JP2009193772A - Electrode for polymer electrolyte fuel cell, its manufacturing method, and polymer electrolyte fuel cell equipped with it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode for a polymer electrolyte fuel cell capable of improving performance of the fuel cell in a high-humidification operation condition. <P>SOLUTION: This electrode for a polymer electrolyte fuel cell is formed by combining perfluoropolyether with an electrode structure comprising a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and supporting a metal catalyst thereto, and a polymer electrolyte impregnated in the carbon fiber layer. The number average molecular weight of the perfluoropolyether is preferably 1,000-8,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrode for a polymer electrolyte fuel cell, a method for producing the same, and a polymer electrolyte fuel cell provided with the electrode for a polymer electrolyte fuel cell, and in particular, a fuel cell under high humidification operation conditions. The present invention relates to an electrode for a polymer electrolyte fuel cell capable of improving the performance.

  In recent years, fuel cells have attracted attention as a battery having high power generation efficiency and a low environmental load, and extensive research and development has been conducted. Among fuel cells, solid polymer fuel cells with high output density and low operating temperature are easier to reduce in size and cost than other types of fuel cells. It is expected to spread widely as a household cogeneration system.

  In general, in a polymer electrolyte fuel cell, a pair of electrodes are arranged with a polymer electrolyte membrane sandwiched between them, a fuel gas such as hydrogen is brought into contact with the surface of one electrode, and oxygen is applied to the surface of the other electrode. The contained gas is brought into contact, and electric energy is taken out from between the electrodes by utilizing an electrochemical reaction that occurs at this time (see Non-Patent Documents 1 and 2). A catalyst layer is disposed on the electrode in contact with the polymer electrolyte membrane, and an electrochemical reaction occurs at the three-phase interface between the polymer electrolyte membrane, the catalyst layer, and the gas. Therefore, in order to improve the power generation efficiency of the polymer electrolyte fuel cell, it is necessary to increase the reaction field of the electrochemical reaction.

  In the polymer electrolyte fuel cell, in order to facilitate transmission of protons generated in the catalyst layer on the fuel electrode side to the air electrode (oxygen electrode) side through the polymer electrolyte membrane, the catalyst layer It is also necessary to contain a polymer electrolyte. Therefore, in order to increase the reaction field of the electrochemical reaction and to ensure a sufficient proton conduction path, the catalyst layer has been conventionally produced by supporting a noble metal catalyst such as platinum on granular carbon such as carbon black. It has been formed by applying a paste or slurry obtained by mixing catalyst powder and polymer electrolyte onto a gas diffusion layer made of carbon paper or the like. However, the polymer electrolyte fuel cell including the catalyst layer formed by this method has low power generation efficiency.

  On the other hand, the present inventors prepared carbon fibers by a specific method on a gas diffusion layer made of carbon paper or the like, supported noble metal on the carbon fiber by electroplating, and further supported the noble metal. It has been found that the power generation efficiency of a solid polymer fuel cell is improved by using an electrode produced by applying a polymer electrolyte solution to a carbon fiber in a polymer electrolyte fuel cell (Patent Document 1). reference).

The Chemical Society of Japan, “Chemical Review No. 49, Material Chemistry of New Batteries”, Academic Publishing Center, 2001, p. 180-182 “Polymer fuel cell <2001 edition>”, Technical Information Association, 2001, p. 14-15 International Publication No. 2004/063438 Pamphlet

  However, as a result of further studies by the present inventor, it has been found that there is room for improvement in the performance of the fuel cell including the electrode described in Patent Document 1 under high humidification operation conditions.

  Accordingly, an object of the present invention is to provide an electrode for a polymer electrolyte fuel cell that can solve the above-described problems of the prior art and can improve the performance of the fuel cell under high humidification operation conditions, and a method for manufacturing the same. There is.

  As a result of earnest studies to achieve the above object, the present inventor has found that a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a high impregnated in the carbon fiber layer. It has been found that by combining perfluoropolyether with an electrode structure composed of a molecular electrolyte, the performance of the fuel cell under high humidification operation conditions is improved, and the present invention has been completed.

