JP5285225B2 - Method for producing solid polymer electrolyte membrane electrode assembly - Google Patents

Description

The present invention relates to a method for producing a solid polyelectrolyte film electrode conjugate.

  FIG. 10 shows a schematic configuration of an example of a conventional solid polymer electrolyte membrane electrode assembly (hereinafter referred to as “cell”).

As shown in FIG. 10, on one surface of the solid polymer electrolyte membrane 111 having proton (H ⁺ ) conductivity, conductive powder (for example, Pt—Ru-based metal etc.) supported on the surface (for example, , Carbon powder, etc.) are bound by a binder made of a solid polymer electrolyte material having proton conductivity. On the other surface of the solid polymer electrolyte membrane 111, conductive powder (for example, carbon powder) carrying catalyst particles (for example, Pt-based metal) is made of a solid polymer electrolyte material having proton conductivity. An oxide electrode film 113 bound by a binder is provided. In FIG. 10, 114 is a conductive gas diffusion layer, and 101 is an external circuit.

In a solid polymer electrolyte fuel cell having a stack in which a plurality of cells 110 configured as described above are stacked, a fuel gas 1 containing hydrogen (H ₂ ) is supplied to the fuel electrode membrane 112 side of the cell 110. At the same time, when the oxidizing gas 2 containing oxygen (O ₂ ) is supplied to the oxide electrode film 113 side, hydrogen comes into contact with the catalyst particles of the fuel electrode film 112 through the gas diffusion layer 114 and protons (H ⁺ ). And electrons (e ⁻ ), the protons are conducted through the binder and the solid polymer electrolyte membrane 111 of the fuel electrode membrane 112 and reach the oxide electrode membrane 113 side, and the electrons are transferred to the gas diffusion layer 114. And oxygen reaches the oxide electrode film 113 side via the external circuit 101, while oxygen comes into contact with the protons and the electrons on the catalyst particles of the oxide electrode film 113 through the gas diffusion layer 114 to form water (H By causing an electrochemical reaction of ₂ O), electricity flows through the external circuit 101.

JP-A-6-236762 ([Claims], [Example 1], [Example 2])

  Incidentally, in the solid polymer electrolyte fuel cell as described above, it is required to improve the power generation performance of the cell 110. For this reason, for example, in Patent Document 1 and the like, carbon particles are mixed with a pore-forming agent in a solvent, and the solidified product obtained by drying is pulverized and dispersed in a solvent, then formed into a film and dried. Then, after forming the porous carbon film by removing the pore forming agent, the catalyst metal is supported, and the pores are filled with a solid polymer electrolyte material and dried to obtain a space between the carbon particles. It has been proposed to improve the power generation performance with a cell obtained by obtaining an electrode film having a hole formed therein and joining the electrode film to a solid polymer electrolyte membrane.

  However, at present, there is a strong demand in the market for a cell with further improved power generation performance compared to the cell proposed in Patent Document 1.

In order to solve the above-mentioned problem, a method for producing a solid polymer electrolyte membrane / electrode assembly according to the first invention comprises a solid polymer electrolyte made of a hydrocarbon-based solid polymer electrolyte material having proton conductivity. A membrane and a conductive powder carrying catalyst particles are bound by a binder made of a solid polymer electrolyte material of a hydrocarbon resin having proton conductivity, and disposed on one surface of the solid polymer electrolyte membrane The other electrode of the solid polymer electrolyte membrane is formed by binding the fuel electrode membrane and the conductive powder carrying the catalyst particles with a binder made of a solid polymer electrolyte material of a hydrocarbon resin having proton conductivity. A solid polymer electrolyte membrane electrode assembly comprising: an oxide electrode membrane disposed on the at least one of the oxide electrode membrane and the fuel electrode membrane; A polymer chain gap forming agent comprising the conductive powder supporting the catalyst particles so as to allow gas molecules to pass through, a binder, and a polymer material dissolved in an organic solvent and water; Forming a film-like material from a mixture obtained by mixing an organic solvent with the organic solvent, forming a film-like material on the solid polymer electrolyte membrane, and washing the film-like material with water A polymer chain gap forming agent removing step of removing the polymer chain gap forming agent from the film-like material , and the organic solvent is dimethylformamide (DMF), dimethylacetamide (DMAc) In addition, the polymer chain gap forming agent is made of at least one of acetone, and the polymer chain gap forming agent is made of polyethylene glycol (PEG) .

