JP2010146850A - Electrode paste for fuel cell, membrane electrode assembly, and manufacturing method of electrode paste - Google Patents

Abstract

[PROBLEMS] To provide a fuel cell in which proton exchange groups of a polymer electrolyte are strongly oriented toward the hydrophilic layer side, excellent in gas diffusibility and proton conductivity of a catalyst layer, and capable of obtaining high output while being lightly humidified or non-humidified. A method for producing an electrode paste is provided.
A method for producing an electrode paste for a fuel cell includes, as a first step, a step in which a mixture containing a catalyst-supporting carbon and water is accommodated in a chamber and then a first intermediate is obtained by a centrifugal stirring method. Steps S4 to S7 for obtaining an electrode paste by mixing S1 to S3 and, as a second step, mixing the first intermediate and a polymer electrolyte solution having a temperature lower than the temperature of the first intermediate; Consists of.
[Selection] Figure 1

Description

  The present invention relates to a fuel cell electrode paste, a membrane electrode assembly, and a method for producing an electrode paste.

  Conventionally, a fuel cell system using a membrane electrode assembly (MEA) 90 as shown in FIG. 10 is known. The membrane electrode assembly 90 includes an electrolyte membrane 91 made of a solid polymer membrane such as Nafion (registered trademark, Nafion (manufactured by Dupon)), and a cathode electrode joined to one surface of the electrolyte membrane 91 and supplied with air. 93 and an anode 92 that is joined to the other surface of the electrolyte membrane 91 and is supplied with a fuel such as hydrogen.

  The cathode electrode 93 includes a gas-permeable base material such as carbon cloth, carbon paper, carbon felt, and the like, and a cathode catalyst layer 93a formed on one surface of the base material. A portion of the cathode electrode 93 other than the cathode catalyst layer 93a is formed of a base material, which is a cathode diffusion layer 93b that diffuses air to the cathode catalyst layer 93a on the non-electrolyte side.

  The anode 92 also includes the base material and an anode catalyst layer 92a formed on one surface of the base material. The portion other than the anode catalyst layer 92a in the anode electrode 92 is also formed of a base material, and this is an anode diffusion layer 92b that diffuses air to the anode catalyst layer 92a on the non-electrolyte side.

  The membrane electrode assembly 90 is sandwiched between separators (not shown) to form a fuel cell as a minimum power generation unit, and a large number of these cells are stacked to form a fuel cell stack. Air is supplied to the cathode catalyst layer 93a by air supply means, and hydrogen or the like is supplied to the anode catalyst layer 92a by hydrogen supply means or the like. Thus, the fuel cell system is configured.

In the membrane electrode assembly 90, hydrogen ions (H ⁺ ; protons) and electrons are generated from the fuel by an electrochemical reaction in the anode catalyst layer 92a. Protons move in the electrolyte membrane 91 toward the cathode catalyst layer 93a in the form of H ₃ O ⁺ accompanied by water molecules. The electrons flow through the load connected to the fuel cell system and flow into the cathode catalyst layer 93a. On the other hand, in the cathode catalyst layer 93a, oxygen contained in the air is reduced to become hydroxide ions, and proton bonds to generate water. The fuel cell system can continuously generate an electromotive force by continuously performing such an electrochemical reaction.

  The characteristics required for the anode catalyst layer 92a and the cathode catalyst layer 93a are as follows: (1) the oxidizing gas and fuel gas can be diffused; and (2) the proton generated by the electrochemical reaction is transferred to the solid electrolyte membrane. And (3) good electron conductivity for extracting current to the outside. And in order to satisfy these characteristics, each electrode paste is applied to a base material such as carbon cloth by mixing a catalyst-carrying carbon having electron conductivity and a polymer solid electrolyte having proton conductivity. A catalyst layer was formed. For example, as shown in FIG. 11, Non-Patent Document 1 discloses a method of pouring a polymer electrolyte solution onto catalyst-carrying carbon and stirring with ultrasonic waves to obtain an electrode paste.

