JP3555999B2 - Method for producing polymer solid electrolyte / electrode assembly for polymer electrolyte fuel cell - Google Patents

Method for producing polymer solid electrolyte / electrode assembly for polymer electrolyte fuel cell Download PDF

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JP3555999B2
JP3555999B2 JP30367294A JP30367294A JP3555999B2 JP 3555999 B2 JP3555999 B2 JP 3555999B2 JP 30367294 A JP30367294 A JP 30367294A JP 30367294 A JP30367294 A JP 30367294A JP 3555999 B2 JP3555999 B2 JP 3555999B2
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solid electrolyte
polymer
sheet
electrode
polymer solid
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JPH08162132A (en
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博 加藤
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ジャパンゴアテックス株式会社
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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
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells
    • Y02E60/52Fuel cells characterised by type or design
    • Y02E60/521Proton Exchange Membrane Fuel Cells [PEMFC]

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present inventionThe present invention relates to a method for producing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell.
[0002]
[Prior art]
Electrochemical devices that use solid polymer electrolytes are required to further improve energy efficiency.To this end, the electrode structure is devised, the electrode reaction points are made three-dimensional to increase the number of reaction active points, and polymer solids are increased. An electrolyte is also arranged inside the electrode so that ions can move quickly. In order to allow the generated ions to move quickly to the counter electrode, it is necessary that the solid electrolyte in the electrode be in good contact with the solid electrolyte membrane, which is a diaphragm, and that the solid electrolyte membrane itself have a low membrane resistance. It is preferable that the film thickness be as thin as possible. Furthermore, if the solid polymer electrolyte membrane used in the fuel cell is not used in a wet state at all times, the ion conductivity will decrease or the polarization will occur, and the performance will decrease. Although the wet state is maintained, the thinner the polymer solid electrolyte membrane, the better the humidification efficiency, and an improvement in the limit current density can be expected.
[0003]
Conventionally, a method is generally used in which a solid electrolyte membrane and an electrode are separately prepared, and these are overlapped and then joined by hot pressing. As a polymer solid electrolyte, a commercially available product is formed into a film shape. (For example, Nafion # 115 manufactured by DuPont, USA) or a solution obtained by casting the solution to form a thin film. It has also been proposed to use it mechanically without hot pressing.
[0004]
[Problems to be solved by the invention]
However, in hot-press bonding, pressure is applied when the film softens due to temperature, so if the film is too thin, the film will be broken, causing gas leakage or short-circuiting between the electrodes. There was a problem that it was easy to do. This becomes a more difficult problem when the smoothness of the electrode is poor, and it has been difficult to extremely reduce the film thickness. In addition, since the electrodes themselves are also compacted during hot pressing, there is a problem that the air permeability, which is an important element of the electrodes for enabling operation at a high current density, is impaired.
[0005]
To solve these problems and to omit the hot press process itself, there has been proposed a method of mechanically sandwiching the electrode, but maintaining uniform contact with the electrode and the contact resistance itself have been proposed. In order to keep the temperature low, a considerable pressure is required, and when the film thickness is reduced, there is a problem similar to the hot press. Further, in a fuel cell configured by stacking a plurality of cells, it is difficult to maintain a constant contact resistance for a long period of time due to stress relaxation of an electrode or a membrane, and the reliability becomes low.
[0006]
In order to solve these problems, a solid electrolyte membrane is formed directly by applying and drying a solution of a polymer solid electrolyte resin on an electrode catalyst, preferably a sheet-shaped electrode or an electrode catalyst surface. And then hot-pressing the bonded bodies thus formed together with the solid electrolyte membrane surfaces, or applying a solid polymer electrolyte resin solution or its solvent and then bonding them together to form a solvent. After removing or applying the solution of the polymer solid electrolyte resin to the electrode or the electrode surface while applying the solution of the polymer solid electrolyte resin to the electrode surface and then drying or applying the polymer solid electrolyte solution to the electrode surface, It has also been proposed to remove the solvent to form an integrated anode / membrane / cathode product. However, in the method of applying a polymer solid electrolyte resin solution on the electrode catalyst layer surface to form a membrane, the film-forming property is poor depending on the electrode structure, and it is necessary to apply the solution excessively. There is a possibility that the permeation of the polymer solid electrolyte resin becomes excessive and the gas diffusibility is hindered. It is also difficult to make the film thickness uniform, and if the film thickness is to be reduced, there is also a high possibility that a short circuit will occur between the electrodes.