Method for producing a solid polymer electrolyte membrane electrode assembly according to a second invention, in the first-th invention, the oxide electrode film, the conductive powder carrying the catalyst particles, carrying a Pt metal It is carbon powder, The said oxidation electrode film contains the hydrophilic carbon powder, It is characterized by the above-mentioned.

Method for producing a solid polymer electrolyte membrane electrode assembly according to a third invention, in the first-th invention, the oxide electrode film, the conductive powder carrying the catalyst particles, carrying a Pt metal a carbon powder having a hydrophilic carbon powder having a hydrophilic supporting Pt-Co alloy, a carbon powder having a mixture carrying hydrophilic and Pt metal and Pt-Co alloy, a hydrophilic support Pt metal carbon with a mixture of carbon powder having a hydrophilic carrying carbon powder and Pt-Co alloy, a carbon powder having a mixture carrying hydrophilic and Pt metal and Pt-Ru alloy, a hydrophilic support Pt metal It is one of a mixture of powder and hydrophilic carbon powder carrying a Pt—Ru alloy.

According to a fourth aspect of the present invention, there is provided a method for producing a solid polymer electrolyte membrane electrode assembly according to any one of the first to third aspects, wherein the polymer chain gap forming agent is mixed in the binder and the binder. The ratio is 1 to 80% by weight based on the total weight of the polymer chain gap forming agent.

According to the manufacturing method of the solid polymer electrolyte membrane electrode assembly according to the present invention, a solid polymer binder of the electrode film has a polymer chain gap for passing the gas molecules between adjacent polymer chains Since the electrolyte membrane electrode assembly can be easily manufactured , the supply of gas to the catalyst particles supported on the conductive powder can be promoted, and the polarization resistance of the electrode reaction can be greatly reduced. the solid polymer electrolyte membrane electrode assembly having further improved performance can it to easily manufactured.

An embodiment of the method for producing a solid polymer electrolyte membrane electrode assembly according to the present invention will be described with reference to Figures 1-4. FIG. 1 is a schematic configuration diagram of a solid polymer electrolyte membrane electrode assembly, FIG. 2 is an enlarged view of extraction of the fuel electrode membrane of FIG. 1, B is an enlarged view of extraction of a binder, and FIG. FIG. 4 is a procedure flow diagram of an embodiment of the method for producing the solid polymer electrolyte membrane electrode assembly of FIG. 1.

  The solid polymer electrolyte membrane electrode assembly (hereinafter referred to as “cell”) according to the present embodiment includes a solid polymer electrolyte membrane 11 made of a solid polymer electrolyte material having proton conductivity, as shown in FIGS. And a conductive electrode 12a carrying the catalyst particles 12b bound by a binder 12c made of a solid polymer electrolyte material having proton conductivity, and disposed on one surface of the solid polymer electrolyte membrane 11 The membrane 12 and the conductive powder 13a carrying the catalyst particles 13b are bound by a binder 13c made of a solid polymer electrolyte material having proton conductivity, and disposed on the other surface of the solid polymer electrolyte membrane 11. The cell 10 includes the oxide electrode film 13, and the fuel electrode film 12 and the binders 12 c and 13 c of the oxide electrode film 13 pass gas molecules between the adjacent polymer chains 12 ca and 13 ca. Is causing the polymer chains gap 12cb, those having a 13 cb.

The solid polymer electrolyte membrane 11 is a cation exchanger made of a fluorine resin or a hydrocarbon resin having a proton conductive group (for example, a sulfonic acid group (SO ₃ ⁻ ) or the like).

The fuel electrode membrane 12 is obtained by binding a conductive powder 12a carrying catalyst particles 12b with a binder 12c made of a solid polymer electrolyte material of fluorine resin or hydrocarbon resin having proton conductivity. And between the conductive powder 12a, pores (radial size: submicron to micron size level) 12d communicating between the surface on the solid polymer electrolyte membrane 11 side and the surface opposite to the surface. And the binder 12c has a polymer chain gap (molecular size level) 12cb that allows hydrogen molecules (H ₂ ) to pass between adjacent polymer chains 12ca.