However, in the catalyst layer formed using the electrode paste manufactured by such a method, the orientation of the hydrophilic functional group present in the polymer solid electrolyte is not taken into consideration. Many hydrophilic functional groups will be present on the pore side. For this reason, since the pore wall becomes hydrophilic and easily wets with water, the water easily accumulates in the pores, and the accumulated water inhibits gas diffusion through the pores.
Further, since a hydrophilic path that is oriented toward the catalyst-carrying carbon and does not communicate is not formed, water generated in the cathode catalyst layer is difficult to back-diffuse to the solid electrolyte membrane side. For this reason, water stays in the cathode catalyst layer and becomes a factor that inhibits gas diffusion.
Furthermore, the catalyst-carrying carbon and the polymer solid electrolyte tend to be large aggregates (agglomerates), and the catalyst-carrying carbon inside the agglomerates cannot contribute to the electrode reaction, which is wasted. In addition, unless the catalyst-carrying carbon adheres uniformly to the solid polymer electrolyte, the hydrophilic path cannot be sufficiently communicated, and the water transfer cannot be performed smoothly.

  The inventors have already developed a method for producing an electrode paste for a fuel cell that solves these problems (Patent Documents 1 and 2). In this production method, as a first step, after containing a mixture containing catalyst-supporting carbon and water in the chamber, the chamber is rotated to revolve the chamber while applying centrifugal force to the mixture by revolving the chamber. The mixture with its own weight. As a result, air can be forced out of the surface of each catalyst-supporting carbon, and the surface can be covered with water. At this time, since foreign substances such as balls and propellers are not used for imparting centrifugal force and stirring, contact between the catalyst-supporting carbons is hardly hindered.

  And as a 2nd process, the polymer electrolyte solution containing isopropyl alcohol is mixed with the mixture obtained at the 1st process, and the paste for electrodes is obtained. At this time, since each catalyst-supporting carbon has wettability to water, the polymer electrolyte orients proton exchange groups of the polymer electrolyte on the catalyst-supporting carbon side. And the paste for electrodes of this invention in which the hydrophilic layer which mutually continues with water was formed between each catalyst support carbon and polymer electrolyte which mutually contact is obtained.

In the electrode paste thus obtained, as shown in FIG. 12, a hydrophilic layer 102 continuous with water is formed between the catalyst-supporting carbon 100 and the polymer electrolyte 101 that are in contact with each other. For this reason, if an anode electrode or a cathode electrode of a fuel cell is manufactured using this electrode paste, protons easily move through the hydrophilic layer in the anode electrode or the cathode electrode. In addition, since the proton exchange group is oriented on the hydrophilic layer side of the polymer electrolyte, the hydrophilic layer is effectively used for proton transfer.
Further, since the hydrophobic portion of the polymer electrolyte is oriented toward the pores and the pores become hydrophobic, it is difficult for water to accumulate, preventing bleeding, and inhibiting gas diffusion. For this reason, in the fuel cell system, H ₃ O ⁺ moves well at the anode electrode, electrolyte membrane, and cathode electrode of the MEA, and a high output can be obtained while being lightly humidified or not humidified.

JP 2006-140061 A JP 2006-140062 JP Handbook of Fuel Cells (John Wiley & Sons Lid. (2003)) vol.3 p538

  However, the electrode pastes described in Patent Documents 1 and 2 have been requested to further increase the output of a fuel cell using the same in light humidification or non-humidification.

  The present invention has been made in view of the above-described conventional circumstances, and is excellent in gas diffusibility and proton conductivity of a catalyst layer, and is a paste for a fuel cell electrode capable of obtaining high output while being lightly humidified or non-humidified. Making it possible to manufacture is a problem to be solved.

  In order to solve the above-described conventional problems, the present inventor has further conducted earnest research on the method for manufacturing the electrode paste described in Patent Document 1. As a result, they have discovered the surprising fact that the temperature at which the mixture of the catalyst-supporting carbon and water and the polymer electrolyte solution are agitated is closely related to the performance of the electrode paste. As a result of further research, it was found that the above problems can be solved when the temperature of the polymer electrolyte solution is lower than the temperature of the mixture of the catalyst-supporting carbon and water, and the present invention has been completed.

That is, the manufacturing method of the paste for an electrode of the fuel cell of the present invention is:
A paste for an electrode by mixing a catalyst-supporting carbon obtained by supporting a catalyst metal on a carbon powder and a polymer electrolyte solution for binding the catalyst-supporting carbons to each other and a gas-permeable substrate. A fuel cell electrode paste manufacturing method for obtaining
After the mixture containing the catalyst-supporting carbon and water is accommodated in the chamber, the mixture is subjected to its own weight by a centrifugal stirring method in which the chamber is rotated while revolving the chamber while applying centrifugal force to the mixture. A first step of stirring to obtain a first intermediate;
And a second step of mixing the first intermediate and a polymer electrolyte solution having a temperature lower than the temperature of the first intermediate to obtain an electrode paste.

