JP4392222B2 - Method for manufacturing membrane-electrode structure - Google Patents

Method for manufacturing membrane-electrode structure Download PDF

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JP4392222B2
JP4392222B2 JP2003371049A JP2003371049A JP4392222B2 JP 4392222 B2 JP4392222 B2 JP 4392222B2 JP 2003371049 A JP2003371049 A JP 2003371049A JP 2003371049 A JP2003371049 A JP 2003371049A JP 4392222 B2 JP4392222 B2 JP 4392222B2
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electrode
conductive material
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catalyst layer
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JP2004221056A (en
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洋 新海
雅樹 谷
克彦 高山
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本田技研工業株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/56Manufacturing of fuel cells

Description

  The present invention relates to a method for producing a membrane-electrode structure used for a polymer electrolyte fuel cell.

  While oil resources are depleted, environmental problems such as global warming due to consumption of fossil fuels are becoming more serious. Therefore, a fuel cell has been attracting attention as a clean electric power source for electric motors that does not generate carbon dioxide, and has been extensively developed, and part of it has begun to be put into practical use. When the fuel cell is mounted on an automobile or the like, a solid polymer fuel cell using a polymer electrolyte membrane is preferably used because a high voltage and a large current can be easily obtained.

  As the membrane-electrode structure used in the polymer electrolyte fuel cell, as shown in FIG. 7, catalyst particles in which a catalyst such as platinum is supported on carbon particles such as carbon black are integrated by an ion conductive polymer binder. A pair of electrode catalyst layers 3, 3 formed so as to sandwich the polymer electrolyte membrane 1 capable of ion conduction between the electrode catalyst layers 3, 3, A membrane-electrode structure 10 in which diffusion electrodes 5 and 5 are laminated on 3 is known.

  In the membrane-electrode structure 10, the electrode catalyst layer 3 is hydrophilic for proton movement, discharge of generated water, and the like. On the other hand, the diffusion electrode 5 has a structure in which a porous water-repellent layer 7 is formed on the carbon base material layer 6 for the diffusion of the reducing gas or the oxidizing gas. The electrode catalyst layer 3 is laminated. The membrane-electrode structure 10 constitutes a polymer electrolyte fuel cell by further laminating a separator also serving as a gas passage on each diffusion electrode 5, 5.

  In the polymer electrolyte fuel cell, one electrode catalyst layer 3 is used as a fuel electrode, and a reducing gas such as hydrogen or methanol is introduced through the diffusion electrode 5 on the fuel electrode side, and the other electrode catalyst layer 3 is supplied with oxygen. An oxidizing gas such as air or oxygen is introduced as an electrode through the diffusion electrode 5 on the oxygen electrode side. In this way, on the fuel electrode side, protons are generated from the reducing gas by the action of the catalyst contained in the electrode catalyst layer 3, and the protons pass through the polymer electrolyte membrane 1 to the oxygen electrode side. It moves to the electrode catalyst layer 3. The protons react with the oxidizing gas introduced into the oxygen electrode by the action of the catalyst contained in the electrode catalyst layer 3 on the oxygen electrode side electrode 3 to produce water. Therefore, an electric current can be taken out by connecting the fuel electrode and the oxygen electrode via a conducting wire.

  Conventionally, the electrode structure is manufactured by laminating the diffusion electrode 5 on a laminate in which the electrode catalyst layers 3 and 3 are bonded to both surfaces of the polymer electrolyte membrane 1, and pressing the electrode under heating. (For example, refer to Patent Document 1).

However, in the conventional manufacturing method, since the diffusion electrode 5 is laminated on the hydrophilic electrode catalyst layer 3 via the water repellent layer 7, the electrode catalyst layer 3 and the diffusion electrode 5 are not pressed even when pressed under heating. Inadequate adhesion may not be obtained. If sufficient adhesion between the electrode catalyst layer 3 and the diffusion electrode 5 cannot be obtained, when a polymer electrolyte fuel cell is constructed using the membrane-electrode structure 10, a resistance overvoltage is generated. Increases power generation performance.
JP 2001-345110 A

  An object of the present invention is to provide a method for producing a membrane-electrode structure that can eliminate such disadvantages and obtain excellent adhesion between an electrode catalyst layer and a diffusion electrode.