The oxide electrode film 13 is obtained by binding a conductive powder 13a carrying catalyst particles 13b with a binder 13c made of a solid polymer electrolyte material of fluorine resin or hydrocarbon resin having proton conductivity. And between the conductive powder 13a, pores (radial size: submicron to micron size level) 13d communicating between the surface on the solid polymer electrolyte membrane 11 side and the surface opposite to the surface The binder 13c has a polymer chain gap (molecular size level) 13cb that allows oxygen molecules (O ₂ ) to pass between adjacent polymer chains 13ca.

  Here, as the solid polymer electrolyte material, in the case of a fluorine-based resin, examples of the resin serving as a skeleton include polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), and four fluorine. Ethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoroethylene copolymer (FEP), tetrafluoroethylene-6 hexafluoride Propylene copolymer (PFEP), polytrifluoroethylene chloride (PCTFE), ethylene trifluoride-ethylene copolymer (ECTFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) ) At least one of them, or a derivative thereof. , Manufactured by DuPont, "Nafion (registered trademark)", manufactured by Asahi Glass Co., Ltd. "Flemion (registered trademark)", mention may be made of Asahi Chemical Industry Co., Ltd. "reed plex (registered trademark)", and the like.

  In the case of a hydrocarbon resin, examples of the resin serving as a skeleton include polybenzoxazole (PBO), polybenzothiazole (PBT), polybenzimidazole (PBI), polyphenylene oxide (PPO), polyphenylene sulfoxide (PPSO), Polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPS / SO2), polyparaphenylene (PPP), polysulfone (PSU), polyphenylene sulfone (PPSU), polyether sulfone (PES), polyether ether sulfone (PEES), polyether Ketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyimide (PI), polyetherimide (PEI), polystyrene (PS), polystyrene Examples thereof include at least one of phenylene ether (PPE) and polyaryl ether sulfone (PAS), or derivatives thereof, vinyl polymers, diene polymers, ether polymers, and condensed ester types. At least one of a polymer and a condensed amide polymer (for example, polyethylene (PE), polypropylene (PP), polyvinylidene chloride (PVDC), polyethernitrile (PEN), polyacrylonitrile (PAN), polymethylpentene (TPX), ethylene-vinyl alcohol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), thermoplastic urethane (TPU), cellulose triacetate (CTA), etc.), or derivatives thereof, benzene in the main chain The thing etc. which provided the ring can be mentioned.

By the way, when the counter ion of the proton conductive group of the solid polymer electrolyte material is not a proton (H ⁺ ) but a metal ion such as a sodium ion, for example, the metal ion is ion-exchanged with an acid to generate a proton. The counter ion of the conductive group may be finally replaced with a proton.

  Examples of the catalyst particles 12b of the fuel electrode film 12 include a Pt—Ru alloy, and examples of the conductive powder 12a of the fuel electrode film 12 include a carbon powder. Can do.

  Examples of the catalyst particles 13b of the oxidation electrode film 13 include Pt metal and Pt-Co alloy. Examples of the conductive powder 13c of the oxidation electrode film 13 include carbon powder. Can be mentioned.

  In FIG. 1, 14 is a conductive gas diffusion layer, and 101 is an external circuit.

  Next, a method for manufacturing the cell 10 having such a structure will be described.

  As shown in FIG. 4, the catalyst particles 12b for the fuel electrode membrane 12 are supported on the conductive powder 12a (S11A), and a binder 12c and a polymer chain gap forming agent (for example, polyethylene glycol or the like) are used as a solvent (for example, In addition, the conductive powder 12a is added and mixed and dispersed (S12A), and this mixture is applied to one surface of the solid polymer electrolyte membrane 11. By drying by spraying or the like to remove the solvent, a film-like material is formed on one surface of the solid polymer electrolyte membrane 11 (S13A).

  Further, the catalyst particles 13b for the oxide electrode film 13 are supported on the conductive powder 13a (S11B), and the binder 13c and the polymer chain gap forming agent (for example, polyethylene glycol) are placed in a solvent (for example, dimethylacetamide). In addition, the conductive powder 12a is added and mixed and dispersed (S12B), and the mixture is applied to the other surface of the solid polymer electrolyte membrane 11 and sprayed or the like to dry. Then, by removing the solvent, a film-like material is formed on the other surface of the solid polymer electrolyte membrane 11 (S13B).