  In the method for producing a paste for a fuel cell electrode according to the present invention, first, as a first step, a mixture containing the catalyst-supporting carbon and water is contained in a chamber, and then the mixture is centrifuged to revolve the mixture. While applying force, the mixture is stirred by its own weight by rotating the chamber to obtain a first intermediate. As a result, air can be forced out of the surface of each catalyst-supporting carbon, and the surface can be covered with water. At this time, since foreign substances such as balls and propellers are not used for imparting centrifugal force and stirring, contact between the catalyst-supporting carbons is hardly hindered.

And as a 2nd process, the 1st intermediate and the polymer electrolyte solution made into temperature lower than the temperature of this 1st intermediate are mixed, and the paste for electrodes is obtained. Thereby, it is possible to obtain a fuel cell electrode paste which is excellent in gas diffusibility and proton conductivity of the catalyst layer, and can obtain high output while being lightly humidified or non-humidified.
The reason why the electrode paste having such excellent properties can be obtained in the second step can be considered as follows. That is, the first intermediate obtained in the first step forms an agglomerate in which many catalyst-carrying carbons are gathered, and is in a state where water is wrapped around the surface of the agglomerate. In the second step, when the polymer electrolyte solution is added and mixed, if the temperature of the polymer electrolyte solution is lower than the temperature of the first intermediate, the temperature of the polymer electrolyte solution existing around the agglomerate is locally increased. Therefore, the mobility of polyelectrolyte molecules is selectively enhanced. The thus activated polyelectrolyte molecules are oriented with a hydrophilic functional group directed toward the agglomerate side that has become hydrophilic due to the presence of water in order to obtain a more stable orientation. Thus, in the electrode paste obtained by the present invention, hydrophilic layers that are continuous with each other by water are formed between the catalyst-supporting carbon and the polymer electrolyte that are in contact with each other. For this reason, if an anode electrode or a cathode electrode of a fuel cell is manufactured using this electrode paste, protons are easily moved by the hydrophilic layer in the anode electrode or the cathode electrode. In addition, since the proton exchange group of the polymer electrolyte is strongly oriented to the water present on the surface of the agglomerate, the hydrophilic layer is effectively used for proton transfer. Furthermore, since the hydrophobic group portion of the polymer electrolyte is arranged away from the water present on the surface of the agglomerate, the gas path becomes hydrophobic and the water prevents the gas path from being blocked. Therefore, if the fuel cell is constituted by the fuel cell electrode paste of the present invention, a high output can be obtained while being lightly humidified or non-humidified.

  In the present invention, the mixing in the second step is preferably performed by a centrifugal stirring method, similarly to the stirring in the first step. As a result, the particle diameter of the agglomerate covered with the polymer electrolyte can be reduced, and many three-phase interfaces necessary for the electrode reaction (that is, the polymer electrolyte responsible for proton conductivity and the electron conductivity) It is possible to form an interface that is composed of three phases of carbon to be borne and vacancies to diffuse oxygen. For this reason, gas diffusion, electrode reaction, ion conduction, and electron conduction are smoothed, and as a result, a fuel cell electrode paste is obtained that provides higher output.

  In addition, the second step includes a temperature adjusting step for setting the first intermediate to a predetermined temperature, a preparatory stirring step for stirring the first intermediate by the centrifugal stirring method after the temperature adjusting step, and the stirred first intermediate And a polyelectrolyte solution having a temperature lower than the temperature of the first intermediate in the chamber, and a main stirring step of stirring by a centrifugal stirring method.

  In the present invention, the temperature of the first intermediate in the second step and the temperature of the polymer electrolyte solution greatly affect the characteristics of the obtained electrode paste. According to the experiment results of the present inventors, the temperature of the first intermediate when mixing the first intermediate and the polymer electrolyte solution is 30 to 70 ° C., and the temperature of the polymer electrolyte solution is 20 to 20 ° C. The temperature is preferably 50 ° C. Particularly preferred is a temperature of the first intermediate of 35-50 ° C. and a temperature of the polymer electrolyte solution of 20-40 ° C., and most preferred is a temperature of the first intermediate of 35-50 ° C. The temperature is 20-30 ° C.

  The method for producing a membrane electrode assembly for a fuel cell according to the present invention comprises a polymer solid electrolyte layer, a cathode electrode joined to one surface of the polymer solid electrolyte layer and supplied with air, and the polymer solid electrolyte layer. In a manufacturing method of a membrane electrode assembly of a fuel cell having an anode electrode joined to another surface and supplied with fuel, an electrode formed by applying the electrode paste on one surface of the substrate is the cathode electrode and the anode. It is used for at least one of the poles.