In order to achieve this object, a method for producing a membrane-electrode structure according to the present invention comprises a sheet of a catalyst paste containing an electron conductive material carrying a catalyst, an ion conductive material, and a pore forming material composed of carbon fibers. A step of forming an electrode catalyst layer by applying it on a substrate-like support and drying, and pressing the electrode catalyst layer under heat on both sides of the polymer electrolyte membrane to perform thermal transfer, and on both sides of the polymer electrolyte membrane. A step of forming a laminated body to which the electrode catalyst layer is bonded, and a first slurry containing a water repellent material and an electron conductive material are applied on the carbon substrate layer and dried to form a water repellent layer. Then, a second slurry containing an electron conductive material, an ion conductive material, and a pore forming material made of carbon fiber is applied onto the water repellent layer and dried to form a hydrophilic layer, A diffusion electrode comprising the carbon substrate, a water repellent layer, and a hydrophilic layer is formed. A step of laminating the diffusion electrode formed in advance on the electrocatalyst layer of the laminate through the hydrophilic layer and pressing under heating to integrate the laminate and the diffusion electrode And a step of performing.

In the production method of the present invention, when forming the diffusion electrode, first, a water-repellent layer is formed on the carbon substrate layer, and then a second slurry is applied on the water-repellent layer, dried, and hydrophilic. Forming a conductive layer. It said second slurry, except that it does not contain catalysts, has the same composition as the catalyst paste. However, the hydrophilic layer can be formed by applying the second slurry onto the water-repellent layer and drying it to obtain excellent adhesion with the water-repellent layer. .

  Next, in the production method of the present invention, a diffusion electrode in which the hydrophilic layer is previously formed on the water-repellent layer as described above is laminated on the electrode catalyst layer via the hydrophilic layer, and heated under heating. Press on. Since the hydrophilic layer formed on the diffusion electrode is formed of the second slurry, it has the same composition as the electrode catalyst layer except that it does not contain a catalyst. Therefore, the hydrophilic layer can be easily joined to the electrode catalyst layer by pressing under heating as described above, and excellent adhesion can be obtained between the electrode catalyst layer. .

  As a result, according to the production method of the present invention, the electrode catalyst layer and the diffusion electrode are integrated through the hydrophilic layer, and excellent adhesion is provided between the electrode catalyst layer and the diffusion electrode. Obtainable.

Moreover, the manufacturing method of this invention is characterized by the said 2nd slurry containing the pore formation material which consists of carbon fibers . By applying the second slurry containing the pre KiHosoana forming material on the water-repellent layer, followed by drying, to obtain a hydrophilic layer which pores are formed between the carbon fibers The reducing gas or oxidizing gas can be diffused through the pores.

The production method of the present invention is characterized in that the catalyst paste includes a pore forming material made of carbon fiber . By applying the catalyst paste containing pre KiHosoana forming material on the sheet-like support, by drying, it is possible to obtain the electrode catalyst layer pores are formed between the carbon fibers The reducing gas or oxidizing gas can be diffused through the pores, and the reducing gas or oxidizing gas and the catalyst can be advantageously brought into contact with each other. Further, the generated water can be advantageously discharged through the pores.

In the manufacturing method of the present invention, before against the pore volume in the range of pore sizes 0.01~1μm formed on the hydrophilic layer by KiHoso pore forming material, a pore forming material into the electrode catalyst layer By forming the hydrophilic layer and the electrocatalyst layer so that the value of the ratio of the volume of pores in the pore diameter range of 0.01 to 1 μm is less than 1.0, the reducing gas or Excellent adhesion between the electrode catalyst layer and the diffusion electrode can be obtained without inhibiting the diffusion of the oxidizing gas. On the other hand, when the value of the ratio is 1.0 or more, even if sufficient adhesion can be obtained between the electrode catalyst layer and the diffusion electrode, the reducing gas or oxidizing property can be obtained. Gas diffusion is hindered and concentration overvoltage increases.

