JP2001243959A - Electrode for solid polymer fuel cell and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode for solid polymer fuel cell that maintains mechanical strength of the electrode and enables to disperse the sufficient gas necessary for reaction and increase adhesion between the electrode substrate and the solid polymer membrane, and further has a good water repellency. SOLUTION: A dispersion layer 9 is formed by spraying by a prescribed sprayer a mixture powder of carbon powder and a fluorine resin material powder treated by sulfonic acid on the surface of the electrode substrate 13 and both sides of the solid polymer membrane 7 treated in advance with water repellency, and on the dispersion layer 9 formed on the surface of the electrode substrate 13, a catalyst layer is further formed. And by the two electrode substrates 13a, 13b formed with the catalyst layer 12 through the dispersion layer 9, a solid polymer membrane 7 formed with the dispersion layer 9 on both sides is clipped in between and then is crimped and heated by hot press and these are integrated. After that, a separator 14 is installed at the outside surface of the electrode substrate 13 and a unit cell 19 is structured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer electrolyte fuel cell, and more particularly, to a structure and a manufacturing method of an electrode of a fuel cell.

[0002]

2. Description of the Related Art In recent years, fuel cells have attracted attention as high-efficiency energy conversion devices. This fuel cell is a device that directly converts the chemical energy of a fuel into electric energy. Usually, a fuel cell has a pair of porous electrodes sandwiching an electrolyte and has a back surface of one electrode such as hydrogen. And the oxidant such as oxygen is brought into contact with the back surface of the other electrode, and the electric energy generated by the electrochemical reaction occurring at this time is taken out from the pair of electrodes.

Depending on the type of electrolyte used, such a fuel cell can be operated at a low temperature, such as an alkaline type, a solid polymer type, or a phosphoric acid type, or at a high temperature, such as a molten carbonate type or a solid oxide type. They are roughly divided into batteries. Among them, a polymer electrolyte fuel cell (hereinafter referred to as PEFC) using a polymer electrolyte membrane having proton conductivity as an electrolyte.
Since it has a compact structure, high power density can be obtained, and can be operated with a simple system, it has attracted attention as a power source for space and vehicles as well as a stationary power source.

As the solid polymer electrolyte membrane (hereinafter, referred to as a solid polymer membrane), a perfluorocarbon sulfonic acid membrane (for example, Nafion: trade name, manufactured by DuPont) or the like is used. Further, since the solid polymer membrane has conductivity at low temperatures, PEFC operates at lower temperatures (60 ° C. to 120 ° C.) as compared with other types of fuel cells. for that reason,
The battery is characterized in that there are few restrictions on the material constituting the battery and the battery can be started in a short time.

FIG. 6 shows the structure of a conventional PEFC cell. That is, in the unit cell 19, the fuel electrode 17 and the oxidant electrode 18 are arranged on both surfaces of the solid polymer film 7. Each of the fuel electrode 17 and the oxidant electrode 18 includes an electrode substrate 13, and a carbon layer (diffusion layer) 9 and a catalyst layer 12 sequentially formed on the surface of the electrode substrate 13. Gas-impermeable separators 14 are provided on the back surfaces of the electrodes 17 and 18, respectively, and a fuel groove 15 serving as a fuel gas flow path is formed in the separator 14a on the fuel electrode 17 side. 14b on the side of the agent electrode 18
Is formed with an air groove 16 serving as a flow path for the oxidizing gas.

Various methods have been disclosed as methods for manufacturing such PEFC electrodes. For example, JP-A-6-203848 discloses that a slurry is formed by mixing a carbon powder carrying a noble metal catalyst on the surface, a solvent solution of an ion exchange resin serving as an electrolyte, and a solvent for dilution, and forming the slurry on an electrode base. A method is described in which a catalyst layer is formed on a surface of an electrode substrate by coating the material on a material and evaporating and removing the solvent.

US Pat. No. 5,620,807 discloses a method for forming a gas diffusion layer between a catalyst layer and an electrode substrate. In this way, by forming a carbon layer containing an electrolyte on the surface of the electrode substrate as a gas diffusion layer, the rate at which water generated at the electrode is diffused / removed can be controlled or included in the supplied gas. By controlling the rate of diffusion of moisture, these actions make it possible for the characteristics of the battery to not be sensitive to external water supply during the operation of the battery.
An object of the present invention is to provide a battery that can operate stably.

