JP2010205657A - Membrane electrode assembly, method for manufacturing the same, and polymer electrolyte fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a membrane electrode assembly hardly aggregating particles during coating ad drying by using catalyst ink in which change with time of viscosity is small, having uniform power generation performance; and to provide a method for manufacturing the membrane electrode assembly and a polymer electrolyte fuel cell. <P>SOLUTION: In the method for manufacturing the membrane electrode assembly forming a coating film on a substrate by applying catalyst ink containing at least particles on which a catalyst material is carried, a polymer electrolyte, and a solvent on the substrate, forming a pair of electrode catalyst layers by removing the solvent of the coating film comprising the catalyst ink coated on the substrate, and transferring the pair of electrode catalyst layers to a polymer electrolyte membrane, the catalyst ink has a rate of change of viscosity (B) after 5 minutes from removing the a shear rate to viscosity (A) immediately after the shear rate is removed ä(B-A)/A}×100[%] existing in a range of 0≤ä(B-A)/A}×100≤100 when a shear rate of 800 s-<SP>1</SP>or more is applied and then the shear rate is removed and the catalyst ink is made to stand. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a membrane electrode assembly, a production method thereof, and a solid polymer fuel cell, and more particularly, a membrane electrode assembly for adjusting the viscosity of a catalyst ink used for an electrode catalyst layer of the membrane electrode assembly, a production method thereof, and a solid The present invention relates to a polymer fuel cell.

  A membrane electrode assembly for a polymer electrolyte fuel cell has a structure in which an electrode catalyst layer is bonded to both surfaces of a polymer electrolyte membrane. By stacking several hundred sets of gas diffusion layers and separators arranged outside the electrode catalyst layer of the membrane electrode assembly, the fuel cell can be used. In producing such a fuel cell, the power generation performance of each membrane electrode assembly needs to be uniform without variation.

  The membrane electrode assembly manufacturing method includes applying a catalyst ink to a base material, forming a coating film on the base material, and removing the solvent of the coating film formed on the base material to form an electrode catalyst layer. A method of manufacturing a membrane electrode assembly is known by a drying step of transferring and a transfer step of transferring an electrode catalyst layer formed on a base material to a polymer electrolyte membrane.

  As a catalyst ink suitable for the production of an electrode catalyst layer having a uniform appearance, Patent Document 1 discloses a catalyst ink having a thixotropic property. When such a catalyst ink is applied using a coating apparatus that has a shear rate at the nozzle tip, the viscosity of the catalyst ink is low during application and the catalyst ink tends to flow. Since the liquid dripping is less likely to occur on the substrate, an electrode catalyst layer with less streaks and unevenness and a constant thickness can be produced (see Patent Document 1).

  However, in Patent Document 1, even if the thickness and appearance of the electrode catalyst layer are uniform, the power generation performance of the membrane electrode assembly is not necessarily constant. Since the cell reaction of the fuel cell is carried out in the electrode catalyst layer of the membrane electrode assembly, if the internal structure of the electrode catalyst layer changes, the gas diffusion performance and proton conduction performance change, so the power generation performance of the membrane electrode assembly Change. Therefore, in order to keep the power generation performance of the membrane electrode assembly uniform, it is necessary to make the structure inside the electrode catalyst layer constant.

  The structure inside the electrode catalyst layer is determined in the process of applying the catalyst ink and drying the solvent in the production of the membrane electrode assembly.

  In order to keep the internal structure of the electrode catalyst layer constant, a catalyst ink that tends to change in viscosity with time is considered undesirable. In a catalyst ink that causes a thixotropic change in viscosity, it is considered that the viscosity is changed by gradually agglomerating particles carrying the catalyst substance. When such a catalyst ink is used, if the agglomeration of particles occurs faster than the time until coating and drying, the internal structure of the coating becomes irregular in the plane, and the performance of the electrode catalyst layer is made uniform. You will not be able to.

JP 2002-270189 A

  The present invention relates to a membrane electrode assembly having a uniform power generation performance, a method for producing the same, and a polymer electrolyte fuel, using a catalyst ink having a small change in viscosity over time, which is less likely to cause particle aggregation during the coating and drying processes. It is to provide a battery.

  The present inventor has found that when a catalyst ink having a small change in viscosity with time is used, it is possible to produce a membrane electrode assembly in which particle aggregation hardly occurs during the coating and drying process and the power generation performance is uniform.