  That is, the electrode for a solid polymer fuel cell of the present invention comprises a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a polymer electrolyte impregnated in the carbon fiber layer. It is characterized in that perfluoropolyether is combined with an electrode structure comprising

  In the polymer electrolyte fuel cell electrode of the present invention, the perfluoropolyether preferably has a number average molecular weight (Mn) of 1000 to 8000.

The production method of the present invention is a method for producing the above polymer electrolyte fuel cell electrode,
Perfluoropolyether is added to the electrode structure comprising a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a polymer electrolyte impregnated in the carbon fiber layer. It is characterized in that the perfluoropolyether is diluted with an active solvent and sprayed or applied with a solution having a perfluoropolyether concentration of 0.01 to 0.2% by weight to compound the perfluoropolyether into the electrode structure.

  In a preferred embodiment of the production method of the present invention, the perfluoropolyether solution is sprayed or applied from the gas diffusion layer side.

  Moreover, the polymer electrolyte fuel cell of the present invention comprises the above-mentioned electrode for a polymer electrolyte fuel cell.

  According to the present invention, an electrode structure comprising a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a polymer electrolyte impregnated in the carbon fiber layer is provided with perfluorocarbon. By combining the polyether, it is possible to provide a polymer electrolyte fuel cell electrode capable of improving the performance of the fuel cell under highly humidified operation conditions.

<Electrode for polymer electrolyte fuel cell and method for producing the same>
Hereinafter, the polymer electrolyte fuel cell electrode of the present invention will be described in detail. An electrode for a polymer electrolyte fuel cell of the present invention comprises a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a polymer electrolyte impregnated in the carbon fiber layer. The electrode structure is formed by combining perfluoropolyether. In the polymer electrolyte fuel cell electrode of the present invention, since the perfluoropolyether is combined with the electrode structure, the water repellency derived from the perfluoropolyether is exerted, and moisture generated by protons and oxygen Can be efficiently delivered to the gas diffusion layer and out of the system without staying in the electrode structure, and the battery performance is hindered by the movement of oxidizing gas, which is caused by moisture retention, into the electrode structure. By preventing a phenomenon called so-called flooding, in which the fuel cell performance is significantly reduced, the performance of the fuel cell can be improved particularly under high humidification operation conditions.

  The above-described electrode for a polymer electrolyte fuel cell of the present invention includes, for example, a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and supporting a metal catalyst, and a high impregnated in the carbon fiber layer. It can be produced by preparing an electrode structure made of a molecular electrolyte and spraying or applying a solution obtained by diluting perfluoropolyether with a fluorine-based inert solvent to the electrode structure.

  The gas diffusion layer of the electrode structure is preferably porous and conductive, and specific examples thereof include carbon paper and porous carbon cloth. Among these, carbon paper is preferable.

  The carbon fiber layer is formed on the gas diffusion layer by, for example, electrolytic oxidation polymerization of a compound having an aromatic ring on the gas diffusion layer to form a fibril polymer layer, and then firing the fibril polymer layer. It can be carried out by carbonizing.

  Examples of the compound having an aromatic ring include a compound having a benzene ring and a compound having an aromatic heterocyclic ring. Here, as the compound having a benzene ring, aniline and aniline derivatives are preferable, and as the compound having an aromatic heterocyclic ring, pyrrole, thiophene and derivatives thereof are preferable. These compounds having an aromatic ring may be used singly or as a mixture of two or more.

In the electrolytic oxidation polymerization, it is preferable to mix an acid together with a raw material compound having an aromatic ring. In this case, the negative ion of the acid is taken into the fibril polymer synthesized as a dopant to obtain a fibril polymer excellent in conductivity. By using this fibril polymer, the conductivity of the carbon fiber is finally improved. Further improvement can be achieved. Here, examples of the acid mixed in the electrolytic oxidation polymerization include HBF ₄ , H ₂ SO ₄ , HCl, HClO _{4 and the} like. The acid concentration is preferably in the range of 0.1 to 3 mol / L, more preferably in the range of 0.5 to 2.5 mol / L.