[0008]

However, the conventional method for manufacturing an electrode of a polymer electrolyte fuel cell as described above has the following problems. That is,
When forming a carbon layer functioning as a gas diffusion layer using a slurry obtained by mixing a carbon powder and a diluting liquid, generally, the slurry is composed of a carbon powder based on water, a fluororesin powder and a diluent thereof, Further, a fluororesin liquid is added as a water repellent, but in this manufacturing method, a problem occurs during the stirring process at the time of mixing. Also,
When the slurry was applied to an electrode substrate, the viscosity and solid content became larger than expected, and the slurry could not be applied due to an increase in viscosity.

Further, when a fluorine-based resin is dispersed in an aqueous system with alcohol, aggregates are easily formed by the carbon powder. Therefore, in order to completely dissolve the aggregates without forming aggregates, the slurry production conditions must be determined experimentally. The manufacturing process must be complicated. On the other hand, if the fluororesin is not mixed, it is difficult to form agglomerates, but there has been a problem that the fluororesin cannot impart water repellency to the catalyst layer. Also, if water repellency cannot be imparted to the carbon layer, condensed water fills the pores of the catalyst layer, particularly when operating at a high current density, and obstructs the diffusion path of the gas required for the reaction. There was a possibility that the performance would be reduced.

In order to solve such a problem, Japanese Patent Application Laid-Open No. 8-106915 discloses a method in which a carbon paper fiber serving as an electrode substrate is provided with water repellency using polytetrafluoroethylene, And a structure in which a catalyst layer is embedded therein.

Incidentally, the thickness of the catalyst layer is usually 10 to 5
At 0 μm, the mechanical support function required for the substrate cannot be expected with a substrate having the same thickness as the catalyst layer. On the other hand, when a thick substrate is used, the thickness of the catalyst layer is increased, which causes poor gas diffusion in the catalyst layer. Also, as in the above publication,
When the solid polymer electrolyte solution is impregnated into the entire carbon paper, the electrolyte that does not contribute to power generation is dispersed inside the substrate, and this electrolyte absorbs moisture and swells, causing the electrode substrate that needs gas diffusion to diffuse. The pores are blocked, and the diffusion of gas required for the reaction is hindered, causing a problem of a voltage drop of the battery.

The present invention has been proposed in order to solve the problems of the prior art as described above, and its object is to maintain the mechanical strength of the electrode and sufficiently remove the gas required for the reaction. An object of the present invention is to provide an electrode of a polymer electrolyte fuel cell which can be diffused, improves the adhesion between the electrode substrate and the solid polymer membrane, and has water repellency, and a method for producing the same.

[0013]

In order to achieve the above object, the invention according to claim 1 comprises a solid polymer electrolyte body, a fuel electrode and an oxidizing agent which are respectively disposed with the electrolyte body interposed therebetween. In an electrode of a polymer electrolyte fuel cell including an electrode, one surface of an electrode substrate constituting the fuel electrode and the oxidant electrode, and both surfaces of the solid polymer electrolyte body, carbon powder and sulfonic acid treatment. A diffusion layer made of a mixed powder of the applied fluorine-based resin material powder is formed.

According to the first aspect of the present invention having the above-described structure, the water-repellent diffusion layer is formed on each of the surfaces of the solid polymer electrolyte body and the electrode substrate, so that the electrode base is formed. Since the surface of the catalyst layer between the material and the solid polymer electrolyte body can be prevented from being covered with excessive moisture,
Stable battery performance can be obtained without hindering gas diffusion. In addition, since the diffusion layer has an action of controlling the rate at which the generated water is diffused and removed at the electrode and an action of controlling the rate of diffusion of the water contained in the supplied gas, the solid polymer electrolyte An electrode for a polymer electrolyte fuel cell that can stably operate without damaging sudden changes in the amount of water supplied to the body and without the cell characteristics being sensitive to external water supply. Obtainable.

According to a second aspect of the present invention, there is provided a method of manufacturing an electrode of a polymer electrolyte fuel cell comprising a solid polymer electrolyte body, and a fuel electrode and an oxidant electrode provided respectively with the electrolyte body interposed therebetween. In the method, a sulfonic acid-treated fluorinated resin powder obtained by crushing a fluorinated resin material to a predetermined particle size and performing sulfonic acid treatment, and carbon powder crushed to a predetermined particle size are mixed, and this mixed powder is mixed. The surface of the electrode substrate constituting the fuel electrode and the oxidant electrode and the surface of the solid polymer electrolyte body are sprayed on both surfaces of the solid polymer electrolyte body using a sprayer, and diffused on the surfaces of the electrode base material and the solid polymer electrolyte body. It is characterized by forming a layer.