  In the production method of the present invention, the ratio of the weight of the ion conductive material contained in the electrode catalyst layer to the weight of the ion conductive material contained in the hydrophilic layer is 1.0 to 1.4. By forming the hydrophilic layer and the electrode catalyst layer so as to be in the range, excellent adhesion between the electrode catalyst layer and the diffusion electrode can be obtained. On the other hand, when the value of the ratio is less than 1.0 or greater than 1.4, the water retention amount balance changes between the electrode catalyst layer and the diffusion electrode, and the activation overvoltage or concentration overvoltage is increased. As a result, the power generation performance may not be sufficient.

  Furthermore, in the production method of the present invention, the ratio of the weight of the solid content contained in the electrode catalyst layer to the weight of the solid content contained in the hydrophilic layer is in the range of 1.0 to 3.5. As described above, by forming the hydrophilic layer and the electrode catalyst layer, excellent adhesion can be obtained between the electrode catalyst layer and the diffusion electrode. On the other hand, when the value of the ratio is less than 1.0 or greater than 3.5, sufficient adhesion may not be obtained between the electrode catalyst layer and the diffusion electrode.

  The present invention also resides in a polymer electrolyte fuel cell using the membrane-electrode structure obtained by the production method. The polymer electrolyte fuel cell of the present invention can be used, for example, as a power source, a backup power source, etc. for electrical devices such as personal computers and mobile phones. The polymer electrolyte fuel cell of the present invention can also be used as power for transportation equipment such as automobiles and submarines.

  Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is a production process diagram schematically showing a method for producing a membrane-electrode structure of this embodiment, and FIGS. 2 and 3 are graphs showing the power generation performance of the membrane-electrode structure of this embodiment. . FIG. 4 is a graph showing the relationship between the pore volume ratio between the hydrophilic layer and the electrode catalyst layer and the power generation performance in the membrane-electrode structure of this embodiment, and FIG. 5 is the graph showing the hydrophilic layer and the electrode catalyst layer. 6 is a graph showing the relationship between the weight ratio of the ion conductive material and the power generation performance, and FIG. 6 is a graph showing the relationship between the solid weight ratio of the hydrophilic layer and the electrode catalyst layer and the power generation performance.

  In the production method of this embodiment, first, a sulfonated polyarylene polymer is prepared. In the present specification, the “sulfonated polyarylene polymer” means a sulfonated polymer having the following formula.


Examples of the divalent organic group include —CO—, —CONH—, — (CF 2 ) p — (p is an integer of 1 to 10), —C (CF 3 ) 2 —, —COO—, —SO—. Electron-withdrawing groups such as —SO 2 —, groups such as —O—, —S—, —CH═CH—, —C≡C—, and electron-donating groups represented by the following formula: Can do.


Examples of the divalent electron-withdrawing group include —CO—, —CONH—, — (CF 2 ) p — (p is an integer of 1 to 10), —C (CF 3 ) 2 —, —COO—. , —SO—, —SO 2 — and the like.

  The sulfonated polyarylene-based polymer can be prepared, for example, by adding concentrated sulfuric acid to the polyarylene-based polymer represented by the formula (1) for sulfonation.


In the formula (1), m: n = 0.5 to 100: 99.5 to 0, and l is an integer of 1 or more.

