces of the hydrocarbon-based electrolyte membrane and thermocompression bonding. [14] The method of claim 11, wherein the step of laminating the anode catalyst layer and the cathode catalyst layer on both surfaces of the hydrocarbon-based electrolyte membrane having the first protective film comprises: forming a first protective film on both surfaces of the hydrocarbon- Wherein the anode catalyst layer and the cathode catalyst layer are positioned so as not to overlap with each other, and thermocompression bonding is performed. [12] The method of claim 11, wherein the step of laminating the second protective film comprises the steps of: laminating the anode catalyst layer or a portion of the cathode catalyst layer on one surface of the anode, And the second protective film is positioned and thermocompression-bonded.

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