[0007]
The present invention makes it possible to reduce the thickness of the solid electrolyte membrane in order to enable the energy efficiency of the electrochemical device using the polymer solid electrolyte membrane and the operation at a high current density, and furthermore, the electrode inherent in Ensures low and reliable contact resistance with electrodes without impairing physical properties, and does not necessarily require a heat press stepFor polymer electrolyte fuel cellsOf electrode / membrane assembly or electrode / membrane / electrode assemblyProduction methodThe purpose is to obtain.
[0008]
[Means for Solving the Problems]
According to the present invention, the following is provided to achieve the above object.
(1)A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising disposing a stretched porous polytetrafluoroethylene sheet on a sheet electrode, applying a polymer solid electrolyte resin solution to the stretched porous polytetrafluoroethylene sheet, A step of joining and integrating the sheet-like electrode and the expanded porous polytetrafluoroethylene sheet with a polymer solid electrolyte resin by removing a solvent of the solution; For producing a polymer electrolyte electrolyte / electrode assembly for a polymer electrolyte fuel cell.
(2)A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising disposing a stretched porous polytetrafluoroethylene sheet pre-impregnated with a polymer solid electrolyte resin solution on a sheet-like electrode, and removing the solvent of the solution to form the sheet. A method for manufacturing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell, comprising a step of joining and integrating a shaped electrode and an expanded porous polytetrafluoroethylene sheet with a polymer solid electrolyte resin.
(3)A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising forming a stretched porous polytetrafluoroethylene sheet in which a polymer solid electrolyte resin solution has been previously impregnated and the solvent has been removed, and then the polymer solid electrolyte resin solution is drawn into the stretched porous polytetrafluoroethylene sheet. Coated on the surface of a porous polytetrafluoroethylene sheet / polymer solid electrolyte resin composite sheet or a sheet-like electrode surface, and the expanded porous polytetrafluoroethylene sheet / polymer solid electrolyte resin composite sheet is formed into a sheet in the presence of a solvent. The sheet-like electrode and the expanded porous polymer are placed on the electrode and the solvent of the solution is removed. The process for producing a polymer electrolyte fuel cell polymer solid electrolyte electrode assembly, characterized in that the tetrafluoroethylene sheet comprising the step of integrally bonding with the solid polymer electrolyte resin.
(4)A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising forming an electrode on one surface of an expanded porous polytetrafluoroethylene sheet, and then applying a polymer solid electrolyte resin solution from the back surface of the expanded porous polytetrafluoroethylene sheet. A method for producing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell, comprising a step of forming a polymer solid electrolyte resin film by applying, impregnating, and removing a solvent.
(5)A polymer solid electrolyte for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin and an expanded porous polytetrafluoroethylene sheet and an electrode are joined and integrated with the polymer solid electrolyte resin A method for producing an electrode assembly, comprising preparing a stretched porous polytetrafluoroethylene sheet in which a polymer solid electrolyte resin solution is previously impregnated or in a semi-dried state or the solvent is completely removed, and the polymer solid electrolyte resin is prepared. The surface of the impregnated and stretched porous polytetrafluoroethylene sheet is coated with an ink or paste comprising at least an electrode forming component containing a polymer solid electrolyte resin component, and the solvent is removed to stretch the electrode to form the porous polytetrafluoroethylene sheet. Polymer electrolysis characterized by including a step of integrally forming an ethylene sheet Method for manufacturing a mold for a fuel cell polymer solid electrolyte electrode assembly.