According to the second aspect of the present invention having the above structure, the carbon powder and the sulfonic acid-treated fluororesin powder are mixed when sprayed with a sprayer, so that uniform dispersion and water repellency can be achieved. A sulfonic acid-treated fluororesin material is embedded in the voids of the carbon material having
A more effective diffusion layer can be formed. as a result,
The rate of diffusion and removal of water generated at the electrodes can be controlled, and the rate of diffusion of water contained in gas supplied from outside the battery can be controlled, so that the water supplied to the solid polymer electrolyte body can be controlled. It is possible to manufacture an electrode of a polymer electrolyte fuel cell that can stably operate without damaging a rapid change in the amount and without the characteristics of the cell reacting excessively to the amount of water supplied from the outside.

According to a third aspect of the present invention, in the method for producing an electrode of a polymer electrolyte fuel cell according to the second aspect, the sprayer is grounded, and the sulfonic acid-treated fluororesin powder and carbon powder are used. It is characterized in that it is configured not to be charged. According to the third aspect of the present invention having the above-described configuration, it is possible to avoid repulsion due to charging generated at the time of spraying.

According to a fourth aspect of the present invention, in the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the second aspect, the sprayer is provided with an ion generator, and the electrode substrate or the solid polymer electrolyte is provided. The body is charged with a positive charge, and the sulfonic acid-treated fluororesin powder and the carbon powder are charged with a negative charge.
According to the fourth aspect of the present invention having the above-described configuration, the sulfonic acid-treated fluororesin powder and the carbon powder easily adhere to the electrode substrate and the solid polymer electrolyte body.

According to a fifth aspect of the present invention, in the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the second aspect, the sprayer includes a nozzle for carbon powder and a nozzle for fluorinated sulfonic acid resin powder. Are separately provided, and spraying is performed while controlling the spraying amount of both powders at the time of spraying. According to the invention as set forth in claim 5 having the above configuration, both powders are simultaneously sprayed from dedicated nozzles, and a diffusion layer is formed while mixing both powders at the time of spraying. Since the dispersibility of the resin material is greatly improved, and the fluorine-based resin material treated with sulfonic acid is embedded in the voids of the carbon material having uniform dispersion and water repellency, the water repellency can also be improved.

According to a sixth aspect of the present invention, in the method for producing an electrode of a polymer electrolyte fuel cell according to the fifth aspect, the sulfonic acid-treated fluorine-based resin powder nozzle is formed in the form of:
The present invention is characterized in that the fluororesin powder material is shaped to be sheared at the time of spraying. According to the invention as set forth in claim 6 having the above configuration, the fluorine-based resin material can be fiberized by shearing at the time of spraying.
Dispersibility can be further improved by further improving water repellency and miniaturization.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention (hereinafter, referred to as embodiments) will be specifically described below with reference to the drawings. The same members as those of the conventional type shown in FIG. 6 are denoted by the same reference numerals, and description thereof will be omitted.

[1. First Embodiment] [1-1. Electrode Configuration] The present embodiment relates to a configuration of an electrode of a polymer electrolyte fuel cell. That is, in the electrode of the polymer electrolyte fuel cell of the present embodiment, as shown in FIG.
A mixed powder of carbon powder and sulfonic acid-treated fluororesin material powder is sprayed on one surface of
Are formed. Further, the catalyst layer 12 is formed on the diffusion layer 9 formed on the surface of the electrode substrate 13 as in the conventional case.

Then, the solid polymer film 7 having the diffusion layer 9 formed on both surfaces thereof is sandwiched by the two electrode bases 13a and 13b having the catalyst layer 12 formed thereon via the diffusion layer 9 and heated by hot pressing. After these are integrated by crimping, the separator 14 is attached to the outer surface of the electrode substrate 13 in the same manner as in the prior art, thereby forming the cell 19. The solid polymer film 7, the diffusion layer 9, and the catalyst layer 12 are
It is configured to be thinner than the electrode substrate 13.

The electrode substrate 13 is generally made of carbon paper (for example, TG, manufactured by Toray Industries, Inc.).
PH-090 etc.) are used. This carbon paper is made of conductive and corrosion-resistant carbon fiber,
Since it is porous and has good gas permeability, it is generally used as an electrode substrate. Further, since it is porous, it is suitable for a structure in which carbon is embedded in pores as in the present invention. Further, the pores of the electrode substrate 13 are paths through which the gas necessary for the reaction is diffused.
It is desirable that 3 has many pores.