Formation of the fibrillar polymer layer is performed by immersing the gas diffusion layer as a working electrode in a solution containing a compound having an aromatic ring, further immersing the counter electrode, and exceeding the oxidation potential of the compound having an aromatic ring between the two electrodes. Or a current having a condition sufficient to secure a voltage sufficient to polymerize the compound having an aromatic ring may be applied, whereby a fibrillated polymer is formed on the gas diffusion layer (working electrode). Is generated. Here, as the counter electrode, a plate made of a highly conductive material such as stainless steel, platinum, or carbon, a porous support, or the like can be used. An example of a method for synthesizing a fibril-like polymer by this electrolytic oxidation polymerization method is as follows. A gas diffusion layer (working electrode) and a counter electrode are provided in an electrolytic solution containing a compound having an acid and an aromatic ring such as H ₂ SO ₄ and HBF _4. Examples include a method in which a fibrillated polymer is polymerized and deposited on the gas diffusion layer (working electrode) side by immersing and applying a current of 0.1 to 1000 mA / cm ² , preferably 0.2 to 100 mA / cm ² between both electrodes. Is done. Here, the concentration of the compound having an aromatic ring in the electrolytic solution is preferably 0.05 to 3 mol / L, and more preferably 0.25 to 1.5 mol / L. Moreover, in addition to the said component, you may add a soluble salt etc. to an electrolyte solution suitably in order to adjust pH.

  The fibrillar polymer obtained by electrolytic oxidation polymerization of the compound having an aromatic ring usually has a three-dimensional continuous structure, has a diameter of 30 to several hundred nm, preferably 40 to 500 nm, and has a length of It is 0.5 μm to 100 mm, preferably 1 μm to 10 mm.

  By baking and carbonizing the fibrillated polymer, a carbon fiber layer can be formed on the gas diffusion layer. In addition, it is preferable to wash | clean a fibril polymer with solvents, such as water and an organic solvent, and to dry before baking of a fibril polymer. Here, the drying method is not particularly limited, and examples thereof include a method using a fluidized bed drying device, an air dryer, a spray dryer, etc., in addition to air drying and vacuum drying.

  The conditions for the firing are not particularly limited, and may be set as appropriate so as to obtain an optimum conductivity. Particularly, when high conductivity is required, the temperature is 500 to 3000 ° C., preferably 600 to Baking is preferably performed at 2800 ° C. for 0.5 to 6 hours. Note that the firing is preferably performed in a non-oxidizing atmosphere, and examples of the non-oxidizing atmosphere include a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere. In some cases, a hydrogen atmosphere can also be used.

The carbon fiber usually has a three-dimensional continuous structure, has a diameter of 30 to several hundred nm, preferably 40 to 500 nm, and a length of 0.5 μm to 100 mm, preferably 1 μm to 10 mm. The surface resistance is 10 ⁶ to 10 ⁻² Ω, preferably 10 ⁴ to 10 ⁻² Ω. The carbon fiber has a residual carbon ratio of 90 to 20%, preferably 80 to 25%. Since the carbon fiber has a structure in which the entire carbon is three-dimensionally continuous, the carbon fiber has higher conductivity than the granular carbon.

  In addition, after forming a carbon fiber layer on the gas diffusion layer, it is preferable to subject the carbon fiber layer to a high temperature treatment at 1500 ° C. or higher, and more preferably to a high temperature treatment at 1800 to 3000 ° C. A polymer electrolyte fuel cell comprising an electrode using a carbon fiber subjected to high temperature treatment as a carrier for a metal catalyst is more solid than a polymer electrolyte fuel cell comprising an electrode using carbon fiber not subjected to high temperature treatment. The battery voltage is high and the internal resistance is low in a wide current range, and good power generation characteristics are exhibited. Here, the high-temperature treatment is preferably performed in a non-oxidizing atmosphere, and examples of the non-oxidizing atmosphere include a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere. In some cases, a hydrogen atmosphere is used. You can also.