The invention according to claim 1 of the present invention is a method of manufacturing a membrane electrode assembly having a structure in which a polymer electrolyte membrane is sandwiched between a pair of electrode catalyst layers, wherein at least particles carrying a catalyst substance, a polymer electrolyte, A catalyst ink containing a solvent is applied to a base material to form a coating film on the base material, a solvent of the coating film made of the catalyst ink applied on the base material is removed to form a pair of electrode catalyst layers, In the method for producing a membrane electrode assembly in which an electrode catalyst layer is transferred to a polymer electrolyte membrane, the catalyst ink is subjected to a shear rate of 800 s ^-1 or more and then left to stand after removing the shear rate. The change rate {(BA) / A} × 100 [%] of the viscosity (B) after 5 minutes with respect to the viscosity (A) immediately after is 0 ≦ {(BA) / A} × 100 ≦ 100 It is a manufacturing method of a membrane electrode assembly characterized by being in the range of .

The invention according to claim 2 of the present invention is the method for producing a membrane electrode assembly according to claim 1, wherein a shear rate of 800 s ^-1 or more is applied to the catalyst ink when applied. It is.

  The invention according to claim 3 of the present invention is a membrane electrode assembly manufactured by the method for manufacturing a membrane electrode assembly according to claim 1 or 2.

  The invention according to claim 4 of the present invention is characterized in that the membrane electrode assembly according to claim 3 is sandwiched between a pair of gas diffusion layers, and the pair of gas diffusion layers is sandwiched between a pair of separators. And a solid polymer fuel cell.

  According to the present invention, using a catalyst ink having a small change in viscosity over time, a membrane electrode assembly having a uniform power generation performance, a method for producing the membrane electrode assembly, and a solid polymer are less likely to cause aggregation of particles during the coating and drying processes. A fuel cell can be provided.

(A) is a schematic perspective view which shows the membrane electrode assembly which concerns on embodiment of this invention, (b) is a schematic sectional drawing which shows the membrane electrode assembly which concerns on embodiment of this invention. It is a schematic diagram which shows the change of the viscosity of the catalyst ink which concerns on embodiment of this invention. 1 is a schematic cross-sectional view showing a polymer electrolyte fuel cell according to an embodiment of the present invention. It is a graph which shows the standard deviation of the voltage of the membrane electrode assembly which concerns on an Example.

  Hereinafter, a membrane electrode assembly (MEA) and a polymer electrolyte fuel cell according to an embodiment of the present invention will be described. Note that the present invention is not limited to the embodiments described below, and modifications such as design changes can be made based on the knowledge of those skilled in the art, and such modifications are added. The embodiments may be included in the scope of the present invention.

  First, a membrane electrode assembly according to an embodiment of the present invention will be described, and a method for manufacturing the membrane electrode assembly will be described.

  FIG. 1A is a schematic perspective view showing a membrane electrode assembly according to an embodiment of the present invention, and FIG. 1B is a schematic cross-sectional schematic diagram showing a membrane electrode assembly according to an embodiment of the present invention. It is. As shown in FIGS. 1A and 1B, a membrane electrode assembly (MEA) 12 according to an embodiment of the present invention has a first electrode catalyst layer 2 and a second electrode catalyst layer 2 on both sides of a polymer electrolyte membrane 1. The electrode catalyst layer 3 is joined and sandwiched. Moreover, as shown in FIG.1 (b), the membrane electrode assembly 12 which concerns on embodiment of this invention is not covered with the 1st electrode catalyst layer 2 and the 2nd electrode catalyst layer 3, but a polymer electrolyte membrane 1 has an exposed outer edge S. The polymer electrolyte membrane 1 is made larger than the first electrode catalyst layer 2 and the second electrode catalyst layer 3, and the outer periphery S of the first electrode catalyst layer 2 and the second electrode catalyst layer 3 has a high height. By exposing the molecular electrolyte membrane 1, it is possible to prevent a short circuit or a leak between the first electrode catalyst layer 2 and the second electrode catalyst layer 3.

  Next, the manufacturing method of the membrane electrode assembly which concerns on embodiment of this invention is demonstrated. The manufacturing method of the membrane electrode assembly which concerns on embodiment of this invention apply | coated catalyst ink to the base material (not shown), and formed the coating process on a base material, and formed on the base material. A drying step of removing the solvent of the coating film to form the first electrode catalyst layer 2 and the second electrode catalyst layer 3, and the first electrode catalyst layer 2 and the second electrode catalyst layer formed on the substrate A transfer step of transferring 3 to the polymer electrolyte membrane 1.