  The polyarylene polymer represented by the formula (1) can be prepared, for example, as follows. First, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF) 67.3 parts by weight, 4,4′-dichlorobenzophenone 53.5 parts by weight Parts and 34.6 parts by weight of potassium carbonate are heated in a mixed solvent of N, N-dimethylacetamide and toluene under a nitrogen atmosphere and reacted at 130 ° C. with stirring. The water produced by the reaction is azeotroped with toluene and removed from the system, and the reaction is carried out until almost no water is observed, and then the reaction temperature is gradually raised to 150 ° C. to remove the toluene. After continuing the reaction at 150 ° C. for 10 hours, 3.3 parts by weight of 4,4′-dichlorobenzophenone is added, and the reaction is further performed for 5 hours.

  After cooling the obtained reaction liquid, the precipitate of the by-produced inorganic compound is removed by filtration, and the filtrate is put into methanol. The precipitated product is filtered off, collected, dried, and dissolved in tetrahydrofuran. By reprecipitating this with methanol, an oligomer represented by the following formula (2) is obtained. In the oligomer of the formula (2) obtained as described above, the average value of l is, for example, 18.9.


Next, 28.4 parts by weight of the oligomer represented by the formula (2), 29.2 parts by weight of 2,5-dichloro-4 ′-(4-phenoxy) phenoxybenzophenone, bis (triphenylphosphine) nickel dichloride, 1. 37 parts by weight, 1.36 parts by weight of sodium iodide, 7.34 parts by weight of triphenylphosphine, and 11.0 parts by weight of zinc powder are placed in a flask and purged with dry nitrogen. Next, N-methyl-2-pyrrolidone is added, and the mixture is heated to 80 ° C. and polymerized for 4 hours with stirring. The polymerization solution is diluted with tetrahydrofuran, coagulated with hydrochloric acid / methanol and recovered. The recovered product is repeatedly washed with methanol and dissolved in tetrahydrofuran. This is purified by reprecipitation with methanol, and the polymer collected by filtration is vacuum dried to obtain a polyarylene polymer represented by the formula (1).

  Sulfonation of the polyarylene polymer represented by the formula (1) can be performed, for example, by adding 96% sulfuric acid to the polyarylene polymer and stirring for 24 hours under a nitrogen stream.

  As the sulfonated polyarylene polymer, a sulfonated polyarylene polymer represented by the following formula (3) may be used instead of the sulfonated product of the polyarylene polymer represented by the formula (1).


The copolymer represented by the formula (3) is obtained by copolymerizing the monomer represented by the following formula (4) and the oligomer represented by the formula (2), and then sulfonate group (—SO 3 CH (CH 3 ) C 2 H 5 ) can be obtained by hydrolyzing the sulfonic acid group (—SO 3 H).


In the production method of this embodiment, the sulfonated polyarylene polymer is then dissolved in a solvent such as N-methylpyrrolidone to prepare a polymer electrolyte solution. Then, a film is formed from the polymer electrolyte solution by a casting method and dried in an oven to form a polymer electrolyte film 1 having a dry film thickness of 20 to 60 μm, for example, as shown in FIG.

  Next, catalyst particles such as platinum are supported on an electron conductive material such as carbon black (furnace black) at a weight ratio of, for example, catalyst: electron conductive material = 50: 50 to prepare catalyst particles. Next, the catalyst particles and carbon fibers (for example, VGCF (trade name) manufactured by Showa Denko KK) as a pore forming material are combined with a perfluoroalkylenesulfonic acid polymer compound (for example, an ion conductive material solution) A catalyst paste is prepared by uniformly dispersing in a Nafion (trade name) manufactured by DuPont, for example, at a weight ratio of catalyst particles: pore forming material: ion conductive material = 5: 2: 7.

Next, on the fluororesin-based release film 2 shown in FIG. 1 (b), the catalyst paste is screen-printed so that the catalyst amount is, for example, 0.4 to 0.5 mg / cm 2, and dried. The electrode catalyst layer 3 is formed. Next, as shown in FIG. 1 (c), the polymer electrolyte membrane 1 is sandwiched between a pair of electrode catalyst layers 3, 3 and hot pressed from above the fluororesin release film 2.