  Next, a metal catalyst is supported on the carbon fiber. Here, as the metal catalyst supported on the carbon fiber, a noble metal is preferable, and Pt is particularly preferable. In the present invention, Pt may be used alone or as an alloy with another metal such as Ru. By using Pt as the noble metal, hydrogen can be oxidized with high efficiency even at a low temperature of 100 ° C. or lower. Further, by using an alloy such as Pt and Ru, it is possible to prevent poisoning of Pt by CO and prevent a decrease in the activity of the catalyst. The particle size of the metal catalyst supported on the carbon fiber is preferably in the range of 0.5 to 20 nm, and the support rate of the metal catalyst is preferably in the range of 0.01 to 2 g with respect to 1 g of the carbon fiber. Here, the method for supporting the metal catalyst on the carbon fiber is not particularly limited, and examples thereof include an impregnation method, an electroplating method (electrolytic reduction method), an electroless plating method, and a sputtering method. .

The metal catalyst is preferably supported on the carbon fiber by an electroplating method in which an electric current is applied in a pulse shape. The surface area of the supported metal catalyst can be improved by applying a current in pulses to electroplate the metal catalyst. In the electroplating, the current density is preferably in the range of 10 to 500 mA / cm ² , and the energization charge amount is preferably in the range of 0.02 to 5 C / cm ² .

Next, the polymer electrolyte is impregnated in the carbon fiber layer on which the metal catalyst is supported. As the polyelectrolyte, an ion conductive polymer can be used. Examples of the ion conductive polymer include polymers having an ion exchange group such as sulfonic acid, carboxylic acid, phosphonic acid, and phosphonous acid. And the polymer may or may not contain fluorine. Examples of the ion conductive polymer include perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark). The amount of impregnation of the polymer electrolyte is preferably in the range of 0.01 mg / cm ^{2 to} 4.0 mg / cm ² , and when the coating amount of the polymer electrolyte is less than 0.01 mg / cm ² , the proton conductivity decreases, If it exceeds 4.0 mg / cm ² , the gas permeability decreases and flooding is likely to occur. The thickness of the catalyst layer is not particularly limited, but is preferably in the range of 0.1 to 100 μm. The amount of the metal catalyst supported on the catalyst layer is determined by the loading rate and the thickness of the catalyst layer, and is preferably in the range of 0.001 to 1 mg / cm ² .

  The electrode structure prepared as described above is sprayed or coated with a solution having a concentration of 0.01 to 0.2% by weight of perfluoropolyether obtained by diluting perfluoropolyether with a fluorine-based inert solvent. The body is compounded with perfluoropolyether. Here, if the concentration of perfluoropolyether is less than 0.01% by weight, the amount of spraying or applying a sufficient amount of perfluoropolyether to exert an effect increases, and the process requires a long time or Problems such as uneven distribution of the fluoropolyether occur. On the other hand, if it exceeds 0.2% by weight, excessive perfluoropolyether is complexed, resulting in high costs or reduced power generation performance. Will arise. In the present invention, the perfluoropolyether solution is preferably sprayed or applied from the gas diffusion layer side.

The perfluoropolyether has a plurality of ether bonds in the molecule and includes a perfluoromethylene group (CF ₂ ). The perfluoropolyether may contain an alkylene group, a trialkoxysilyl group, etc. in addition to an ether bond and a perfluoromethylene group in the molecule, where the alkylene group includes a methylene group, ethylene Examples of the trialkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a dimethoxyethoxysilyl group, and a methoxydiethoxysilyl group. Further, as the perfluoropolyether, specifically, the following formula (I):
(CH ₃ O) ₃ Si—C ₃ H ₆ —O—CH ₂ CF ₂ — (OC ₂ F ₄ ) _n — (OCF ₂ ) _m —OCF ₂ CH ₂ —O—C ₃ H ₆ —Si (OCH _{3 3} ... (I)
A polymer represented by [wherein n and m represent the degree of polymerization] is preferred.

  The perfluoropolyether preferably has a number average molecular weight (Mn) of 1000 to 8000. If the number average molecular weight of the perfluoropolyether used is less than 1000, the reason is not clear, but the sustainability of the effect deteriorates, and if it exceeds 8000, the effect itself is not exhibited.

  The fluorine-based inert solvent used for diluting the perfluoropolyether is not particularly limited, and for example, perfluorohexane, perfluoromethylcyclohexane, perfluoroethylcyclohexane, perfluorodimethylcyclohexane and the like can be used.