  In the membrane electrode assembly thus obtained, hydrophilic layers that are continuous with each other are formed by water between the catalyst-supporting carbon and the polymer electrolyte that are in contact with each other. For this reason, protons tend to move in the anode and cathode by the hydrophilic layer. In addition, since the polymer electrolyte has proton exchange groups highly oriented on the hydrophilic layer side, the hydrophilic layer is effectively used for proton transfer.

  DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention will be described below with reference to the drawings.

(Examples 1-4)
-Manufacture of electrode paste The electrode paste of an Example was manufactured according to the flowchart shown in FIG. First, 1 g of commercially available catalyst-supporting carbon was put in a beaker, vacuum-dried in a vacuum drying chamber at 150 ° C. for 1 hour, and then pulverized by a pulverizer (pulverization step S1). The reason why the catalyst-carrying carbon is vacuum-dried is to remove the impurities on the surface of each catalyst-carrying carbon as much as possible and to bring it close to hydrophilicity. The catalyst-supporting carbon is obtained by supporting 60% by weight of a catalyst metal composed of Pt on a substantially spherical carbon powder.

Thereafter, in the water addition step S2, 12 g of water was added to the vacuum-dried catalyst-supported carbon, and in the stirring step S3, centrifugal stirring was performed by the following method to obtain a first intermediate. That is, first, a rotation / revolution centrifugal stirrer (manufactured by Keyence Corporation, trade name “Hybrid Mixer HM-500”) having the chamber 10 shown in FIG. 2 was prepared. The chamber 10 includes a container 10a, the container 10a made of a lid 10b which seals the, to the center point O ₁ about, the axis P of the self is revolved at a high speed to draw a cone extending from the central point O ₁ And can be rotated around the axis P at high speed (see FIG. 3). In this chamber 10, a mixture 20 containing the aggregate 11 and water 12 equivalent to eight times the aggregate 11 was accommodated. Thereafter, the chamber 10 was revolved by rotating the chamber 10 by rotating the chamber 10 while applying centrifugal force to the mixture 20 by revolving the chamber 10.

  In the stirring step S3, as shown in FIG. 4, the water 12 having a low viscosity and a low specific gravity moves at high speed on the mixture 20 having a high viscosity and a high specific gravity. For this reason, the mixture 20 receives a large shearing force and is peeled off from the surface to form an agglomerate 32 composed of small lumps. In this way, as shown in FIG. 5, the water 33 surrounds the agglomerate 32 in which the catalyst-supporting carbon 31 is gathered, and the first intermediate 30 imparted with wettability to water is obtained. At this time, since foreign substances such as balls and propellers are not used for applying centrifugal force and stirring, contact between the catalyst-supporting carbons 31 is not hindered. The above pulverization step S1, water addition step S2 and stirring step S3 are the first step.

And in temperature control process S4 shown in FIG.
After heating on a warm bath at 0 ° C., the preparatory stirring step S5 is performed. This preparatory stirring step S5 is the same centrifugal stirring method as the stirring step S3, and its purpose is to cause a phenomenon in which water and catalyst-supported carbon are separated by evaporation and aggregation of water during heating in the temperature adjustment step S4. In this case, this is to return to the original state (that is, the state in which the water 33 surrounds the agglomerate 32 in which the catalyst-carrying carbon 31 is gathered as shown in FIG. 5).