  The polymer electrolyte membrane 1 used for the membrane electrode assembly 12 according to the embodiment of the present invention may be any one having proton conductivity, for example, a fluorine polymer electrolyte or a hydrocarbon polymer electrolyte. Can be used. Examples of the fluoropolymer electrolyte include Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by Asahi Glass Co., Ltd., Aciplex (registered trademark) manufactured by Asahi Kasei Co., Ltd., and Gore Select (registered trademark) manufactured by Gore. Etc. can be used. Among them, a Nafion (registered trademark) material manufactured by DuPont can be suitably used as the polymer electrolyte membrane 1.

  The catalyst ink used in the method for producing the membrane / electrode assembly 12 according to the embodiment of the present invention contains at least particles carrying a catalyst substance, a polymer electrolyte, and a solvent.

  As a catalyst used in the embodiment of the present invention, platinum, palladium, ruthenium, iridium, rhodium, osmium, platinum group elements, iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, A metal such as aluminum or an alloy thereof, an oxide, a double oxide, or the like can be used. The particle size of these catalysts is preferably 0.5 nm or more and 20 nm or less. More preferably, 1 nm or more and 5 nm or less are good. When the particle size of the catalyst exceeds 20 nm, the activity of the catalyst is lowered, and when the particle size of the catalyst material is less than 0.5 nm, the stability of the catalyst is lowered.

  Carbon particles can be used as the particles for supporting the catalyst. Any carbon particles can be used as long as they are in the form of fine particles and have conductivity and are not affected by the catalyst. Carbon black, graphite, graphite, activated carbon, carbon fiber, carbon nanotube, and fullerene are used. it can. The particle size of the carbon particles is preferably about 10 nm to 1000 nm. More preferably, it is 10 nm or more and 100 nm or less. When the particle size of the carbon particles is less than 10 nm, it becomes difficult to form an electron conduction path, and when the particle size of the carbon particles exceeds 1000 nm, the gas diffusibility of the electrode catalyst layer and the utilization rate of the catalyst are decreased. End up.

  As the polymer electrolyte contained in the catalyst ink according to the embodiment of the present invention, any material having proton conductivity may be used, and the same material as the polymer electrolyte membrane 1 described above can be used. -Based polymer electrolytes and hydrocarbon-based polymer electrolytes can be used. As the fluorine-based polymer electrolyte, for example, a Nafion (registered trademark) material manufactured by DuPont can be used. As the hydrocarbon polymer electrolyte membrane, polymer electrolytes such as sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene can be used. Among these, a Nafion (registered trademark) material manufactured by DuPont can be suitably used as the polymer electrolyte. In consideration of the adhesion between the first electrode catalyst layer 2 and the second electrode catalyst layer 3 and the polymer electrolyte membrane 1, it is preferable to use the same material as the polymer electrolyte membrane 1.

  In the case of the catalyst ink, a solvent is used to disperse the particles carrying the catalyst substance and the polymer electrolyte. Desirably, the solvent includes particles carrying a catalyst substance and a volatile organic solvent that does not react with the polymer electrolyte. These solvents are selected in consideration of the dispersibility of the particles carrying the catalyst substance and the polymer electrolyte. The amount is determined in consideration of the viscosity of the catalyst ink. Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, 2-heptanol, benzyl alcohol, and the like, acetone, methyl ethyl ketone , Ketones such as methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, pentanone, heptanone, cyclohexanone, methyl cyclohexanone, acetonyl acetone, diethyl ketone, dipropyl ketone, diisobutyl ketone, tetrahydrofuran, tetrahydropyran , Dioxane, diethylene glycol dimethyl ether, anisole, methoxytoluene, diethyl ether, dipropyl ether, dibutyl ether Ethers such as Tell, amines such as isopropylamine, butylamine, isobutylamine, cyclohexylamine, diethylamine, aniline, propyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, acetic acid Esters such as pentyl, isopentyl acetate, methyl propionate, ethyl propionate, butyl propionate, other acetic acid, propionic acid, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monomethyl ether , Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diacetone alcohol, 1-methoxy-2-propano Le and the like are used. Moreover, water can also be used as a solvent. Moreover, what mixed 2 or more types of these solvents can also be used.