  The hot pressing is performed at a temperature in the range of 100 to 160 ° C., for example, with a surface pressure in the range of 2 to 5 MPa, for 5 to 30 minutes. As a result, the electrode catalyst layer 3 is transferred to the polymer electrolyte membrane 1 side and joined to the polymer electrolyte membrane 1. Next, when the fluororesin-based release film 2 is peeled off, a laminate 4 in which the polymer electrolyte membrane 1 is sandwiched between a pair of electrode catalyst layers 3 and 3 is obtained as shown in FIG.

  Since the electrode catalyst layer 3 is formed of the catalyst paste containing the carbon fibers, the electrode catalyst layer 3 is a porous body in which pores are formed in the gaps between the carbon fibers.

  Next, the diffusion electrode 5 shown in FIG. 1 (e) is formed. The diffusion electrode 5 is formed by first using polytetrafluoroethylene (PTFE) particles as a water repellent material and carbon black as an electron conductive material, for example, a weight of water repellent material: electron conductive material = 5: 4. A first slurry is prepared by uniformly dispersing the mixture obtained by mixing at a ratio in ethylene glycol. And the said 1st slurry is apply | coated on the carbon paper 6 as a carbon base material layer, and it is made to dry, and the water-repellent layer 7 with a dry film thickness of 10-20 micrometers is formed, for example.

  Next, carbon black as an electron conductive material and the carbon fiber as a pore forming material are combined with a perfluoroalkylene sulfonic acid polymer compound (for example, Nafion (trade name, manufactured by DuPont) as an ion conductive material solution. )) A second slurry is prepared by uniformly dispersing the solution in a weight ratio of, for example, electron conductive material: pore forming material: ion conductive material = 5: 4: 14. Then, the second slurry is applied on the water-repellent layer 7 and dried to form the hydrophilic layer 8 having a dry film thickness of 2 to 10 μm, for example.

  As a result, the diffusion electrode 5 including the water repellent layer 7 on the carbon paper 6 and further including the hydrophilic layer 8 on the water repellent layer 7 is formed. Since the hydrophilic layer 8 is formed by the second slurry containing the carbon fibers, it is a porous body in which pores are formed in the gaps between the carbon fibers.

  Once the diffusion electrode 5 is formed, the diffusion electrode 5 is next laminated on the electrode catalyst layer 3 via the hydrophilic layer 8 and hot pressed from above the carbon paper 6 as shown in FIG. . The hot press is performed for 2 to 10 minutes at a temperature in the range of 80 to 140 ° C. with a surface pressure in the range of 1 to 5 MPa. As a result, a membrane-electrode structure 9 in which the diffusion electrode 5 is bonded to the electrode catalyst layer 3 through the hydrophilic layer 8 is obtained.

  Next, in the membrane-electrode structure 9, the pore diameter range of 0.01 to 1 μm formed in the electrode catalyst layer 3 with respect to the pore volume in the pore diameter range of 0.01 to 1 μm formed in the hydrophilic layer 8. The value of the volume ratio of the pores is less than 1.0. The ratio of the weight of the ion conductive material contained in the electrode catalyst layer 3 to the weight of the ion conductive material contained in the hydrophilic layer 8 is in the range of 1.0 to 1.4. The ratio of the weight of the solid content contained in the electrode catalyst layer 3 to the weight of the solid content contained in the hydrophilic layer 8 is in the range of 1.0 to 3.5.

  Next, except that the membrane-electrode structure 9 obtained by the production method of the present embodiment and the hydrophilic layer 8 are not formed using the sulfonated product of the polyarylene polymer represented by the formula (1). Using the membrane-electrode structure 10 shown in FIG. 7 obtained by the same manufacturing method as in the present embodiment, a solid polymer fuel cell is configured to generate power, and the terminal voltage with respect to the current density and the resistance overvoltage And measured. FIG. 2 shows changes in terminal voltage with respect to current density, and FIG. 3 shows changes in resistance overvoltage with respect to current density.