(6) The sheet-like electrode forms a conductive gas diffusion sheet having a conductive gas-permeable sheet formed on the surface of a mixture of conductive particles and polytetrafluoroethylene in the form of a sheet. A catalyst layer containing a catalyst and a polymer electrolyte is formed on the conductive permeable sheet.The above (1) to (4)The method for producing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell according to any one of the above.
(7) The method according to any one of (1) to (5), further including a step of preparing two polymer solid electrolyte / electrode assemblies and joining and integrating the polymer solid electrolytes. 13. The method for producing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell according to item 6.
[0009]
That is, when a polymer solid electrolyte resin solution is applied on the electrode surface to form a film, an expanded porous polytetrafluoroethylene (PTFE) film is placed on the electrode surface in advance, so that most of the resin component is stretched and porous. The resin contained in the voids of the porous PTFE and partially penetrated to the back surface contributes to the bonding as a binder with the electrode. Generally, a solid polymer electrolyte resin is often included inside the electrode in order to increase the number of reaction points of the electrode, but in this case, the bonding strength becomes stronger.
[0010]
A similar structure and effect can also be obtained by disposing a stretched porous PTFE membrane in which a polymer solid electrolyte resin solution has been impregnated beforehand on the electrode surface and then removing the solvent. In this case, in order to prevent the solid electrolyte resin in the expanded porous PTFE membrane from excessively penetrating into the electrodes and the expanded porous PTFE membrane / polymer solid electrolyte resin composite membrane from becoming porous (porous). In addition, it is preferable to appropriately remove the solvent before disposing the solvent on the electrode surface. However, if the solvent is removed too much, the adhesive strength decreases and the resistance increases.
[0011]
Therefore, after the solid electrolyte resin solution is impregnated into the expanded porous PTFE membrane in advance, the solvent is removed to form the expanded porous PTFE membrane / solid electrolyte resin composite membrane, and then the solid electrolyte resin solution is again applied as a binder to the surface or After coating on the electrode surface, it may be disposed on the electrode surface in the presence of a solvent, and then the solvent may be removed to form a joined body. In joining the above solid polymer electrolyte and the electrode, a small solid polymer electrolyte solution may be applied in advance to the surface of the electrode material. This has the effect of improving the adhesion between the solid polymer electrolyte and the electrode.
[0012]
On the other hand, the same structure and effect can be obtained in the case where an electrode is previously formed on one surface of the expanded porous PTFE. That is, an expanded porous PTFE membrane having a pore size such that the polymer solid electrolyte resin component can penetrate but the solid component such as catalyst powder cannot penetrate, and at least the catalyst powder or the electrode component as an electrode forming component is provided on the surface thereof. These inks and the like are deposited on the surface by applying an ink or paste containing components containing powder and the polymer solid electrolyte resin, or by filtering a solution or dispersion containing these components, and then depositing these inks and the like. After removing the solvent or the dispersion medium, an electrode is formed on one surface of the expanded porous PTFE, and then a polymer solid electrolyte resin solution is applied and impregnated from the back surface, and the solvent is removed to form a polymer solid electrolyte membrane. It may be formed into a joined body.
[0013]
Conversely, the structure and effect of the present invention can also be obtained by forming an electrode on the surface after forming a polymer solid electrolyte membrane in advance. That is, the porous solid PTFE is impregnated with the polymer solid electrolyte resin solution in the voids in advance or a semi-dried or completely removed one by appropriately removing the solvent is prepared. An ink or paste composed of an electrode forming component containing at least a polymer solid electrolyte resin component is applied to the surface, and a solvent can be removed to form a joined body. In this case, it is an essential condition that the electrode forming component solution contains the polymer solid electrolyte resin, and if it does not contain the resin, the joining becomes incomplete, so that it is necessary to further heat-breath, and No performance is obtained.