  The electrode for a polymer electrolyte fuel cell of the present invention can be used as a fuel electrode or an air electrode (oxygen electrode). Here, in the polymer electrolyte fuel cell electrode, a carbon fiber layer on which a metal catalyst is supported and impregnated with a polymer electrolyte functions as a catalyst layer. The gas diffusion layer has a function as a current collector for transferring generated electrons in addition to a function of supplying fuel such as hydrogen gas or an oxygen-containing gas such as oxygen or air to the catalyst layer by diffusion. .

<Solid polymer fuel cell>
Next, a polymer electrolyte fuel cell using the polymer electrolyte fuel cell electrode of the present invention will be described with reference to FIG. The illustrated polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) 1 and separators 2 located on both sides thereof. The membrane electrode assembly (MEA) 1 includes a solid polymer electrolyte membrane 3 and a fuel electrode 4A and an air electrode (oxygen electrode) 4B located on both sides thereof, and at least the fuel electrode 4A and the air electrode (oxygen electrode) 4B. One is an electrode for a polymer electrolyte fuel cell of the present invention. In the fuel electrode 4A, a reaction represented by 2H ₂ → 4H ⁺ + 4e ⁻ occurs, the generated H ⁺ passes through the solid polymer electrolyte membrane 3 to the air electrode 4B, and the generated e ⁻ is taken out to the outside. Current. On the other hand, in the air electrode 4B, a reaction represented by O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O occurs, and water is generated. The fuel electrode 4A and the air electrode 4B are composed of a catalyst layer (carbon fiber layer supporting a metal catalyst and impregnated with a polymer electrolyte) 5 and a gas diffusion layer 6, and the catalyst layer 5 is in contact with the solid polymer electrolyte membrane 3 Are arranged to be.

  In the polymer electrolyte fuel cell of the present invention, an ion conductive polymer can be used as the solid polymer electrolyte membrane 3, and the carbon fiber layer can be impregnated as the ion conductive polymer. What was illustrated as a possible polymer electrolyte can be used. Moreover, as the separator 2, the normal separator with which flow paths (not shown), such as fuel, air, and produced | generated water, were formed in the surface can be used.

  In the polymer electrolyte fuel cell of the present invention, performance under high humidification operation conditions is improved as a result of the perfluoropolyether being combined with the electrode structure comprising the catalyst layer 5 and the gas diffusion layer 6. is doing.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Example 1)
<Electropolymerization process>
In an aqueous solution containing 1.0 mol / L of sulfuric acid and 0.5 mol / L of aniline, carbon paper (manufactured by Toray Industries, Inc.) is installed as a working electrode, a counter electrode made of SUS316L is installed, and polyaniline is placed on the working electrode by the constant current method. Produced. The size of the carbon paper is prepared so that the effective dimension for polyaniline formation is 5 × 5 cm, and polymerization is performed at room temperature at a current density of 40 mA / cm ² until the energization amount is 3.7 C / cm ^2. Continued. After completion of the polymerization, the obtained polyaniline was thoroughly washed with pure water. The mass was measured after drying, and the amount of polyaniline produced was determined to be 1.4 mg / cm ² .

<Baking process>
The obtained polyaniline was calcined together with carbon paper in an electric furnace under an Ar reduced pressure atmosphere from room temperature to 1200 ° C. over 3 hours and held at 1200 ° C. for 1 hour. Then, it cooled to room temperature, taken out the carbonized polyaniline (carbon fiber) from the electric furnace, measured the mass, and the residual carbon rate of polyaniline was 35%.

<High temperature treatment process>
Next, the carbonized polyaniline is heated together with carbon paper in a high-temperature electric furnace in an Ar reduced pressure atmosphere from room temperature to 1200 ° C for 1 hour, from 1200 ° C to 2700 ° C over 2 hours, and held at 2700 ° C for 15 minutes. The crystallization treatment was performed. Then, it cooled to room temperature, when the high temperature crystallized polyaniline carbide (carbon fiber) was taken out from the high temperature electric furnace and the mass was measured, the residual carbon rate of polyaniline was 25%.