  From FIG. 2, according to the membrane-electrode structure 9 (Example) in which the hydrophilic layer 8 was formed, the terminal voltage was higher than that in the membrane-electrode structure 10 (Comparative Example) in which the hydrophilic layer 8 was not formed. It is clear that high power generation performance can be obtained. Further, according to the membrane-electrode structure 9 (Example) in which the hydrophilic layer 8 is formed, the resistance overvoltage is lower than that in the membrane-electrode structure 10 (Comparative Example) in which the hydrophilic layer 8 is not formed. It is clear that excellent power generation performance can be obtained.

  As shown in FIGS. 2 and 3, excellent power generation performance is obtained in the membrane-electrode structure 9 (Example) in which the hydrophilic layer 8 is formed. Therefore, in the membrane-electrode structure 9, the electrode catalyst layer 3 and It is clear that excellent adhesion with the diffusion electrode 5 is obtained.

Next, in the membrane-electrode structure 9, the pore diameter formed in the electrode catalyst layer 3 with respect to the pore volume (V A ) in the pore diameter range of 0.01 to 1 μm formed in the hydrophilic layer 8 is 0.01. the value of the ratio (V B / V a) of the pore volume range of ~1μm (V B), when varying between 0.5 and 1.5, the ratio (V B / V a The change of the terminal voltage with respect to the value of) is shown in FIG. In FIG. 4, the terminal voltage of the test membrane-electrode structure 9 having the highest terminal voltage was expressed as a ratio to the terminal voltage, where 100 was the terminal voltage.

From FIG. 4, when the value of the ratio (V B / V A ) is less than 1.0, excellent adhesion between the electrode catalyst layer 3 and the diffusion electrode 5 can be obtained, and power generation performance can be improved. It is clear that it has no effect. On the other hand, when the value of the ratio (V B / V A ) exceeds 1.0, the diffusion of gas is inhibited by the hydrophilic layer 8, so that the concentration overvoltage rises and the power generation performance is reduced. ing.

Next, in the membrane-electrode structure 9, the ratio of the weight (W B1 ) of the ion conductive material contained in the electrode catalyst layer 3 to the weight (W A1 ) of the ion conductive material contained in the hydrophilic layer 8 ( the value of W B1 / W A1), when varying between 0.8 to 1.6, shown in Figure 5 the value change in the terminal voltage with respect to the ratio (W B1 / W A1). In FIG. 5, the terminal voltage of the sample membrane-electrode structure 9 having the highest terminal voltage is defined as 100, and the terminal voltage is expressed as a ratio to the terminal voltage.

From FIG. 5, when the value of the ratio (W B1 / W A1 ) is in the range of 1.0 to 1.4, excellent adhesion is obtained between the electrode catalyst layer 3 and the diffusion electrode 5. It is clear that power generation performance is not affected. On the other hand, when the value of the ratio (W B1 / W A1 ) is less than 1.0, the activation overvoltage increases, and when the value of the ratio (W B1 / W A1 ) exceeds 1.4 The concentration overvoltage increases and the power generation performance decreases.

Therefore, only when the value of the ratio (W B1 / W A1 ) is in the range of 1.0 to 1.4, the power generation performance is not deteriorated between the electrode catalyst layer 3 and the diffusion electrode 5. Excellent adhesion can be obtained.

Next, in the membrane-electrode structure 9, the ratio (W B2 / W) of the solid content (W B2 ) contained in the electrode catalyst layer 3 to the solid content (W A2 ) contained in the hydrophilic layer 8. the value of A2), when varying between 0.8 to 4.0, Figure 6 shows the change in the terminal voltage with respect to the value of the ratio (W B2 / W A2). In FIG. 6, the terminal voltage of the sample membrane-electrode structure 9 having the highest terminal voltage is defined as 100, and the terminal voltage is expressed as a ratio to the terminal voltage.