Then, the solid polymer electrolyte membrane 11 provided with the membrane on both sides is immersed in a water bath and washed with water to elute and remove the polymer chain gap forming agent from the membrane (S14). By removing moisture by drying (S15), pores 12d communicating between the surface of the solid polymer electrolyte membrane 11 and the surface facing the surface between the conductive powders 12a and 13a. , 13d and polymer chain gaps 12cb, 13cb of a molecular size level allowing gas molecules (H ₂ and O ₂ ) to pass between adjacent polymer chains 12ca, 13ca of the binders 12c, 13c. The cell 10 including the electrode films 12 and 13 thus manufactured can be easily manufactured.

  That is, the electrode films 12 and 13 are capable of expressing the binding and proton conductivity of the conductive powders 12a and 13a as necessary, but the surfaces of the solid polymer electrolyte membrane 11 and the side facing the surface. By adjusting the amount of the binders 12c and 13c used so that the gas can be sufficiently and sufficiently circulated between the surfaces, the pores 12d and 13d having a submicron to micron size level between the conductive powders 12a and 13a. Are formed, and the binders 12c and 13c and the polymer chain gap forming agent are uniformly mixed and dissolved in the solvent, so that the polymer chain gap forming agent is adjacent to the binders 12c and 13c. By intervening between the molecular chains 12ca and 13ca at the molecular level and being eluted and removed from the binders 12c and 13c, the binders 12c and 13c are subjected to molecular support. Zureberu of the polymer chains gap 12cb, is the 13cb are formed (see FIGS. 2 and 3).

  The steps S11A and S11B for supporting the catalyst particles 12b and 13b on the conductive powders 12a and 13a are omitted when the commercially available conductive powders 12a and 13a on which the catalyst particles 12b and 13b are previously supported are used. The In steps S12A and S12B, binders 12c and 13c previously dissolved in a solvent can be used.

  Here, examples of the solvent include organic solvents such as ethanol, propanol, acetone, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and mixtures thereof. Examples of the polymer chain gap forming agent include polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polymethyl methacrylate (PMM), sodium polyacrylate, hydroxyethyl methylcellulose (HEMC) and hydroxypropyl. Examples thereof include a water-soluble cellulose such as methylcellulose (HPMC) (for example, “Metroze (registered trademark)” manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and a polymer material that dissolves in the solvent and water.

  When the polymer chain gap forming agent is a metal salt type polymer material that dissolves in the solvent and water, such as sodium polyacrylate, the solid polymer electrolyte material of the binders 12c and 13c. Since the counter ion of the proton conductive group may be replaced with the metal ion (for example, sodium ion), the electrode ion is washed after the electrode film is prepared to ensure the proton conductive group counter ion is Substitution with protons is preferred.

  By using such water and a polymer material that dissolves in the solvent as the polymer chain gap forming agent, the binders 12c and 13c and the polymer chain gap forming agent can be easily dissolved and mixed uniformly at the molecular level. At the same time, the polymer chain gap forming agent can be removed from the binders 12c and 13c without adversely affecting water, and it is excellent in workability and low cost.

Then, with the cell 10 of the gas diffusion layer 14 is disposed on the electrode film 12 side having a gas permeability and electrical conductivity, hydrogen (H ₂₎ fuel gas flow passage for flowing the fuel gas 1 containing the By alternately laminating a plurality of oxidant gas passages formed on one surface and having an oxidant gas flow passage for circulating an oxidant gas 2 containing oxygen (O ₂ ) formed on the other surface, A stack can be manufactured, and by providing the stack, the solid polymer electrolyte fuel cell according to the present embodiment can be obtained.

In such a solid polymer electrolyte fuel cell, the fuel gas 1 is circulated through the fuel gas flow passages of the separators of the stack, and the fuel gas 1 is supplied to the fuel electrode membrane 12 side of each cell 10. When supplying the oxidizing gas 2 to the oxidizing gas flow passages of the separators of the stack and supplying the oxidizing gas 2 to the oxidation electrode film 13 side of each cell 10, Is brought into contact with the catalyst particles 12b of the fuel electrode membrane 12 through the gas diffusion layer 14 to generate protons (H ⁺ ) and electrons (e ⁻ ), and the protons are converted into the binder 12c and the fuel electrode membrane 12 While conducting the solid polymer electrolyte membrane 11 and reaching the oxide electrode membrane 13 side, the electrons pass through the gas diffusion layer 14, the separator and the like and the external circuit 101. While reaching the oxide electrode film 13 side Te, oxygen, electricity on the catalyst particles 13b of the oxide electrode film 13 through the gas diffusion layer 14 in contact with the proton and the electron becomes water (H ₂ O) By causing a chemical reaction, electricity flows through the external circuit 101.