  In addition, those using lower alcohol as the solvent have a high risk of ignition, and when using such a solvent, it is preferable to use a mixed solvent with water. The amount of water added is not particularly limited as long as the polymer electrolyte is not separated to cause white turbidity or gelation.

  Considering the drying temperature, the catalyst ink solvent preferably has a boiling point in the range of 60 ° C to 120 ° C.

  FIG. 2 is a schematic diagram showing the behavior of the viscosity of the catalyst ink according to the embodiment of the present invention. FIG. 2 shows viscosity on the vertical axis and time [minutes] on the horizontal axis. As shown in FIG. 2, the viscosity of the catalyst ink according to the embodiment of the present invention decreases when shear is applied, and then gradually recovers and increases when the ink is left to stand except for shear. It is thought that the change in viscosity is caused by the destruction and construction of the aggregate structure. When shear is applied to the catalyst ink, the aggregated structure is destroyed and the viscosity is lowered. However, when the catalyst ink is left to stand except for shear, the aggregated structure is gradually built up and the viscosity increases.

  In the production of the first electrode catalyst layer 2 and the second electrode catalyst layer 3, the structure of the first electrode catalyst layer 2 and the second electrode catalyst layer 3 of the membrane electrode assembly 12 is the coating process and the drying process. It is determined that the process after the drying process does not change significantly. The structure of the 1st electrode catalyst layer 2 and the 2nd electrode catalyst layer 3 is the arrangement | positioning of the particle | grains and the polymer electrolyte which carry | supported the catalyst substance, and the 1st electrode catalyst layer 2 and the 2nd electrode by these arrangement | positioning. The gas diffusion performance and proton conduction performance of the catalyst layer 3 change.

  When a catalyst ink having a fast agglomeration structure is used, particles agglomerate inside the coating film after the catalyst ink is applied. When such agglomeration of particles occurs irregularly faster than the time until the coating film is dried, the arrangement of the particles becomes uneven in the plane of the coating film, and the power generation of the membrane electrode assembly 12 is performed. Performance is not uniform.

  Although the time required for the coating process and the drying process varies depending on the type and amount of the solvent, it is desirable that the time is shorter than the time when the aggregation of particles occurs, and within 5 minutes considering the productivity of the membrane electrode assembly 12. Is desirable. In the catalyst ink according to the embodiment of the present invention, when the viscosity immediately after starting to stand except shear is A, and the viscosity 5 minutes after starting standing is B, the viscosity change after 5 minutes The rate [%] was set to {(BA) / A} × 100. In the embodiment of the present invention, in order to manufacture the membrane electrode assembly 12 with uniform power generation performance, the rate of change in the viscosity of the catalyst ink after 5 minutes from the start of standing is 0 ≦ {(BA ) / A} × 100 ≦ 100 was found to be preferable. More preferably, the range of 0 ≦ {(BA) / A) × 100 ≦ 50 is good.

  If the rate of change of the viscosity of the catalyst ink 5 minutes after starting to stand is in the range of 0 ≦ {(B−A) / A} × 100 ≦ 100, the change with time of viscosity is small and particle aggregation is small. A catalyst ink that does not easily occur can be used, and the in-plane variation of the structure inside the coating film is reduced, and a membrane electrode assembly with uniform power generation performance can be obtained.

  A catalyst ink having a viscosity change rate in the above range can be produced by a method such as addition of a dispersant, change in solid content, or conditions for dispersion treatment.

  Any dispersant may be used as long as it prevents aggregation of particles carrying the catalyst substance, and an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used.

  The solid content in the catalyst ink is preferably 1% by mass or more and 50% by mass or less. If the solid content in the catalyst ink exceeds 50% by mass, the surfaces of the first electrode catalyst layer 2 and the second electrode catalyst layer 3 are likely to crack, and if it is less than 1% by mass. This is because the time for producing a coating film having a predetermined thickness becomes longer and the productivity is lowered.

The solid content is composed of particles carrying a catalyst substance and a polymer electrolyte, but if the content of particles carrying the catalyst substance exceeds 90% by mass, the viscosity increases even at the same solid content, and 20% by mass. If it is less than 1, the viscosity tends to be low. From this viewpoint, the proportion of the particles carrying the catalyst substance in the solid content is preferably 20% by mass or more and 90% by mass or less. Further, the viscosity of the catalyst ink at this time is preferably about 1 × 10 ⁻⁵ Pa · s to 2 Pa · s, more preferably 5 × 10 ⁻³ Pa · s to 0.2 Pa · s.