From FIG. 6, when the value of the ratio (W B2 / W A2 ) is in the range of 1.0 to 3.5, excellent adhesion can be obtained between the electrode catalyst layer 3 and the diffusion electrode 5. It is clear that power generation performance is not affected. On the other hand, when the value of the ratio (W B2 / W A2 ) is less than 1.0, the activation overvoltage increases, and when the value of the ratio (W B2 / W A2 ) exceeds 3.5 The concentration overvoltage increases and the power generation performance decreases.

The manufacturing process figure which shows typically an example of the manufacturing method of the membrane-electrode structure of this invention. The graph which shows an example of the electric power generation performance of the membrane-electrode structure of this invention. The graph which shows an example of the electric power generation performance of the membrane-electrode structure of this invention. The graph which shows the relationship between the pore volume ratio of the hydrophilic layer and electrode catalyst layer in the membrane-electrode structure of this invention, and power generation performance. The graph which shows the relationship between the weight ratio of the ion conductive material of the hydrophilic layer and electrode catalyst layer in the membrane-electrode structure of this invention, and power generation performance. The graph which shows the relationship between the weight ratio of the solid content of the hydrophilic layer and electrode catalyst layer in the membrane-electrode structure of this invention, and power generation performance. Explanatory sectional drawing which shows the example of 1 structure of the conventional membrane-electrode structure.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Polymer electrolyte membrane, 2 ... Sheet-like support body, 3 ... Electrode catalyst layer, 4 ... Laminated body, 5 ... Diffusion electrode, 6 ... Carbon base material layer, 7 ... Water-repellent layer, 8 ... Hydrophilic layer, 9 ... Membrane-electrode structure.

Claims (7)