[0014]
In any method, the structure of the polymer solid electrolyte resin is stabilized by sufficiently heating at a temperature of about 120 ° C. to 180 ° C. after the removal of the solvent, and the adhesive strength becomes sufficient even without applying a pressing pressure. . Of course, further heat pressing may be performed, but is not particularly necessary.
Furthermore,Anode cathodeThe same method can be applied to the bonding of That is, as described above, the electrode / membrane assembly isCathode, anodeAfter preparing for each or one of them, apply an appropriate amount of polymer solid electrolyte solution as a binder to the surface on the membrane side or the surface of the counter electrode in contact with it, then butt together and remove the solvent And by heatingCathode/film/anodeZygote orCathode/ Membrane / membrane /anodeA conjugate can be obtained. Of course, it is also possible to configure the electrode / membrane / electrode in one step instead of after preparing the electrode / membrane assembly. That is, the electrode / membrane / electrode assembly can be manufactured as described below.
[0015]
{Circle around (1)} A solvent or solution of a polymer solid electrolyte resin is applied to the surface of the electrode / polymer solid electrolyte joined body, and the same electrode / polymer solid electrolyte joined body or electrodes are joined together. And then heat treated.
{Circle around (2)} After the expanded porous PTFE film is placed on the electrode, a polymer solid electrolyte resin solution is applied and impregnated on the surface thereof, and a similar electrode / polymer solid electrolyte junction or electrode is further placed on the surface. Subsequently, the solvent is removed, followed by a heat treatment.
[0016]
{Circle around (3)} On the surface of the electrode catalyst layer, a film was previously placed in which the porous solid PTFE was impregnated with a polymer solid electrolyte resin solution in the voids, and the solvent was removed after the electrode was placed on the surface, followed by heat treatment. I do.
(4) A porous solid PTFE membrane / polymer solid electrolyte resin-composite electrolyte prepared by previously impregnating the voids of the expanded porous PTFE membrane with the polymer solid electrolyte resin solution and removing the solvent is prepared. Alternatively, after a solvent or solution of a polymer solid electrolyte resin is applied to the electrode surface, electrodes are arranged on both surfaces of the composite electrolyte, the solvent is removed, and heat treatment is performed.
[0017]
(5) Similar to (3) or (4), a porous solid PTFE membrane in which voids have been impregnated with a polymer solid electrolyte resin solution in advance, or a solvent has been once removed therefrom, or the polymer has been further removed after removal of the solvent. After applying a paste-like or ink-like component having an electrode-forming component (for example, a catalyst powder and a polymer solid electrolyte resin or PTFE or a mixture thereof) on both surfaces of the solid electrolyte solution applied thereto, the solvent is removed, followed by heat treatment. I do.
[0018]
In the electrode / membrane assembly or the electrode / membrane / electrode assembly obtained in this way, the polymer solid electrolyte is formed directly on the electrode, or the polymer / solid electrolyte is formed on the electrode in a state of good adhesion after the film is formed. Because it is bonded, it has a high adhesion to the electrode and can be bonded with low resistance without performing heat pressing, etc., and uses an expanded porous PTFE membrane as a matrix for forming a solid polymer electrolyte. Therefore, even on a porous electrode, it can be surely formed as a thin film having a constant thickness and a high strength film. Further, for example, it is possible to prevent short-circuiting due to creep of the polymer solid electrolyte resin due to compression or the like at the time of heat pressing or battery assembly, and to prevent occurrence of variation in resistance. Also, in the case where the expanded porous PTFE / polymer solid electrolyte composite membrane is used in advance, the polymer electrolyte resin still contains a solvent and has adhesiveness, but has no strength by itself and can be handled in a state where it cannot be handled. I do. This has the same advantage even when a resin solution is applied to the surface, and it has become possible to obtain a bonded article like the present invention for the first time by combining it with an expanded porous PTFE membrane.