  At this time, since the cell 10 has the pores 12d and 13d of submicron to micron level between the conductive powders 12a and 13a in the electrode films 12 and 13, the gas 1 2 circulates in the electrode films 12 and 13, and the binders 12c and 13c have the polymer chain gaps 12cb and 13cb at the molecular size level, so that the gas that circulates through the pores 12d and 13d. 1 and 2 are very easily brought into contact with the catalyst particles 12b and 13b carried on the conductive powders 12a and 13a.

  In other words, in the conventional cell proposed in the above-mentioned Patent Document 1 or the like, carbon particles are filled by filling a necessary and sufficient amount of a solid polymer electrolyte material in the pores of a porous carbon film supporting a catalyst metal. However, as a result of intensive studies by the present inventors, it was found that the catalyst particles supported on the conductive powder had a gas If the gas permeability of the binder itself used for the electrode film is increased so that it can be easily contacted, a new finding that the polarization resistance of the electrode reaction can be greatly reduced can be obtained. In such a cell 10, the conductive powder 12a, 13a carrying the catalyst metals 12b, 13b is contained in a necessary and sufficient amount of the binder 12c containing the polymer chain gap forming agent uniformly at the molecular level. 13c and removing the polymer chain gap forming agent to form submicron to micron-sized pores 12d and 13d between the conductive powders 12a and 13a, as well as the binder. The electrode films 12 and 13 are formed by further forming polymer chain gaps 12cb and 13cb at the molecular size level in 12c and 13c.

  Therefore, in the cell 10 according to the present embodiment, the gas 1 to the catalyst particles 12b and 13b supported on the conductive powders 12a and 13a is higher than that of the conventional cell proposed in Patent Document 1 described above. , 2 can be promoted, and the polarization resistance of the electrode reaction can be greatly reduced.

  Therefore, according to the present embodiment, the power generation performance can be further improved as compared with the conventional case.

  In the present embodiment, the case of the cell 10 having the polymer chain gaps 12cb and 13cb in both the fuel electrode film 12 and the oxide electrode film 13 has been described. However, at least one of the fuel electrode film and the oxide electrode film is used. In addition, even in the cell having the polymer chain gap, the power generation performance can be improved as compared with the conventional case.

However, in the oxidation electrode film, the water generated by the electrochemical reaction tends to hinder the supply of the oxidizing gas to the catalyst particles supported on the conductive powder, the oxygen reduction reaction resistance tends to increase, Since (O ₂ ) has a larger molecular size than hydrogen molecules (H ₂ ) and does not easily pass through the inside of the binder, it is preferable that the cell has at least the polymer chain gap in the oxide electrode film.

  The conductive powder 13a carrying the catalyst particles 13b is a carbon powder carrying Pt metal, and the oxide electrode film 13 contains a hydrophilic carbon powder, or carbon carrying Pt metal. Powder, carbon powder supporting Pt—Co alloy, carbon powder supporting a mixture of Pt metal and Pt—Co alloy, mixture of carbon powder supporting Pt metal and carbon powder supporting Pt—Co alloy, Pt Any one of a carbon powder carrying a mixture of a metal and a Pt—Ru alloy, a mixture of a carbon powder carrying a Pt metal and a carbon powder carrying a Pt—Ru alloy, or the carbon powder is hydrophilic Therefore, it is very preferable because the power generation performance can be further improved. The reason for this is not clear, but the familiarity between the conductive powder 13a carrying the catalyst particles 13b and the binder 13c increases, and the binder 13c covers the conductive powder 13a and the catalyst particles 13b evenly. This is because the contact area between the conductive powder 13a and the catalyst particles 13b and the binder 13c is increased, and the reaction efficiency is increased.

  Here, in the case of a mixture of carbon powder supporting Pt metal and carbon powder supporting Pt—Ru alloy, the ratio of carbon powder supporting Pt metal to carbon powder supporting Pt—Ru alloy is 99: 1 to 50:50 (preferably 95: 5 to 90:10) is preferable because the above-described effects can be obtained efficiently. When carbon powder carrying a mixture of a Pt metal and a Pt—Ru alloy is used. When the ratio of Pt metal to Pt—Ru alloy is 99: 1 to 50:50 (preferably 95: 5 to 90:10), the above-described effects can be obtained efficiently. When the oxide electrode film 13 contains a hydrophilic carbon powder, the ratio of the carbon powder to the hydrophilic carbon powder is 99.8: 0.2-80. 20 (preferably 99.5: 0.5 to 95: 5) If it is, it is possible to efficiently obtain the effect described above preferable.