  Distributed processing can be performed using various apparatuses. Examples thereof include a ball mill, a roll mill, a shear mill, a wet mill, an ultrasonic dispersion treatment, and a homogenizer.

  As a method for applying the catalyst ink, any method may be used as long as shear is applied to the catalyst ink in the application step. Even when the catalyst ink is aggregated immediately before the coating step, if the aggregated structure is destroyed by applying shear to the catalyst ink, the viscosity is lowered and unevenness can be suppressed.

When a die coater is used in the coating apparatus, a shear rate can be applied to the catalyst ink at the tip of the nozzle. The shear rate applied at this time varies depending on the shape of the nozzle and the like, but is preferably 800 s ⁻¹ or more. More preferably, it is in the range of 800 s ⁻¹ or more to several thousand s ⁻¹ .

When a shear rate of 800 s ⁻¹ or more is given in the coating process, even when the catalyst ink is agglomerated until immediately before coating, the viscosity of the catalyst ink is low during coating and the catalyst ink tends to flow, and there is little unevenness. One electrode catalyst layer 2 and second electrode catalyst layer 3 can be formed.

  A transfer film or a gas diffusion layer can be used as the substrate used in the coating process. The transfer film may be made of any material having good transferability, such as ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroperfluoroalkyl vinyl ether copolymer. Fluorine resins such as (PFA) and polytetrafluoroethylene (PTFE) can be used. Polymer films such as polyimide, polyethylene terephthalate, polyamide (nylon), polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyetherimide, polyarylate, and polyethylene naphthalate can also be used. When a transfer film is used as the substrate, the transfer film can be peeled off after the transfer step to form a membrane electrode assembly having catalyst layers on both sides of the polymer electrolyte membrane.

  Moreover, as a gas diffusion layer, what is used for the normal fuel cell can be used. Specifically, porous carbon materials such as carbon cloth, carbon paper, and nonwoven fabric can be used as the gas diffusion layer. The gas diffusion layer can also be used as a substrate. At this time, it is not necessary to peel off the base material that is the gas diffusion layer after the transfer step.

  When the substrate is a gas diffusion layer, it is not necessary to peel the substrate after hot pressing. As a gas diffusion layer, what is used for the normal fuel cell can be used. Specifically, porous carbon materials such as carbon cloth, carbon paper, and nonwoven fabric can be used as the gas diffusion layer. A target layer may be formed between the gas diffusion layer and the first electrode catalyst layer 2 and the second electrode catalyst layer 3. The mesh layer is a layer that prevents the catalyst ink from penetrating into the gas diffusion layer, and deposits on the mesh layer to form a three-phase interface even when the coating amount is small. Such a filler layer can be formed, for example, by kneading carbon particles and a fluororesin and sintering them at a temperature equal to or higher than the melting point of the fluororesin. As the fluororesin, polytetrafluoroethylene (PTFE) or the like can be used.

  The temperature of the drying step is not particularly limited, but it is preferable to carry out at a room temperature or higher and 150 ° C. or lower. If the temperature exceeds 150 ° C., it is not appropriate because unevenness of drying of the electrode catalyst layer and the effect of heat treatment on the polymer electrolyte increase. When the boiling point of the solvent in the catalyst ink is not lower than the boiling point of the solvent, the evaporation rate is remarkably increased.

  As the transfer step, a method in which the first electrode catalyst layer 2 and the second electrode catalyst layer 3 formed on the base material and the polymer electrolyte membrane 1 are heated, pressurized and pressure-bonded can be used. A press method or the like can be used. In the hot press method, the first electrode catalyst layer 2 and the second electrode catalyst layer 3 formed on the base material are formed on both sides of the polymer electrolyte membrane 1 by using the first electrode catalyst layer 2 and the second electrode. The catalyst layer 3 is disposed so as to be in contact with the polymer electrolyte membrane 1. For the purpose of evenly distributing the pressure, a hot press member may be disposed on the outer side.

  The temperature of hot pressing is generally set in the vicinity of the glass transition point of the polymer electrolyte of the polymer electrolyte membrane 1, the first electrode catalyst layer 2, and the second electrode catalyst layer 3, but is 100 ° C or higher. Is desirable.