[0019]
The electrode used in the present invention is not particularly limited in its manufacturing method, structure and the like, and any electrode having a form as an electrode can be used. That is, {circle around (1)} a catalyst powder and PTFE, or a mixed powder obtained by further adding a polymer solid electrolyte resin or the like onto a current collector such as carbon paper, metal fiber nonwoven fabric, or mesh. (2) A paste having the same mixed components as in (1), also coated and formed on a current collector, (3) A mixture, as in (1), formed into a film by casting or the like, (4) ▼ The same components as in <1> may be formed into a sheet by extrusion or roll rolling, but the invention is not particularly limited thereto. Conversely, as described above, after the polymer solid electrolyte is impregnated in the voids of the EPTFE, a paste or ink having the same mixed components as in (1) is applied to the surface thereof. It may be something.
[0020]
The expanded porous polytetrafluoroethylene (PTFE) membrane used in the present invention is obtained by expanding a PTFE sheet into a plurality of micro nodules and extends from the micro nodules to three-dimensionally interconnect the micro nodules. It is a porous PTFE membrane having a structure composed of fine fibers. The preferred thickness of the expanded porous PTFE membrane of the present invention is 1 to 100 μm, preferably 3 to 30 μm, the pore size is 0.05 to 5 μm, preferably 0.5 to 2 μm, and the porosity is 60 to 98%, preferably 80 ~ 92%. If the film thickness is too thin, short-circuiting and gas leakage (cross leak) are liable to occur, and if the film thickness is too thick, the electric resistance increases, and the advantages of the present invention are lost. If the pore size is too small, it becomes difficult to impregnate the solid polymer electrolyte, and if the pore size is too large, the holding power of the solid polymer electrolyte is weakened, and the reinforcing effect is also weakened. If the porosity is too small, the resistance as a solid electrolyte membrane increases, and if it is too large, the strength of EPTFE itself generally becomes weak, and a reinforcing effect cannot be obtained.
[0021]
Further, in some cases, the expanded porous PTFE may contain various fine powders such as a catalyst powder such as platinum, a conductive powder such as carbon black and graphite, and a ceramic powder such as alumina as long as electron conductivity is not generated. good. In this case, after mixing the dispersion after the emulsion polymerization of PTFE and the dispersion of these powders, prepare a homogeneous mixed raw material at the primary particle level as obtained by co-aggregation, and then mix with the PTFE simple raw material. It is obtained by similar processing.
[0022]
As polymer solid electrolyte resinExamples thereof include a polyethylene oxide-alkali metal salt composite and a product obtained by impregnating expanded porous PTFE and then performing a crosslinking treatment. AlsoPerfluorosulfonate resin, which is sold by DuPont as Nafion (registered trademark), is available as Nafion NR-50 as a solution. In addition, various hydrocarbon-based and fluorine-based ion exchange resins are used. In some cases, a catalyst such as platinum, a carbon powder, or various ceramic powders may be added to the polymer solid electrolyte as long as electronic conductivity does not occur.
[0023]
As a solvent for these resin solutions, various hydrocarbon-based organic solvents, water, or a mixed solvent thereof is generally used.
When the resin solution is applied and impregnated on the expanded porous PTFE membrane, it may be difficult to impregnate the resin solution depending on the molecular weight of the resin and the type of the solvent. In this case, concentration adjustment, addition of a surfactant, and the surface of the expanded porous PTFE membrane are performed. An appropriate process such as a process may be appropriately performed.
[0024]
1 (A) and 1 (B) show a polymer solid electrolyte / electrode assembly of the present invention. In FIG. 1, 1 is a solid polymer electrolyte, 2 is an electrode, 3 is a micro nodule of EPTFE in the solid polymer electrolyte membrane, and 4 is a fine fiber in the solid polymer electrolyte membrane.
The mode of using the polymer solid electrolyte / electrode assembly of the present invention in various electrochemical devices can be the same as in a conventional device.