<Platinum loading process>
A plating solution was prepared by dissolving 10 g of chloroplatinic acid hexahydrate in 1000 mL of pure water. In the plating solution, a high-temperature crystallized polyaniline carbide integrated with carbon paper was installed as a working electrode, a platinum-plated titanium counter electrode was installed, and platinum was supported on the carbide by a pulse method. The pulse current was 100 mA / cm ² per projected area of the working electrode, the on time was 0.003 seconds, the off time was 0.006 seconds, and the energization amount was 0.6 C / cm ² . After the platinum loading was completed, the obtained sample was thoroughly washed with pure water, and after drying, the mass was measured to determine the platinum loading, which was 0.25 mg / cm ² .

<Production of MEA>
Two pieces of platinum-supported polyaniline carbide / carbon paper obtained as described above were cut out into 5 × 5 cm squares, and Nafion (registered trademark) solution [ Nafion: water: isopropyl alcohol = 5: 47.5: 47.5 (mass ratio)] was applied with a brush so that the mass of Nafion after drying was 0.3 mg / cm ² . The obtained Nafion-coated platinum-supported polyaniline carbide / carbon paper was sandwiched between Nafion 112 membranes and pressed by hot pressing to obtain a membrane electrode assembly (MEA).

<Water repellent treatment>
From the gas diffusion layer (carbon paper) side of the membrane electrode assembly obtained, 0.1% by weight of a fluorine-based mold release agent [Daikin Chemicals Sales, Durasurf HD-2101Z, perfluoropolyether with a number average molecular weight of 2000] The solution was diluted with perfluorohexane (fluorinated inert solvent) at a concentration] with a brush, and then left overnight.

<Performance evaluation of fuel cell>
A fuel cell was assembled using the obtained membrane electrode assembly, a graphite bipolar plate, a silicone gasket, and a gold-plated copper plate current collector, and fully conditioned by flowing hydrogen to the anode and air to the cathode. Later performance was recorded. The cell temperature was 80 ° C., the anode humidification temperature was 80 ° C., the cathode humidification temperature was 85 ° C., the hydrogen flow rate was 0.5 L / min, and the air flow rate was 2 L / min. The back pressure was set to 0.05 MPa on both the anode side and the cathode side. The results are shown in Table 1.

(Comparative Example 1)
A membrane electrode assembly (MEA) was produced in the same manner as in Example 1 except that the water repellent treatment was not performed, a fuel cell was assembled, and power generation performance was evaluated. The results are shown in Table 1.

From Table 1, it can be seen that Example 1 in which the MEA was subjected to water repellent treatment has high power generation performance from the low current region to the high current region even under high humidification operation conditions. On the other hand, Comparative Example 1 in which the MEA was not subjected to the water repellent treatment had lower power generation performance than that of Example 1, and measurement was impossible when the voltage reached a current density of 1.0 A / cm ² .

It is sectional drawing of an example of the polymer electrolyte fuel cell of this invention.

Explanation of symbols

1 Membrane electrode assembly (MEA)
2 Separator 3 Solid polymer electrolyte membrane 4A Fuel electrode 4B Air electrode (oxygen electrode)
5 Catalyst layer 6 Gas diffusion layer

Claims (5)

  A perfluoropolyether is combined with an electrode structure comprising a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a polymer electrolyte impregnated in the carbon fiber layer. An electrode for a polymer electrolyte fuel cell.   The electrode for a polymer electrolyte fuel cell according to claim 1, wherein the perfluoropolyether has a number average molecular weight of 1000 to 8000.   Perfluoropolyether is added to the electrode structure comprising a gas diffusion layer, a carbon fiber layer formed on the gas diffusion layer and carrying a metal catalyst, and a polymer electrolyte impregnated in the carbon fiber layer. 3. The perfluoropolyether is combined with the electrode structure by spraying or applying a solution having a concentration of 0.01 to 0.2% by weight of a perfluoropolyether diluted with an active solvent. The manufacturing method of the electrode for solid polymer type fuel cells as described in any one of.   4. The method for producing an electrode for a polymer electrolyte fuel cell according to claim 3, wherein the perfluoropolyether solution is sprayed or applied from the gas diffusion layer side.   A polymer electrolyte fuel cell comprising the electrode for a polymer electrolyte fuel cell according to claim 1.

Images