Then, further as a polymer electrolyte addition step S6, the first intermediate product 30 which is a temperature T _1, by adding a predetermined temperature T ₂ and is Nafion® solution lower than the temperature T ₁ (Example 1 T ₁ = 40 ° C., T ₂ = 20 ° C., Example 2 T ₁ = 40 ° C., T ₂ = 35 ° C., Example 3 T ₁ = 30 ° C., T ₂ = 20 ° C., Example 4 T ₁ = 15 ° C., T ₂ = 20 ° C.), and further the main stirring step S7 is performed. The stirring method in the main stirring step S7 is also the same centrifugal stirring method as the stirring step S3 and the preparatory stirring step S5. For this reason, as shown in FIG. 6, a solution of Nafion (registered trademark) 34 having a low viscosity and a low specific gravity moves at a high speed on the first intermediate 30 having a high viscosity and a high specific gravity. For this reason, the first intermediate 30 receives a large shearing force and is peeled off from the surface to become a small agglomerate 32. At this time, since the temperature of the solution of Nafion (registered trademark) 34 present in the surroundings is lower than that of the first intermediate 30, the temperature of the solution of Nafion (registered trademark) 34 is locally higher only around the agglomerate 32. This will selectively enhance the mobility of the Nafion® molecule. The activated Nafion (registered trademark) 34 is oriented with the sulfonic acid group directed toward the agglomerate 32 that has become hydrophilic due to the presence of water 33 in order to obtain a more stable orientation. For this reason, as shown in FIG. 7, the water 33 surrounds the agglomerate 32 in which the catalyst-supporting carbon 31 is gathered, and the water 33 has a structure surrounded by Nafion (registered trademark) 34 in which sulfonic acid groups are strongly oriented. An electrode paste is obtained. In the electrode pastes of Examples 1 to 4 thus obtained, hydrophilic layers that are continuous with each other by water 33 are formed between each catalyst-supporting carbon 31 and Nafion (registered trademark) 34 that are in contact with each other.

(Comparative Example 1)
In Comparative Example _1, T 1 = 20 _℃, was T 2 = 20 ℃. Others are the same as in the above embodiment, and a description thereof will be omitted.

(Comparative Example 2)
In Comparative Example 2, T ₁ = 15 ° C. and T ₂ = 20 ° C. Others are the same as in the above embodiment, and a description thereof will be omitted.

Table 1, for each of Examples and Comparative Examples, the temperature T ₁ of the first intermediate 30 in the polymer electrolyte addition step S6, are summarized the temperature T ₂ of the Nafion® solution.

<Manufacture of fuel cell single layer cells>
Fuel cell single-layer cells were produced using the electrode pastes of Examples 1 to 4 and Comparative Examples 1 and 2 and evaluated.
That is, first, the electrode paste was printed on the surface of the carbon cloth so that the amount of Pt supported was 0.05 mg / cm ² and dried to obtain a diffusion layer. Instead of printing on the diffusion layer to form the reaction layer, the catalyst paste is printed on a polytetrafluoroethylene sheet, dried, and peeled to produce a self-supporting reaction layer film. The reaction layer may be formed by thermocompression bonding with a diffusion layer.

  A fuel cell single-layer cell shown in FIG. 8 was prepared using the diffusion layer prepared as described above. That is, two diffusion layers 1a and 1b are prepared, and reaction layers 3a and 3b are sandwiched between both sides of a polymer electrolyte membrane 2 made of Nafion (registered trademark), and are integrated by pressure bonding by hot pressing. Obtain a zygote. Further, separators 4a and 4b serving as oxygen and hydrogen gas supply passages are pressed against the outside by a mounting jig (not shown). In this way, the fuel cell single-layer cell 20 is manufactured, and the fuel cell single-layer cell 20 is further laminated to complete the fuel cell stack.

<Evaluation>
About the fuel cell single layer cell (electrode area 20.25cm < ² >) which concerns on Examples 1-4 and Comparative Examples 1 and 2 produced as mentioned above, cell temperature 70 degreeC-bubbler temperature 50 degreeC (humidity 40% RH) The relationship between the current density and the cell voltage and the relationship between the current density and the battery resistance were measured under the conditions of high temperature and low humidity. Air and hydrogen are parallel flow at normal pressure, air is 3.4 L / min, stoichiometric ratio 10 (at 1.0 A / cm ² ), hydrogen gas is 0.2 L / min, stoichiometric ratio 1.3 (at 1.0 A / cm ² ).

As a result, in the relationship between the current density and the cell voltage, in Comparative Example 1 and Comparative Example 2 where (temperature T ₁ of the first intermediate) <(temperature T _{2 of the} Nafion (registered trademark) solution), FIG. As shown in FIG. 4, the cell voltage is significantly reduced with the increase of the current density, and a rapid voltage drop is recognized particularly when the current density is 0.8 A / cm ² or more. As for the relationship between current density and battery resistance, an increase in resistance was observed at 0.7 A / cm ² or more.
In contrast, in the T _1> T ₂ and the Examples 1 and 2, a gradual decrease of the cell voltage with increasing current density, observed rapid decline even 0.8 A / cm ² or more I couldn't. Moreover, also in the relationship between the current density and the battery resistance, the resistance gradually decreased to 1.0 A / cm ² and was lower than those of Comparative Examples 1 and 2.
Although not shown in FIG. 9, the results of Examples 3 and 4 were almost the same as those of Example 2.