[0025]
FIG. 2 shows an example of a fuel cell. In FIG. 2, 1 is a polymer solid electrolyte resin / PTFE composite membrane, 2 and 3 are electrodes, 7 and 8 are current collectors, 9 and 10 are separator plates, and 11 and 12 are gas supply grooves. The polymer solid electrolyte / electrode assembly of the present invention is used as a polymer solid electrolyte 1 / electrode 2 joint or an electrode 2 / polymer solid electrolyte 1 / electrode 3 joint.
[0026]
In the solid polymer electrolyte fuel cell configured as described above, referring to FIG.2To groove 122Is supplied, O2+ 4H++ 4e→ 2H2O, 2H in electrode 32→ 4H++ 4eReaction occurs and 4H+Flows from the electrode 3 to the electrode 2 through the polymer solid electrolyte 1 and 4eBecomes electric energy by passing through an external load. The operating temperature is about 60 ° C to 100 ° C, preferably about 80 ° C.
[0028]
【Example】
Reference example
A mixed solution of an alkylene oxide polymer oligomer to which a crosslinking agent is added and lithium chlorate is applied to the surface of a sheet-like graphite electrode for lithium ion batteries composed of 95% graphite and 5% PTFE. % Expanded porous PTFE (manufactured by Japan Gore-Tex; Gore-Tex) is fixed on the surface, and the same solution as that applied to the electrode is applied and impregnated from above, then irradiated with a UV lamp and crosslinked to form an electrode / electrolyte junction Got a body.
[0029]
Example 1
Solvent naphtha as a liquid lubricant was mixed with a mixture composed of 65% of carbon black and 35% of PTFE, and then extruded and rolled. After heating and removing the liquid lubricant, the film was stretched 5 times at the same time. After heating at 350 ° C., a conductive air-permeable sheet having a film thickness of 50 μm, a pore diameter of 1 μm, and a porosity of 78% was obtained. The sheet was bonded by hot pressing to a 0.2 mm thick carbon paper impregnated with Teflon (registered trademark of DuPont) to form a gas diffusion layer using the carbon paper as a current collector.
[0030]
Separately, carbon black carrying 25% by weight of platinum (hereinafter referred to as platinum carbon) is used.Isopropyl alcohol (IPA)After that, a perfluorosulfonate resin solution was added and further dispersed to prepare an ink-like solution containing a ratio of perfluorosulfonate resin 30 to platinum carbon 70. After this solution was applied onto the gas diffusion layer, the solvent was removed by air drying to form a catalyst layer, and an electrode of a polymer solid oxide fuel cell was produced. At this time, the amount of platinum was 0.3 mg / cm.2  Met.
[0031]
Next, an expanded porous PTFE sheet having a thickness of 20 μm and a porosity of 89% was fixed on the catalyst layer of the electrode, and a perfluorosulfonate resin solution having a concentration of 5% was applied to the surface thereof, followed by air drying. This coating and air-drying were repeated five times to form a translucent film in which the porous portion and the surface of the expanded porous PTFE film were filled with perfluorosulfonesan resin. The molded body thus obtained was heated at 130 ° C. for 24 hours to obtain a joined body A of the present invention.
[0032]
Example 2
15 μm thickExample 1After fixing the four sides of the same expanded porous PTFE sheet as used in the above, a 5% concentration of a perfluorosulfonate resin solution was applied, impregnated and dried. This was repeated three times to obtain a completely translucent expanded porous PTFE / perfluorosulfonate resin composite film, and then a perfluorosulfonate resin solution was further applied.Example 1After bonding the electrodes of the same solid polymer electrolyte fuel cell as used in the above, the solvent was removed, and the mixture was further heated at 130 ° C. for 24 hours to obtain a joined body B of the present invention.
[0033]
Example 3
Example 2Instead of applying a perfluorosulfonate resin solution at the end of the above, an electrode was coated with isopropyl alcohol (IPA), and immediately thereafter adhered to a stretched porous PTFE / perfluorosulfonate resin composite membrane. The joined body C of the present invention was obtained.