The average bulk density of the carbon paper is 0.40 to 0.58 g / cm ³ , but the lower the bulk density, the larger the ratio of pores and the larger the gas diffusion coefficient. The density is desirably 0.40 g / cm ³ or less. Further, in order to maintain the mechanical strength, it is desirable that the thickness of the electrode substrate 13 be about 100 μm or more.

As a method of treating the electrode substrate 13 for water repellency, the pores of the electrode substrate 13 are impregnated with a dispersion solution of a fluororesin, and after drying the electrode substrate 13,
A method is used in which a heat treatment is performed at a temperature of 300 ° C. or more, and the surface of the material constituting the electrode base material 13 is coated with a fluororesin.

Furthermore, in order to avoid repulsion due to charging during spraying, the sprayer may be grounded and a stainless steel wire mesh may be provided to ground the sprayer. Conversely, by installing an ion generator in the sprayer and applying a positive charge to the electrode base material and a negative charge to the fluororesin material and the carbon material, these can be easily attached to the electrode base material.

In order to smooth the surface of the diffusion layer 9, a means such as compression with a roller after spraying or suction from the back surface of the electrode substrate is used. In addition, the fluorine-based resin material forming the diffusion layer functions as an adhesive with the electrode base material, so that electrical contact resistance can be reduced.

[1-2. Function / Effect] In the electrode of the polymer electrolyte fuel cell according to the present embodiment having the above-described configuration, the sulfonic acid-treated fluororesin material in the polymer electrolyte membrane 7 and the diffusion layer 9 is uniformly dispersed. When the solid polymer film 7 and the diffusion layer 9 are buried in the voids of the carbon material having water repellency, the solid polymer film 7 and the diffusion layer 9 come into contact with the electrode substrate 13 having water repellency. It is easily volatilized and removed from the fiber surface. Further, the electrode substrate 13
Has a water repellency, the fluorinated resin material powder treated with sulfonic acid does not penetrate deep into the electrode substrate 13, and can be present only near the surface of the electrode substrate 13.

As described above, according to the present embodiment,
By forming a water-repellent film (diffusion layer) on each surface of the solid polymer film 7 and the electrode substrate 13, the surface of the catalyst layer 12 between the electrode substrate 13 and the solid polymer film 7 is formed. Can be prevented from being covered with excessive moisture, so that gas diffusion is not hindered and stable battery performance can be obtained. In addition, since the entire electrode substrate is not covered with the electrolyte, the electrolyte absorbs moisture and swells, thereby preventing pores from being blocked and preventing gas diffusion. Since a film can be formed, stable battery performance can be obtained.

The diffusion layer 9 formed on both the electrode substrate 13 and the solid polymer film 7 functions to control the rate at which the water produced at the electrodes is diffused and removed, and to control the rate of gas supply. It has the effect of controlling the diffusion rate of water contained in the battery, so it buffers sudden changes in the amount of water supplied to the solid polymer membrane, and the characteristics of the battery do not react excessively to the amount of water supplied from the outside. In addition, it is possible to obtain an electrode of a polymer electrolyte fuel cell capable of performing stable operation.

[2. Second Embodiment] [2-1. Electrode Manufacturing Method] The present embodiment relates to a method for manufacturing an electrode of a polymer electrolyte fuel cell. That is, in the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the present embodiment, as shown in FIGS. 1 and 2, first, a fluorine-based resin material is finely pulverized by a pulverizer (a homogenizer, a chemical cutter, or the like). Acid-treated fluororesin powder obtained by subjecting a substance to sulfonic acid treatment (particle size: 0.1 μm or less)
And finely pulverized carbon powder (having a particle size of 0.1 μm or less), which were similarly pulverized by a pulverizer, and sprayed on the electrode substrate 13 and the solid polymer film 7 using a sprayer.
3 and a diffusion layer 9 is formed on the surface of the solid polymer film 7 (steps 1 to 3).

Subsequently, the surface of the diffusion layer 9 is smoothed by a roller, so that the electrode substrate 13 and the solid polymer film 7 are formed.
(Step 4). And
The solid polymer film 7 having the diffusion layer 9 formed on both surfaces thereof is sandwiched between the two electrode bases 13a and 13b on which the catalyst layer 12 is formed with the diffusion layer 9 interposed therebetween. Thus, adhesion is obtained (step 5).