  After the transfer step, when a transfer film is used as the base material, the transfer film is peeled off, and the membrane electrode joint is provided with the first electrode catalyst layer 2 and the second electrode catalyst layer 3 on both surfaces of the polymer electrolyte membrane 1. It can be the body 12. Further, when the gas diffusion layer is used as the base material, it is not necessary to peel off the base material.

  Next, a polymer electrolyte fuel cell using the membrane electrode assembly according to the embodiment of the present invention will be described. FIG. 3 is a schematic exploded view showing a polymer electrolyte fuel cell.

  As shown in FIG. 3, the polymer electrolyte fuel cell according to the embodiment of the present invention has an air electrode facing the first electrode catalyst layer 2 and the second electrode catalyst layer 3 of the membrane electrode assembly 12. A side gas diffusion layer 4 and a fuel electrode side gas diffusion layer 5 are disposed. Thereby, the air electrode 6 and the fuel electrode 7 are comprised. Then, a set of separators 10 made of a conductive and impermeable material, which is provided with a gas flow path 8 for gas flow and is provided with a cooling water flow path 9 for cooling water flow on the opposing main surface, is disposed. For example, hydrogen gas is supplied as a fuel gas from the gas flow path 8 of the separator 10 on the fuel electrode 7 side. On the other hand, a gas containing oxygen, for example, is supplied as an oxidant gas from the gas flow path 8 of the separator 10 on the air electrode 6 side. An electromotive force can be generated between the fuel electrode 7 and the air electrode 6 by causing an electrode reaction between hydrogen and oxygen gas of the fuel gas in the presence of the catalyst.

  The solid polymer fuel cell shown in FIG. 3 includes a set of separators 11 and a polymer electrolyte membrane 1, a first electrode catalyst layer 2, a second electrode catalyst layer 3, an air electrode side gas diffusion layer 5, and a fuel electrode side. A solid polymer fuel cell having a so-called single cell structure in which the gas diffusion layer 6 is sandwiched, but in the embodiment of the present invention, a plurality of cells are stacked via a separator 11 to form a fuel cell. It can also be.

(Preparation of catalyst ink)
A platinum-supported carbon catalyst (support: Ketjen) with a platinum-supporting amount of 30% by mass and Nafion (registered trademark, manufactured by Dupont) of a 20% by mass polymer electrolyte solution are placed in a container, and a mixed solvent of water and ethanol is used as a solid content. Was added at a ratio of 5% by mass, and dispersion treatment was performed with a planetary ball mill.

(Preparation of membrane electrode assembly 12)
The catalyst ink was applied using a doctor blade with a PTFE sheet as a base material and dried in an oven set at 80 ° C. for 5 minutes. A pair of this was punched into a square, and the polymer electrolyte membrane was placed using Nafion 212 (registered trademark, manufactured by Dupont) so as to face both sides of the polymer electrolyte membrane, and hot pressed at 130 ° C. for 10 minutes. . After hot pressing, the membrane electrode assembly 12 was produced by peeling off the PTFE as the base material.

(Preparation of catalyst ink)
To the same platinum-supported carbon catalyst and polymer electrolyte as in Example 1, a mixed solvent of water and ethanol was added at a ratio of 20% by mass of solid content, and a solid acid (1% by mass of solid content) was further added as a dispersant. In addition, dispersion processing was performed with a planetary ball mill.

(Production of membrane electrode assembly)
A membrane / electrode assembly was produced in the same manner as in Example 1.

[Comparative Example 1]
(Preparation of catalyst ink)
A platinum-supported carbon catalyst (support: Ketjen) with a platinum-supporting amount of 30% by mass and Nafion (registered trademark, manufactured by Dupont) of a 20% by mass polymer electrolyte solution are placed in a container, and a mixed solvent of water and ethanol is used as a solid content. Was added at a rate of 20% by mass, and dispersed with a planetary ball mill.

(Production of membrane electrode assembly)
The catalyst ink was applied with a PTFE sheet as a base material using a doctor blade, dried in an oven set at 80 ° C. for 5 minutes, punched into a square, and Nafion 212 (registered trademark) on the polymer electrolyte membrane. , Manufactured by Dupont Co., Ltd.) so as to face both surfaces of the polymer electrolyte membrane, and hot-pressed at 130 ° C. for 10 minutes. After hot pressing, the base electrode PTFE was peeled off to produce a membrane electrode assembly.