Example 4
Example 1Is prepared, and a 2% concentration of a perfluorosulfonate resin solution is applied to the surface of one of the perfluorosulfonate resin films, and air is prevented from entering between the two. The two sheets were pressed together with the perfluorosulfonate resin film surfaces in contact with each other, and the solvent was removed by air drying, followed by heating at 130 ° C. for 24 hours to obtain an electrode / membrane / membrane / electrode assembly AA of the present invention.
[0034]
Example 5
Other than using expanded porous PTFE having a thickness of 30 μm,Example 2After obtaining an expanded porous PTFE / perfluorosulfonic acid resin in the same manner as described above, a 2% concentration of a perfluorosulfonic acid resin solution is further applied to both surfaces thereof, and subsequently,Example 1The two electrodes of the solid polymer electrolyte fuel cell used in the above were pressed in such a manner that they were sandwiched, and then the solvent was removed by air drying, followed by heating at 130 ° C. for 24 hours to obtain the electrode / membrane / electrode of the present invention. A conjugate was obtained.
[0035]
Example 6
Example 1After fixing expanded porous PTFE having a thickness of 40 μm and a porosity of 92% on the same electrode of the solid polymer electrolyte fuel cell as prepared in the above, a perfluorosulfonate resin solution having a concentration of 5% was applied and dried. . After repeating this three times, after applying the fourth time, without drying, another electrode is pressed into contact, the solvent is removed by air drying, and heated at 130 ° C. for 24 hours to form the electrode / membrane / electrode of the present invention. A conjugate was obtained.
[0036]
Example 7
Example 4The humidified hydrogen was supplied to one side of the joined body AA obtained in the above, oxygen was supplied to the other side, and the fuel cell was operated at 80 ° C. under heating at 1 A / cm.Two , A performance of 0.78 V was obtained.
[0037]
【The invention's effect】
According to the present invention, there is provided a polymer solid electrolyte / electrode assembly in which a polymer solid electrolyte composed of expanded porous PTFE and a polymer solid electrolyte resin contained in a porous void portion thereof is integrally formed on an electrode surface. This makes it possible to reduce the thickness of the polymer solid electrolyte membrane without impairing the physical properties of the electrodes, while maintaining a low contact resistance with the electrodes, and without necessarily requiring a heat pressing step. It is possible to improve the energy efficiency and current density of the device.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a polymer solid electrolyte / electrode assembly (A) and an electrode / polymer solid electrolyte / electrode assembly (B) of an example of the present invention.
FIG. 2 is a cross-sectional view illustrating an example of a fuel cell.
[Explanation of symbols]
1: Polymer solid electrolyte composite membrane
2 ... Electrode
3 ... minute nodule
4: Fine fiber
7, 8 ... current collector
9,10 ... separator
11, 12 ... gas supply groove

Claims (7)

  1. A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising disposing a stretched porous polytetrafluoroethylene sheet on a sheet electrode, applying a polymer solid electrolyte resin solution to the stretched porous polytetrafluoroethylene sheet, A step of joining and integrating the sheet-like electrode and the expanded porous polytetrafluoroethylene sheet with a polymer solid electrolyte resin by removing a solvent of the solution; For producing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell.
  2. A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising disposing a stretched porous polytetrafluoroethylene sheet pre-impregnated with a polymer solid electrolyte resin solution on a sheet-like electrode, and removing the solvent of the solution to form the sheet. A method for manufacturing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell, comprising a step of joining and integrating a shaped electrode and an expanded porous polytetrafluoroethylene sheet with a polymer solid electrolyte resin.
  3. A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising forming a stretched porous polytetrafluoroethylene sheet in which a polymer solid electrolyte resin solution has been previously impregnated and the solvent has been removed, and then the polymer solid electrolyte resin solution is drawn into the stretched porous Coated on the surface of a porous polytetrafluoroethylene sheet / polymer solid electrolyte resin composite sheet or a sheet-like electrode surface, and the expanded porous polytetrafluoroethylene sheet / polymer solid electrolyte resin composite sheet is formed into a sheet in the presence of a solvent. The sheet-like electrode and the expanded porous polymer are placed on the electrode and the solvent of the solution is removed. The process for producing a polymer electrolyte fuel cell polymer solid electrolyte electrode assembly, characterized in that the tetrafluoroethylene sheet comprising the step of integrally bonding with the solid polymer electrolyte resin.