Incidentally, in order to smooth the surface of the diffusion layer 9, in addition to the method of compressing with a roller after spraying as described above, a method of sucking from the back surface of the electrode substrate can also be used. Further, the mixed powder of the carbon powder and the fluorine-based resin material powder sprayed by the sprayer is dried at a temperature lower than the melting temperature of the fluorine-based resin material. If time permits, it may be left as it is after spraying and dried.

As a method for spraying the carbon powder and the sulfonic acid-treated fluororesin powder, as shown in FIG.
A method of spraying the carbon powder 1 and the sulfonic acid-treated fluororesin powder 2 on the surface of the solid polymer film 7 is used. In this case, the carbon and sulfonic acid-treated fluororesin may be sprayed not only in a powder state but also as a low-viscosity slurry, or polytetrafluoroethylene may be used as a fluorine-based material in addition to the electrolyte.

Further, in FIG. 3, reference numeral 8 denotes an electrode base moving table, on which the electrode base 13 or the solid polymer film 7 is mounted, and on which the nozzle 4 of the sprayer is mounted. And spraying a mixed powder of the carbon powder 1 and the sulfonic acid-treated fluororesin powder 2 on the surface of the electrode substrate 13 or the solid polymer film 7 by adjusting the opening of the valve 3. Have been.

[2-2. Function / Effect] According to the method for manufacturing an electrode of a polymer electrolyte fuel cell of the present embodiment having the above-described configuration, carbon powder and sulfonic acid-treated fluororesin powder are mixed when sprayed by a sprayer. So
The fluorinated resin material treated with sulfonic acid is embedded in the voids of the carbon material having uniform dispersion and water repellency, so that a more effective diffusion layer can be formed. As a result, it is possible to control the rate at which the generated water is diffused / removed at the electrode, and to control the diffusion rate of the water contained in the gas supplied from the outside of the battery. It is possible to manufacture an electrode of a polymer electrolyte fuel cell capable of performing a stable operation without buffering a sudden change in the amount of water to be supplied so that the characteristics of the cell are not sensitive to an external water supply amount. it can.

[3. Third Embodiment] [3-1. Electrode Manufacturing Method] This embodiment relates to a method for manufacturing an electrode of a polymer electrolyte fuel cell, and is a modification of the second embodiment. That is, in the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the present embodiment, as shown in FIG. 4, the nozzle of the sprayer has two nozzles, a carbon powder nozzle 20a and a fluorine resin material nozzle 20b. It is composed of a nozzle and sprays both powders at the same time while controlling the respective flow rates, and forms a film (diffusion layer) on the surfaces of the solid polymer film 7 and the electrode substrate 13 while mixing the two at the time of spraying. It is configured. The other configurations and steps are the same as those in the second embodiment, and a description thereof will not be repeated.

[3-2. Function / Effect] In the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the present embodiment having the above-described configuration, both powders are simultaneously sprayed from dedicated nozzles, and the two powders are mixed while spraying. Since the layer is formed, the dispersibility of the carbon powder and the fluorine-based resin material is significantly improved, and the fluorine-based resin material treated with sulfonic acid is embedded in the voids of the carbon material having uniform dispersion and water repellency. Also, the water repellency is improved.

Further, by providing two nozzles, the spraying amounts of the carbon powder and the fluororesin material powder can be separately controlled, so that appropriate manufacturing conditions can be easily set. Further, since the carbon powder and the fluorine-based resin material powder can be mixed during the spraying, the production becomes easy and the production becomes stable, so that the performance of the battery can be further improved.

The fluorine resin material nozzle 20b
The structure may be such that the fluorine-based resin material is subjected to shearing at the nozzle outlet, and the fluorine-based resin material is turned into fibers by shearing during spraying. By making the fluororesin material into a fiber in this manner, the water repellency is further improved, and by making it finer, the dispersibility is further improved.

[4. Fourth Embodiment] [4-1. Electrode Manufacturing Method] The present embodiment relates to a method for manufacturing an electrode of a polymer electrolyte fuel cell, and is a modification of the third embodiment. That is, in the method for manufacturing an electrode of a polymer electrolyte fuel cell according to the present embodiment, as shown in FIG. 5, an airless spray is used instead of an air spray for a sprayer, and a carbon powder and a sulfonic acid-treated fluorine-based An electrode is formed by spraying a resin material powder under pressure. In this case, the carbon powder and the fluorine-based resin material powder may be sprayed as a high-viscosity slurry, or they may be sprayed with high viscosity without dilution regardless of the powder or slurry. Other configurations and steps are the same as those in the third embodiment, and thus description thereof is omitted.