  The present invention is not limited to the description of the embodiments of the invention. Various modifications may be included in the present invention as long as those skilled in the art can easily conceive without departing from the description of the scope of claims.

  The present invention can be used for a moving power source for an electric vehicle or the like, or a stationary power source.

It is a flowchart which shows the manufacturing method of the paste for electrodes of the fuel cell of an Example and a comparative example. It is a schematic diagram of the chamber of a rotation / revolution type centrifugal stirrer. It is a schematic diagram which shows the rotation state of the chamber of a rotation / revolution type centrifugal stirrer. It is an expansion schematic diagram which shows the stirring state in stirring process S3. It is the expansion schematic diagram which showed the state of the agglomerate after completion | finish of stirring process S3. It is an expansion schematic diagram which shows the stirring state in this stirring process S7. It is the expansion schematic diagram which showed the state of the agglomerate after this stirring process S7 completion | finish. It is a schematic cross section of a fuel cell single layer cell. It is a graph which shows the relationship between a current density and a cell voltage, and the relationship between a current density and battery resistance. It is a schematic cross section which shows the conventional MEA. It is a figure which shows the manufacturing method of the conventional paste for electrodes. It is a model expanded sectional view of the catalyst layer using the paste for electrodes manufactured by the method described in patent documents 1.

Explanation of symbols

S1, S2, S3 ... 1st process (S1 ... crushing process, S2 ... water addition process, S3 ... stirring process)
S4, S5, S6, S7 ... 2nd process (S4 ... temperature control process, S5 ... preparatory stirring process, S6 ... polymer electrolyte addition process, S7 ... main stirring process)
DESCRIPTION OF SYMBOLS 10 ... Chamber 11 ... Aggregate 12 ... Water 31 ... Catalyst support carbon 1a, 1b ... Base material (diffusion layer)
30 ... first intermediate 10 ... chamber 3a ... cathode electrode (reaction layer)
3b ... Anode electrode (reaction layer)
1a, 1b, 2, 3a, 3b ... membrane electrode assembly (1a, 1b ... diffusion layer, 2 ... polymer electrolyte membrane, 3a, 3b ... reaction layer)

Claims (6)

A paste for an electrode by mixing a catalyst-supporting carbon obtained by supporting a catalyst metal on a carbon powder and a polymer electrolyte solution for binding the catalyst-supporting carbons to each other and a gas-permeable substrate. A fuel cell electrode paste manufacturing method for obtaining
After the mixture containing the catalyst-supporting carbon and water is accommodated in the chamber, the mixture is subjected to its own weight by a centrifugal stirring method in which the chamber is rotated while revolving the chamber while applying centrifugal force to the mixture. A first step of stirring to obtain a first intermediate;
A fuel cell comprising: a second step of mixing the first intermediate and a polymer electrolyte solution having a temperature lower than the temperature of the first intermediate to obtain an electrode paste. Manufacturing method of electrode paste.   2. The method for producing an electrode paste for a fuel cell according to claim 1, wherein the mixing in the second step is performed by the centrifugal stirring method. The second step includes
A temperature adjusting step of setting the first intermediate to a predetermined temperature;
A preparatory stirring step of stirring the first intermediate by the centrifugal stirring method after the temperature adjustment step;
A main stirring step of containing the stirred first intermediate and the polymer electrolyte solution having a temperature lower than the temperature of the first intermediate in a chamber and stirring by the centrifugal stirring method;
A method for producing a paste for an electrode of a fuel cell according to claim 1, wherein the paste is provided.   The temperature of the first intermediate when the first intermediate and the polymer electrolyte solution are accommodated in the chamber in the main stirring step is 30 to 70 ° C., and the temperature of the polymer electrolyte solution is 20 to The method for producing a paste for a fuel cell electrode according to any one of claims 1 to 3, wherein the temperature is set to 50 ° C.   A fuel cell electrode paste produced by the method according to any one of claims 1 to 4. A solid polymer electrolyte layer, a cathode electrode joined to one surface of the polymer solid electrolyte layer and supplied with air, and an anode electrode joined to the other surface of the polymer solid electrolyte layer and supplied with fuel In the method of manufacturing a fuel cell membrane electrode assembly,
A method for producing a membrane electrode assembly for a fuel cell, comprising using an electrode formed by applying the electrode paste according to claim 5 on one surface of the substrate as at least one of the cathode electrode and the anode electrode.

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