  In this embodiment, a mixture obtained by mixing and dispersing the conductive powders 12a and 13a carrying the catalyst particles 12b and 13b in a solvent in which the binders 12c and 13c and the polymer chain gap forming agent are uniformly mixed and dissolved is mixed. The molecular electrolyte membrane 11 is coated and sprayed and dried to provide a membrane-like material on the solid polymer electrolyte membrane 11, that is, the membrane-like material forming step and the membrane-like material arranging step are performed simultaneously. However, as another embodiment, for example, after the mixture is applied or sprayed on a fluororesin sheet or a glass plate and dried to form a film on the sheet or the plate (film-like material) Forming step), this is pressed against the solid polymer electrolyte membrane 11, the sheet or the plate is separated from the solid polymer electrolyte membrane 11, and the membrane is transferred to the solid polymer electrolyte membrane 11 (membrane) Article arrangement work In addition, the gas diffusion layer 14 is applied to or sprayed on the gas diffusion layer 14 and dried to form a film-like material on the gas diffusion layer 14 (film-like material forming step). It is also possible to provide the molecular electrolyte membrane 11 (film-like material disposing step), that is, to perform the film-like material disposing step after the film-like material forming step.

  Moreover, in this embodiment, after providing the above-mentioned membrane-like material on the solid polymer electrolyte membrane 11 (membrane-like material disposing step), the membrane-like material is washed with water together with the solid polymer electrolyte membrane 11, The polymer chain gap forming agent is eluted and removed from the film-like material (polymer chain gap forming agent removing step), that is, the polymer chain gap forming agent removing step is performed after the film-like material arranging step. However, as another embodiment, for example, the film-like material formed on the fluororesin sheet, the glass plate, the gas diffusion layer 14 or the like as in the other embodiments described above, the fluororesin sheet, the glass plate, After washing with the gas diffusion layer 14 and the like with water to elute and remove the polymer chain gap forming agent from the film-like material (polymer chain gap forming agent removing step), this is pressed against the solid polymer electrolyte membrane 11 To the solid polymer electrolyte membrane 11 Jo product (electrode film 12, 13) provided (film-like material arranged step), i.e., it is also possible to perform the film-like material arranged step after the polymer chain gap forming agent removing step.

  The mixing amount of the polymer chain gap forming agent is preferably 1 to 80% by weight (more preferably 10%) with respect to the total weight of the binders 12c and 13c and the polymer chain gap forming agent. -50 wt%). This is because if the amount is less than 1% by weight, the polymer chain gaps 12cb and 13cb cannot be formed sufficiently and sufficiently, and if the amount exceeds 80% by weight, the proton conductivity is excessively lowered and sufficient power generation performance is obtained. It is because it becomes impossible to obtain.

In order to confirm the effect of the method for producing a solid polymer electrolyte membrane electrode assembly according to the present invention, the following confirmation test was performed.

[A. Gas permeability confirmation test]
(1) Preparation of test body A solid polymer electrolyte material composed of a hydrocarbon resin and a polymer chain gap forming agent were added to a solvent and uniformly dissolved on the substrate and dried. Thereafter, the film-like test bodies AA1 to AA3, AB1 and AB2 having the conditions shown in Table 1 below were prepared by washing with water to remove the polymer chain gap forming agent and peeling off from the substrate.

(2) Test method The gas permeability was measured for the specimens AA1 to AA3, AB1 and AB2 based on “JIS K7126-2 (isobaric GC method)” (temperature 85 ° C., humidity 95% RH). Humidification on both sides).

(3) Test Results FIG. 5 shows the test results performed based on the test method described above.
As can be seen from FIG. 5, the hydrocarbon-based solid polymer electrolyte material specimen AB1 has a lower gas permeability than the fluorine-based solid polymer electrolyte material specimen AB2 having sufficient gas permeability. It can be confirmed that the test bodies AA1 to AA3 of the hydrocarbon-based solid polymer electrolyte material in which the chain gap is formed can exhibit higher gas permeability than the test body AB2.

[B. Power generation performance confirmation test]
(1) Manufacture of cells Based on the manufacturing method described in the above-described embodiment, cell specimens BA1, BA2, BB1, CA1, CA2, and CB1 were manufactured under the following conditions.