  1. Applying a catalyst paste containing an electron conductive material supporting a catalyst, an ion conductive material, and a pore-forming material made of carbon fiber on a sheet-like support and drying to form an electrode catalyst layer;
    A step of pressing the electrode catalyst layer on both sides of the polymer electrolyte membrane under heat to thermally transfer, and forming a laminate in which the electrode catalyst layer is bonded to both sides of the polymer electrolyte membrane; and
    A first slurry containing a water repellent material and an electron conductive material is applied onto the carbon substrate layer and dried to form a water repellent layer, and then from the electron conductive material, the ion conductive material and the carbon fiber. A second slurry containing a pore-forming material is applied onto the water-repellent layer and dried to form a hydrophilic layer, and the diffusion comprising the carbon substrate, the water-repellent layer and the hydrophilic layer Forming an electrode;
    Laminating the diffusion electrode formed in advance on the electrocatalyst layer of the laminate through the hydrophilic layer and pressing it under heating to integrate the laminate and the diffusion electrode; A process for producing a membrane-electrode structure, comprising:
  2. The pore diameter formed in the electrode catalyst layer by the pore forming material is 0.01-1 μm with respect to the volume of pores in the pore diameter range of 0.01-1 μm formed in the hydrophilic layer by the pore forming material. 2. The membrane-electrode structure according to claim 1 , wherein the hydrophilic layer and the electrode catalyst layer are formed so that the value of the ratio of the volume of pores in the range is less than 1.0. Method.
  3. The hydrophilic ratio is such that the ratio of the weight of the ion conductive material contained in the electrode catalyst layer to the weight of the ion conductive material contained in the hydrophilic layer is in the range of 1.0 to 1.4. The method for producing a membrane-electrode structure according to claim 1 or 2, wherein a conductive layer and an electrode catalyst layer are formed.
  4. The hydrophilic layer and the electrode so that the ratio of the weight of the solid content contained in the electrode catalyst layer to the weight of the solid content contained in the hydrophilic layer is in the range of 1.0 to 3.5. The method for producing a membrane-electrode structure according to any one of claims 1 to 3, wherein a catalyst layer is formed.
  5. Applying a catalyst paste containing an electron conductive material supporting a catalyst, an ion conductive material, and a pore-forming material made of carbon fiber on a sheet-like support and drying to form an electrode catalyst layer;
    A step of pressing the electrode catalyst layer on both sides of the polymer electrolyte membrane under heat to thermally transfer, and forming a laminate in which the electrode catalyst layer is bonded to both sides of the polymer electrolyte membrane; and
    A first slurry containing a water repellent material and an electron conductive material is applied onto the carbon substrate layer and dried to form a water repellent layer, and then from the electron conductive material, the ion conductive material and the carbon fiber. A second slurry containing a pore-forming material is applied onto the water-repellent layer and dried to form a hydrophilic layer, and the diffusion comprising the carbon substrate, the water-repellent layer and the hydrophilic layer Forming an electrode;
    Laminating the diffusion electrode formed in advance on the electrocatalyst layer of the laminate through the hydrophilic layer and pressing it under heating to integrate the laminate and the diffusion electrode; A solid polymer fuel cell comprising a membrane-electrode structure obtained by a production method comprising:
  6. Applying a catalyst paste containing an electron conductive material supporting a catalyst, an ion conductive material, and a pore-forming material made of carbon fiber on a sheet-like support and drying to form an electrode catalyst layer;
    Thermally transferring the electrode catalyst layer to both surfaces of the polymer electrolyte membrane, and forming a laminate in which the electrode catalyst layer is bonded to both surfaces of the polymer electrolyte membrane;
    A first slurry containing a water repellent material and an electron conductive material is applied onto the carbon substrate layer and dried to form a water repellent layer, and then from the electron conductive material, the ion conductive material and the carbon fiber. A second slurry containing a pore-forming material is applied onto the water-repellent layer and dried to form a hydrophilic layer, and the diffusion comprising the carbon substrate, the water-repellent layer and the hydrophilic layer Forming an electrode;
    Laminating the diffusion electrode formed in advance on the electrocatalyst layer of the laminate through the hydrophilic layer and pressing it under heating to integrate the laminate and the diffusion electrode; An electrical apparatus comprising a polymer electrolyte fuel cell comprising a membrane-electrode structure obtained by a production method comprising:
  7. Applying a catalyst paste containing an electron conductive material supporting a catalyst, an ion conductive material, and a pore-forming material made of carbon fiber on a sheet-like support and drying to form an electrode catalyst layer;
    Thermally transferring the electrode catalyst layer to both surfaces of the polymer electrolyte membrane, and forming a laminate in which the electrode catalyst layer is bonded to both surfaces of the polymer electrolyte membrane;
    A first slurry containing a water repellent material and an electron conductive material is applied onto the carbon substrate layer and dried to form a water repellent layer, and then from the electron conductive material, the ion conductive material and the carbon fiber. A second slurry containing a pore-forming material is applied onto the water-repellent layer and dried to form a hydrophilic layer, and the diffusion comprising the carbon substrate, the water-repellent layer and the hydrophilic layer Forming an electrode;
    Laminating the diffusion electrode formed in advance on the electrocatalyst layer of the laminate through the hydrophilic layer and pressing it under heating to integrate the laminate and the diffusion electrode; A transportation apparatus characterized by using a polymer electrolyte fuel cell comprising a membrane-electrode structure obtained by a production method comprising:
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JP5257589B2 (en) * 2008-08-19 2013-08-07 トヨタ自動車株式会社 Method for manufacturing membrane electrode assembly, membrane electrode assembly manufactured by the method, and fuel cell including the membrane electrode assembly
JP2010153145A (en) * 2008-12-24 2010-07-08 Toshiba Corp Anode electrode for direct-methanol fuel cells, and membrane-electrode complex and fuel cell using the same
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JP6009252B2 (en) * 2012-07-13 2016-10-19 日本バイリーン株式会社 Moisture management sheet, gas diffusion sheet, membrane-electrode assembly, and polymer electrolyte fuel cell

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