[4-2. Function / Effect] In the method of manufacturing an electrode of a polymer electrolyte fuel cell according to the present embodiment having the above-described configuration, the sulfonic acid-treated fluororesin material powder is compared with the case where air spray is used. And carbon powder can be efficiently processed without waste.
In addition, since the fluorine-based resin material powder and the carbon powder can be sprayed with high viscosity without being diluted, the applicable range can be expanded.

[0044]

According to the present invention, the mechanical strength of the electrode can be maintained, the gas required for the reaction can be sufficiently diffused, the adhesion between the electrode substrate and the solid polymer film can be improved, Furthermore, an electrode of a polymer electrolyte fuel cell having water repellency and a method for producing the same can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a configuration of an electrode of a polymer electrolyte fuel cell according to the present invention.

FIG. 2 is a flowchart showing a method for manufacturing an electrode of a polymer electrolyte fuel cell according to the present invention.

FIG. 3 is a conceptual diagram showing a state of forming a diffusion layer according to a second embodiment of the present invention.

FIG. 4 is a conceptual diagram showing a state of forming a diffusion layer according to a third embodiment of the present invention.

FIG. 5 is a conceptual diagram showing a state of forming a diffusion layer by an airless spray method according to a fourth embodiment of the present invention.

FIG. 6 is a cross-sectional view showing a configuration of a unit cell of a general polymer electrolyte fuel cell.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Carbon powder 2 ... Fluororesin material powder 3 ... Valve 4 ... Nozzle 5 ... Spraying condition 6 ... Diffusion layer formed by spraying 7 ... Solid polymer film 8 ... Electrode substrate moving table 9 ... Diffusion layer 10 ... Airless heating Pressurized carbon powder 11 Airless pressurized fluororesin material powder 12 Catalyst layer 13 Electrode substrate 14 Separator 15 Fuel groove 16 Air groove 17 Fuel electrode 18 Oxidant electrode 19 Single cell 20 Nozzle

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Atsushi Matsunaga 2-4, Suehirocho, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 5H018 AA06 BB08 BB11 BB12 EE05 EE18 5H026 AA06 BB00 BB04 BB06 BB08 CC03 EE05 EE19

Claims (6)

[Claims] 1. An electrode of a polymer electrolyte fuel cell comprising a solid polymer electrolyte body, and a fuel electrode and an oxidant electrode disposed respectively with the electrolyte body interposed therebetween, wherein the fuel electrode and the oxidant electrode A diffusion layer composed of a mixed powder of carbon powder and a fluorinated resin material powder that has been subjected to sulfonic acid treatment is formed on one surface of the electrode base material and on both surfaces of the solid polymer electrolyte body. Of a polymer electrolyte fuel cell. 2. A method for manufacturing an electrode of a solid polymer electrolyte fuel cell comprising a solid polymer electrolyte body, and a fuel electrode and an oxidant electrode respectively disposed with the electrolyte body interposed therebetween, comprising: Are mixed with a sulfonic acid-treated fluororesin powder obtained by pulverizing the fuel electrode to a predetermined particle size and then subjected to a sulfonic acid treatment, and a carbon powder pulverized to a predetermined particle size. One surface of the electrode substrate constituting the electrode, and sprayed on both surfaces of the solid polymer electrolyte body using a sprayer to form a diffusion layer on the surface of the electrode substrate and the solid polymer electrolyte body. A method for producing an electrode of a polymer electrolyte fuel cell. 3. The polymer electrolyte fuel cell according to claim 2, wherein the sprayer is grounded so that the sulfonic acid-treated fluororesin powder and the carbon powder are not charged. Manufacturing method of electrode. 4. The sprayer is provided with an ion generator for charging the electrode substrate or the solid polymer electrolyte body with a positive charge, and charging the sulfonic acid-treated fluororesin powder and the carbon powder with a negative charge. The method for producing an electrode of a polymer electrolyte fuel cell according to claim 2, wherein the electrode is configured to be charged. 5. The spraying machine is provided with a nozzle for carbon powder and a nozzle for fluorinated fluorinated resin powder separately and configured to spray while controlling the amount of spraying of both powders during spraying. The method for producing an electrode of a polymer electrolyte fuel cell according to claim 2, characterized in that: 6. The polymer electrolyte fuel cell according to claim 5, wherein the sulfonic acid-treated fluorine resin powder nozzle is shaped so as to shear the fluorine resin powder material during spraying. Method for manufacturing electrodes.