<Specimen BA1>
(I) Solid polymer electrolyte membrane Hydrocarbon solid polymer electrolyte material “Vatelion (product name)” manufactured by Battelle Memorial Laboratory, USA

(Ii) Fuel electrode membrane / conductive powder Pt—Ru alloy catalyst particle-supported carbon powder / 460 mg (0.5 mg Pt / cm ² )
・ Binder Hydrocarbon-based solid polymer electrolyte material "Vatelion (product name)" manufactured by Battelle Memorial Laboratory / 80mg
-Polymer chain gap forming agent None-Solvent Mixed liquid of acetone (22g) and dimethylacetamide (38g)

(Iii) Oxide electrode film / conductive powder Pt metal catalyst particle-supported carbon powder / 205 mg (0.5 mg Pt / cm ² )
・ Binder Hydrocarbon-based solid polymer electrolyte material “Vatelion (product name)” manufactured by Battelle Memorial Laboratory / 103 mg
・ Polymer chain gap forming agent Polyethylene glycol / 26mg
(Percentage of total weight with binder: 20% by weight)
-Solvent A mixture of acetone (7 g) and dimethylacetamide (12 g)

<Specimen BA2>
(I) Solid polymer electrolyte membrane * Same as specimen BA1 (ii) Fuel electrode membrane * Same as specimen BA1 (iii) Oxide electrode membrane / polymer chain gap forming agent Polyethylene glycol / 103 mg
(Percentage of total weight with binder: 50% by weight)
* Others are the same as specimen BA1

<Specimen BB1>
(I) Solid polymer electrolyte membrane * Same as test specimen BA1 (ii) Fuel electrode membrane * Same as test specimen BA1 (iii) No addition of oxide electrode membrane / polymer chain gap forming agent * Others are the same as test specimen BA1

<Specimen CA1>
(I) Solid polymer electrolyte membrane Hydrocarbon solid polymer electrolyte material “Vatelion (product name)” manufactured by Battelle Memorial Laboratory, USA
(Ii) Fuel Electrode Membrane / Binder Hydrocarbon-based solid polymer electrolyte material “Vatelion (product name)” manufactured by Battelle Memorial Laboratory / 80 mg
* Others are the same as specimen BA1 (iii) Oxide electrode membrane / binder Hydrocarbon-based solid polymer electrolyte material “Vatelion (product name)” manufactured by Battelle Memorial Laboratory / 75 mg
・ Polymer chain gap forming agent Hydroxypropylmethylcellulose (HPMC) /8.3mg
(Percentage of total weight with binder: 10% by weight)
* Others are the same as specimen BA1

<Specimen CA2>
(I) Solid polymer electrolyte membrane * Same as specimen CA1 (ii) Fuel electrode membrane * Same as specimen CA1 (iii) Oxide membrane / polymer chain gap forming agent Hydroxypropylmethylcellulose (HPMC) /40.4mg
(Percentage of total weight with binder: 35% by weight)
* Others are the same as specimen CA1

<Specimen CB1>
(I) Solid polymer electrolyte membrane * Same as specimen CA1 (ii) Fuel electrode membrane * Same as specimen CA1 (iii) No addition of oxide electrode membrane / polymer chain gap forming agent * Others are the same as specimen CA1

(2) Test conditions A power generation test of the specimens BA1, BA2, BB1, CA1, CA2, and CB1 was performed under the following conditions.
・ Fuel gas Hydrogen gas (humidity: 100%)
・ Oxidizing gas air (humidity: 100%)
・ Cell temperature: 85 ℃
Pressure: Atmospheric pressure Hydrogen utilization rate: 75%
Oxygen utilization rate: 40%

(3) Test results The power generation test results of the test bodies BA1, BA2, and BB1 are shown in FIGS. 6 and 7, and the power generation test results of the test bodies CA1, CA2, and CB1 are shown in FIGS.
As can be seen from FIGS. 6 and 7, it was confirmed that the test bodies BA1 and BA2 can improve the power generation performance more than the test body BB1. Further, as can be seen from FIGS. 8 and 9, it was confirmed that the test bodies CA1 and CA2 can improve the power generation performance more than the test body CB1.

The method for producing a solid polymer electrolyte membrane / electrode assembly according to the present invention can easily produce a solid polymer electrolyte membrane / electrode assembly that further improves the power generation performance, and is therefore extremely useful in various industries. be able to.

