JP2002319412A - Solid polymer electrolyte fuel cell and solid polymer electrolyte membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid polymer electrolyte fuel cell that is superior in mass-producibility and can be manufactured at low cost by a simple device, and has a high performance and a long life, and a solid polymer electrolyte membrane to be used for its material. SOLUTION: In the fuel cell, all or either of the solid polymer electrolyte membrane, the reaction layer, and the gas supply layer, which form the solid polymer electrolyte fuel cell, are formed by electrophoresis on the porous body built on the cathode or in the vicinity of the cathode in the solid polymer electrolyte solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte fuel cell and a solid polymer electrolyte membrane which is a basic component of the fuel cell, and more particularly to a solid polymer electrolyte fuel prepared by a specific method. The present invention relates to a battery and a solid polymer electrolyte membrane, and more particularly to a solid polymer electrolyte fuel cell and a solid polymer electrolyte membrane which can be prepared in a short time and by a simple means, and belongs to a battery manufacturing technique. Things.

[0002]

2. Description of the Related Art The structure of a solid polymer electrolyte fuel cell is as follows.
It is composed of three elements: an oxygen electrode (cathode) for supplying oxygen, a solid polymer electrolyte, and a fuel electrode (anode) to which fuel is supplied. In other words, it has a structure in which gas diffusion electrodes are arranged on both sides of an ion exchange membrane (solid polymer electrolyte membrane).

In this gas diffusion electrode, in a normal state, a three-phase interface is formed by supplying a reaction gas of an electrolyte and a gas on an electrode which is a fixed surface, and an electrochemical reaction proceeds at the three-phase interface. And generate electricity, catalyst,
It is composed of carbon black, fluororesin and current collector,
Usually the thickness is about 0.6mm, of which 0.5mm
The structure has a structure in which a layer is a gas supply layer and about 0.1 mm is a reaction layer.

The performance of this polymer electrolyte fuel cell is determined by how to form the above-described three-phase (band) interface. Various proposals have been made for a method of forming the three-phase band interface. It has been done.

The basic method of forming the three-phase zone interface is as follows.
A solid polymer electrolyte (fluorine-based ion exchange resin; liquid Nafion manufactured by DuPont) solution was added to and mixed with the carbon black dispersion carrying the catalyst, and then a flocculant was added and entangled with the fluorocarbon resin. After obtaining a liquid in which the catalyst-supporting carbon black and the fluororesin are mixed, the liquid is used as a liquid for forming a reaction layer, and is coated and dried on a Teflon (registered trademark) film to form a reaction layer film. This is a method of obtaining a reaction layer-solid polymer electrolyte assembly by thermocompression bonding of a layer membrane and a solid polymer electrolyte membrane (fluorine-based ion exchange resin; Nafion manufactured by DuPont, etc.). Proposals have been made, some of which are as follows.

A method in which a dispersion of an organic solvent of a carbon powder carrying a noble metal catalyst and an alcohol solution of a solid polymer electrolyte are mixed to form a solid polymer electrolyte in the form of a colloid and adsorbed on the carbon powder is applied. Kaihei 10-302805
JP-A-11-4573), a method of applying a dispersion of a catalyst and a solid polymer electrolyte, followed by treatment with an acidic solution.
No. 0), a method in which an ink-like or paste-like catalyst mixture containing a catalyst is applied to the surface of an electrolyte membrane, and a gas diffusion layer is heated and pressure-welded (Japanese Patent Laid-Open No. 2000-90944). A method using a porous electrolyte having three-dimensionally communicating pores obtained by applying a polymer electrolyte solution to a membrane and then immersing the membrane in an organic solvent having a polar group (Japanese Patent Laid-Open No. 2000-106200). .

[0007]

However, all of these methods require complicated steps such as agglomeration, coating and drying, and the production cost is still high. Therefore, the production cost is reduced and the performance is not improved. At present, there is a strong demand for improvement.