(Evaluation)
(Measurement of change in viscosity of catalyst ink over time)
The catalyst ink was processed with a stirring defoamer to perform defoaming treatment and to apply shear. After the defoaming treatment, a change rate [%] of the viscosity of the catalyst ink after 5 minutes from the end of the defoaming treatment was determined using a vibration viscometer (Viscomate, manufactured by Yamaichi Electronics Co., Ltd.).

(Power generation characteristic measurement)
The membrane electrode assemblies of Example 1, Example 2, and Comparative Example 1 were bonded to each other so as to sandwich a carbon cloth as a gas diffusion layer, and installed in a power generation evaluation cell. This was measured at a cell temperature of 80 ° C. using a fuel cell measuring device. The humidification condition was 25% RH for both the anode (fuel electrode 8) and the cathode (air electrode 6). Hydrogen was used as the fuel gas and air was used as the oxidant gas. The back pressure was 100 kPa. The power generation characteristics of the three membrane electrode assemblies were evaluated. As shown in FIG. 4, the current density values were 0.2 A / cm ² , 1.0 A / cm ² , and 1.2 A / cm ^2. The standard deviation of power was obtained.

(result)
Table 1 shows the rate of change in the viscosity of the catalyst ink. As shown in Table 1, the rate of change in viscosity after 5 minutes was 20% or less for the catalyst inks of Examples 1 and 2, but 71% for the catalyst ink of Comparative Example 1.

FIG. 4 is a graph showing the standard deviation of the voltage of the membrane electrode assembly according to the example of the present invention. As shown in FIG. 4, the vertical axis indicates standard deviation mV, and the horizontal axis indicates current density A / cm ² . The standard deviation mV of the electromotive force of the membrane electrode assembly 12 is 10 mV or less in each of the current density A / cm ² values in Example 1 and Example 2, and the electromotive force is larger than that of the membrane electrode assembly of Comparative Example 1. It can be seen that the standard deviation mV of is decreased.

  The present invention can produce a membrane electrode assembly in which particle agglomeration is unlikely to occur during the coating and drying process using a catalyst ink having a small change in viscosity with time, and the power generation performance is uniform using the membrane electrode assembly. A solid polymer electrolyte fuel cell could be obtained.

  The present invention can be suitably used for a polymer electrolyte fuel cell using a polymer electrolyte membrane, particularly a stationary cogeneration system and an automobile.

DESCRIPTION OF SYMBOLS 1 ... Polymer electrolyte membrane, 2 ... 1st electrode catalyst layer, 3 ... 2nd electrode catalyst layer, 4 ... Air electrode side gas diffusion layer, 5 ... Fuel electrode side gas diffusion layer, 6 ... Air electrode, 8 ... Fuel electrode, 8 ... Gas channel, 9 ... Cooling water channel, 10 ... Separator, 12 ... Membrane / electrode assembly, A ... Viscosity immediately after starting to stand except for shearing, B ... 5 minutes after starting to stand Viscosity of

Claims (4)

A method for producing a membrane electrode assembly having a structure in which a polymer electrolyte membrane is sandwiched between a pair of electrode catalyst layers,
A catalyst ink containing at least particles carrying a catalyst substance, a polymer electrolyte, and a solvent is applied to the substrate to form a coating film on the substrate;
Removing the solvent of the coating film made of the catalyst ink applied on the substrate to form the pair of electrode catalyst layers,
In the method of manufacturing a membrane electrode assembly for transferring the pair of electrode catalyst layers to the polymer electrolyte membrane,
When the catalyst ink is allowed to stand after removing a shear rate after giving a shear rate of 800 s ⁻¹ or more, the viscosity (B) after 5 minutes with respect to the viscosity (A) immediately after removing the shear rate. The rate of change {(BA) / A} × 100 [%] is in the range of 0 ≦ {(BA) / A} × 100 ≦ 100. 2. The method for producing a membrane electrode assembly according to claim 1, wherein a shear rate of 800 s ⁻¹ or more is applied to the catalyst ink when the coating is performed.   A membrane / electrode assembly produced by the method for producing a membrane / electrode assembly according to claim 1. 4. A polymer electrolyte fuel cell, wherein the membrane electrode assembly according to claim 3 is sandwiched between a pair of gas diffusion layers, and the pair of gas diffusion layers is sandwiched between a pair of separators.