  4. A polymer for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin, and the expanded porous polytetrafluoroethylene sheet and a sheet electrode are joined and integrated with the polymer solid electrolyte resin A method for producing a solid electrolyte / electrode assembly, comprising forming an electrode on one surface of an expanded porous polytetrafluoroethylene sheet, and then applying a polymer solid electrolyte resin solution from the back surface of the expanded porous polytetrafluoroethylene sheet. A method for producing a polymer solid electrolyte / electrode assembly for a polymer electrolyte fuel cell, comprising a step of forming a polymer solid electrolyte resin film by applying, impregnating, and removing a solvent.
  5. A polymer solid electrolyte for a polymer electrolyte fuel cell in which an expanded porous polytetrafluoroethylene sheet is impregnated with a polymer solid electrolyte resin and an expanded porous polytetrafluoroethylene sheet and an electrode are joined and integrated with the polymer solid electrolyte resin A method for producing an electrode assembly, comprising preparing a stretched porous polytetrafluoroethylene sheet in which a polymer solid electrolyte resin solution is previously impregnated or in a semi-dried state or the solvent is completely removed, and the polymer solid electrolyte resin is prepared. The surface of the impregnated and stretched porous polytetrafluoroethylene sheet is coated with an ink or paste comprising at least an electrode forming component containing a polymer solid electrolyte resin component, and the solvent is removed to stretch the electrode to form the porous polytetrafluoroethylene sheet. Polymer electrolysis characterized by including a step of integrally forming an ethylene sheet Method for manufacturing a mold for a fuel cell polymer solid electrolyte electrode assembly.
  6. The sheet-shaped electrode forms a conductive gas diffusion sheet having a conductive gas-permeable sheet formed on a surface of a mixture of conductive particles and polytetrafluoroethylene, and the conductive gas diffusion sheet has a conductive gas diffusion sheet. The polymer solid electrolyte for a polymer electrolyte fuel cell according to any one of claims 1 to 4 , wherein a catalyst layer containing a catalyst and a polymer electrolyte is formed on a gas-permeable sheet. -A method for manufacturing an electrode assembly.
  7. The polymer according to any one of claims 1 to 5, further comprising a step of preparing two polymer solid electrolyte / electrode assemblies and joining and integrating the polymer solid electrolytes. A method for producing a polymer solid electrolyte / electrode assembly for an electrolyte fuel cell.
JP30367294A 1994-12-07 1994-12-07 Method for producing polymer solid electrolyte / electrode assembly for polymer electrolyte fuel cell Expired - Lifetime JP3555999B2 (en)

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JP30367294A JP3555999B2 (en) 1994-12-07 1994-12-07 Method for producing polymer solid electrolyte / electrode assembly for polymer electrolyte fuel cell
US08/568,100 US6054230A (en) 1994-12-07 1995-12-06 Ion exchange and electrode assembly for an electrochemical cell
DE69527033A DE69527033D1 (en) 1994-12-07 1995-12-07 Ion exchange membrane electrode assembly for an electrochemical cell
DE69527033T DE69527033T2 (en) 1994-12-07 1995-12-07 Ion exchange membrane electrode assembly for an electrochemical cell
EP01129420A EP1217680B1 (en) 1994-12-07 1995-12-07 Method for producing a unitary assembly for an electrochemical cell
EP95308882A EP0718903B1 (en) 1994-12-07 1995-12-07 An ion exchange membrane and electrode assembly for an electrochemical cell
US10/372,961 US7125626B2 (en) 1994-12-07 2003-02-26 Ion exchange assembly for an electrochemical cell

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JP3555999B2 true JP3555999B2 (en) 2004-08-18

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