The present inventor has conducted intensive studies on the problems of the conventional technology, analyzed the processes of the conventional technology, and performed intensive research on the basis of the analysis results. They studied a means for producing a polymer electrolyte fuel cell, a solid polymer electrolyte membrane which is a basic element of a solid polymer electrolyte fuel cell, and a gas diffusion electrode.

As a result, the present inventor has reported that the solid polymer electrolyte in solution (fluorine-based ion exchange resin; Nafion solution manufactured by DuPont, etc.) A solid polymer electrolyte dissolved in alcohol at a high temperature. Since the zeta potential is negative in the liquid, electrophoresis is performed by electrophoresis on the anode side when an electric field is applied. Fluororesin fine particles dispersed in water are also usually
B. Since it has negative ions, it adheres to the other electrode by electrophoresis and is easily separated from the dispersion medium. C. Carbon black and the like that do not exhibit zeta potential in ethanol and do not cause electrophoresis, and coexist with these solid polymer electrolyte and fluororesin microparticles during electrophoresis of a solid polymer electrolyte solution or a dispersion containing fluoropolymer fine particles. They have found that rejection can be achieved and that this problem can be solved by applying this finding.

An object of the present invention is to provide a solid polymer electrolyte fuel cell which is excellent in mass productivity, can be manufactured at a low cost with a simple apparatus, and has a high performance and a long life, and a solid polymer electrolyte membrane as a raw material thereof. It is to be.

[0011]

In order to achieve the above object, the invention according to claim 1 of the present invention provides a solid polymer electrolyte membrane, a reaction layer and a gas supply layer which form a battery.
Alternatively, a solid polymer electrolyte fuel cell is characterized in that one of them is formed by electrophoresis.

According to a tenth aspect of the present invention, a solid polymer electrolyte is electrodeposited by electrophoresis on a porous body provided on or near an anode in a solid polymer electrolyte solution to form a film. A solid polymer electrolyte membrane characterized in that:

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, all or any of a solid polymer electrolyte membrane constituting a solid polymer electrolyte fuel cell and a reaction layer and a gas supply layer constituting a gas diffusion electrode are formed by electrophoresis. It is characterized by having been done. Hereinafter, a method for preparing a solid polymer electrolyte membrane, a reaction layer, and a gas supply layer by electrophoresis will be described.

The solid polymer electrolyte membrane is prepared by electrophoresis by immersing the cathode and the anode in an electrophoresis solution comprising a solution of a solid polymer electrolyte such as Nafion (manufactured by DuPont) (hereinafter referred to as a solution). In this method, a solid polymer electrolyte is electrophoresed on the anode side by passing an electric current, and is electrodeposited on a substrate, specifically a porous body, provided on or near the anode to form a film.

On the other hand, the preparation of the reaction layer and the gas supply layer constituting the gas diffusion electrode by electrophoresis is basically carried out using the above-mentioned solution. However, the solid polymer electrolyte or fluorine is prepared in water. A dispersion in which resin fine particles are dispersed (hereinafter referred to as
It is called a dispersion. ) Or a mixture of the above solution and a dispersion can also be used as an electrophoresis liquid. To form a reaction layer, the electrophoresis liquid contains hydrophobic carbon black,
It is prepared by dispersing hydrophilic carbon black, a catalyst, metal fine particles or metal oxide fine particles, and, in the case of a gas supply layer, fine particles such as hydrophobic carbon black in an electrophoretic liquid and performing electrophoresis.

Examples of the fluororesin used in the electrophoresis liquid include ethylene tetrafluoride resin, ethylene tetrafluoride / propylene hexafluoride copolymer, ethylene trifluoride chloride resin, and perfluoroalkoxy resin.

The fine particles of carbon black or the like dispersed in the electrophoresis liquid are preferably adjusted to a particle size of 1 micron or less, and have a particle size according to the required characteristics. For those having poor dispersibility in water as described above, a surfactant is used in combination, and the particles are dispersed in water to a particle size of 1 micron or less using a jet mill or the like.

The electrophoresis basically includes an electrophoresis tank having an anode and a cathode installed in parallel and facing each other, and a DC stabilized power supply as essential components. The anode is made of stainless steel, aluminum, Any conductive substrate such as silver, iron, platinum, or carbon can be used, and any metal can be used for the cathode. Nickel, platinum, palladium, and the like are preferable because hydrogen is generated.