It is a schematic block diagram of embodiment of the solid polymer electrolyte membrane electrode assembly which concerns on this invention. A is an enlarged view of extraction of the fuel electrode membrane of FIG. 1, and B is an enlarged view of extraction of a binder. FIG. 4A is an extraction enlarged view of the oxide electrode film of FIG. 1, and B is an extraction enlarged view of a binder. It is a procedure flowchart of embodiment of the manufacturing method of the solid polymer electrolyte membrane electrode assembly of FIG. It is a graph showing the gas-permeability test result of test body AA1-AA3, AB1, AB2. It is a graph showing the power generation performance confirmation test result of test body BA1, BA2, BB1. It is a graph showing the power generation performance confirmation test result of test body BA1, BA2, BB1. It is a graph showing the power generation performance confirmation test result of test body CA1, CA2, CB1. It is a graph showing the power generation performance confirmation test result of test body CA1, CA2, CB1. It is a schematic block diagram of an example of the conventional solid polymer electrolyte membrane electrode assembly.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fuel gas 2 Oxidation gas 10 Solid polymer electrolyte membrane electrode assembly (cell)
11 solid polymer electrolyte membrane 12 fuel electrode membrane 12a conductive powder 12b catalyst particle 12c binder 12ca polymer chain 12cb polymer chain gap 12d pore 13 oxide electrode membrane 13a conductive powder 13b catalyst particle 13c binder 13ca polymer chain 13cb high Molecular chain gap 13d Pore 14 Gas diffusion layer 101 External circuit

Claims (4)

A solid polymer electrolyte membrane made of a hydrocarbon-based resin solid polymer electrolyte material having proton conductivity;
A fuel electrode in which conductive powder supporting catalyst particles is bound with a binder made of a solid polymer electrolyte material of a hydrocarbon resin having proton conductivity, and is disposed on one surface of the solid polymer electrolyte membrane. A membrane,
An oxide electrode provided on the other surface of the solid polymer electrolyte membrane by binding conductive powder carrying catalyst particles with a binder made of a solid polymer electrolyte material of a hydrocarbon resin having proton conductivity. A method for producing a solid polymer electrolyte membrane electrode assembly comprising a membrane,
The binder of at least one of the oxide electrode membrane and the fuel electrode membrane has a polymer chain gap that allows gas molecules to pass between adjacent polymer chains.
A film that forms a film-like material from a mixture obtained by mixing the conductive powder carrying the catalyst particles, the binder, and a polymer chain gap forming agent made of a polymer material dissolved in an organic solvent and water in an organic solvent. A step of forming a material,
A membranous material disposing step of providing the membranous material on the solid polymer electrolyte membrane;
Performing a polymer chain gap forming agent removing step of removing the polymer chain gap forming agent from the film by washing the film with water ,
The organic solvent comprises at least one of dimethylformamide (DMF), dimethylacetamide (DMAc), and acetone;
The method for producing a solid polymer electrolyte membrane / electrode assembly, wherein the polymer chain gap forming agent comprises polyethylene glycol (PEG) . In claim 1 ,
The conductive powder carrying the catalyst particles of the oxide electrode film is a carbon powder carrying Pt metal,
The method for producing a solid polymer electrolyte membrane / electrode assembly, wherein the oxidized electrode membrane contains a hydrophilic carbon powder. In claim 1 ,
Wherein the oxide electrode film, the conductive powder carrying the catalyst particles, carbon powder having a carbon powder, a hydrophilic carrying Pt-Co alloy having a hydrophilic supporting Pt metal, Pt metal and Pt-Co a mixture of carbon powder having a carbon powder, a hydrophilic carrying carbon powder and Pt-Co alloy having a hydrophilic supporting Pt metal having a mixture carrying hydrophilic and alloys, Pt metal and Pt-Ru alloys it carbon powder, a mixture of carbon powder having a hydrophilic carrying carbon powder and Pt-Ru alloy having a hydrophilic supporting Pt metal is any one of which having a mixture carrying hydrophilic and A method for producing a solid polymer electrolyte membrane electrode assembly characterized by the following. In any one of Claims 1-3 ,
The amount of the polymer chain gap forming agent mixed is 1 to 80% by weight with respect to the total weight of the binder and the polymer chain gap forming agent. Manufacturing method of joined body.

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