The shape of the metal used as the anode and the cathode is preferably a net shape, but may be a plate shape. In the case of a mesh, the mesh is 0.5 to
The one of about 2 mm is good. The distance between the electrodes is preferably 5 to 100 mm. If it is too close, there is a risk of short circuit, and if it is wide, a high voltage power supply is required. It is also possible to install a filter between the anode and the cathode.

In the electrophoresis, the anode and the cathode can be theoretically performed in any state in which the anode and the cathode are horizontally or vertically arranged. However, fine particles such as hydrophobic carbon black and hydrophilic carbon black are dispersed therein. In the case of using a dispersed liquid, the fine particles tend to settle due to gravity,
The anode and the cathode are preferably arranged horizontally, and the direction in which the fluororesin particles move by electrophoresis and the direction of sedimentation due to gravity are the same. By arranging, you can shorten the travel time, not only efficient, but also
Electrodeposition can be performed uniformly on the anode, and the composition can be made equal.

In the electrophoresis, it is not necessary to fix the anode, and if the anode is continuously moved, a porous film attached to the anode can be manufactured continuously. In particular, a metal mesh serving as a base of a porous membrane is used as an anode and is continuously moved to continuously manufacture a solid polymer electrolyte membrane, a reaction layer, a gas supply layer, and the like supported by the base. be able to.

The voltage used for electrophoresis is 5 to 100 V
/ Cm, and the electrophoresis amount is proportional to the voltage, so that the electrodeposition speed can be controlled by changing the voltage.

It is desirable that the electric conductivity of the solution or dispersion used for electrophoresis is 1 mS or less. However, those having high electric conductivity require a correspondingly high voltage. It is preferable to remove the resin with an exchange resin or the like and keep the electric conductivity of the electrophoretic solution at 0.05 mS or less. The pH of the electrophoretic solution also affects the electric conductivity. .

In the present invention, the solid polymer electrolyte membrane constituting the solid polymer electrolyte fuel cell and the reaction layer and / or the gas supply layer constituting the gas diffusion electrode are formed by electrophoresis. Therefore, it is preferable that the whole is formed by electrophoresis, but a part of the existing one may be used and the remaining part may be formed by electrophoresis. Hereinafter, the outline of the production methods will be described.

1) A stainless steel foil or the like is used as an anode, and a gas supply layer (electrophoresis using a dispersion containing fluorocarbon fine particles in which hydrophobic carbon black fine particles are dispersed) and a reaction layer (hydrophobic carbon black, hydrophilic Electrophoresis using a dispersion or solution of a fluorocarbon resin in which conductive carbon black, a catalyst, metal fine particles or metal oxide fine particles are dispersed) and a solid polymer electrolyte membrane (electrophoresis using a solution). Then, at the time of fresh drying, the two stainless steel foils on which the obtained gas supply layer, reaction layer and solid polymer electrolyte membrane were laminated were heated and pressed together with the laminated body in the middle, and then the outer stainless steel foil was bonded. Used after peeling. 2) A laminate of a reaction layer and a solid polymer electrolyte membrane obtained by electrophoretically forming a reaction layer and a solid polymer electrolyte membrane on a stainless steel foil in the same manner as in 1) above, and water repellency. Carbon paper or the like is used as a gas supply layer. 3) In the same manner as in 1) above, a stainless steel foil having a reaction layer and a gas supply layer obtained by electrodepositing a reaction layer and a gas supply layer sequentially on a stainless steel foil by electrophoresis was used. ,
At the time of fresh drying, the solid polymer electrolyte membrane is heated and pressure-contacted and joined, and then the outer stainless steel foil is peeled off. In that case, in the preparation of the reaction layer by electrophoresis, it is preferable to use a solution of a solid polymer electrolyte in combination with the electrophoresis solution,
Thereby, the adhesion between the reaction layer and the solid polymer electrolyte membrane can be improved. 4) In the electrophoresis tank, a solid polymer electrolyte membrane is provided between the anode and the cathode, and fine particles moving by electrophoresis are adhered to the solid polymer electrolyte membrane, and a reaction layer and a gas supply layer are formed on the membrane. Is formed. 5) A reaction layer on a stainless steel foil in the same manner as in 1) above,
A reaction layer / solid polymer electrolyte membrane / reaction layer laminate obtained by sequentially electrodepositing a solid polymer electrolyte membrane and a reaction layer by electrophoresis, and water-repellent carbon paper are used as a gas supply layer. . 6) In the same manner as in 1), a gas supply layer, a reaction layer, a solid polymer electrolyte membrane, a reaction layer, and a gas supply layer are sequentially electrodeposited on a stainless steel foil by electrophoresis. /
Used as a laminate of solid polymer electrolyte membrane / reaction layer / gas supply layer.

The solid polymer electrolyte fuel cell of the present invention is prepared by the above method, but the preparation method is not limited to the above method, and the reaction layer and the reaction layer formed by electrophoresis are prepared. And / or drying the gas supply layer,
Solvent naphtha or the like can be added and rolled to form a sheet, which can be used as a reaction layer and / or gas supply layer sheet.

Further, the formed reaction layer and gas supply layer are
When heating and pressing at the time of raw drying, drying and joining can be performed more efficiently by using a porous body for a press plate or the like.

Further, in order to impart long-term stability to the solid polymer electrolyte fuel cell, a fluororesin water-repellent layer is formed on the entire surface of the gas supply layer in the form of dots having a diameter of about 1 mm or partially. It can also be provided in a belt shape.

[0029]

The solid polymer electrolyte fuel cell and the solid polymer electrolyte membrane of the present invention are formed by electrophoresis in an electrophoresis solution formed of a solution and / or a dispersion, and the solid polymer electrolyte (fluorine ion (Exchange resin; Nafion solution manufactured by DuPont) dissolved in alcohol at high temperature, the zeta potential is negative in the electrophoresis solution. However, also in the case of a dispersion liquid containing fluororesin microparticles and the like in the electrophoresis liquid, since the fluororesin microparticles are dispersed in water and usually have negative ions, they adhere to the negative electrode by electrophoresis, It can be easily separated from the dispersion medium.
In ethanol, the zeta potential is not shown, and carbon black, which does not cause electrophoresis, is also repelled when dispersed together with the solid polymer electrolyte or the fine particles of the fluororesin, and the fine particles can adhere to the anode by electrophoresis. It is possible.

Therefore, in the solution and / or dispersion,
A conductive substance was immersed in an electrophoretic liquid in which hydrophobic carbon black, hydrophilic carbon black, a catalyst, metal fine particles or metal oxide fine particles were dispersed, and the electrode was immersed in the electrophoretic liquid. Passing a current between the other electrode and forming a solid polymer electrolyte membrane, a fluororesin-containing film, and a fluororesin-containing film containing the various additives on the surface of the conductive substance body by electrophoresis; It is possible to use them as a gas supply layer of a gas diffusion electrode or a base material of a reaction layer, and thus to manufacture a solid polymer electrolyte fuel cell.

[0031]

EXAMPLES Hereinafter, the solid polymer electrolyte fuel cell and the solid polymer electrolyte membrane of the present invention will be described more specifically with reference to preferred embodiments. Example 1 Preparation of Solid Polymer Electrolyte Membrane A 6 cm square stainless foil with an insulating lead wire was laid on the bottom of a 6 cm square, 2 cm deep acrylic container, and its upper part 1 c
The thickness is 2 mm and the hole diameter is 50 pp, which is the counter electrode parallel to the position of m.
A foamed nickel cathode of i was installed. Fill a solution of solid polymer electrolyte (Aldrich, Nafion 5 wt% solution) until the foamed nickel cathode placed in the container is immersed.
When a voltage of 0 V is applied for 30 seconds, 60
A micron solid polymer electrolyte (Nafion) membrane was formed.

Example 2 Preparation of Solid Polymer Electrolyte Fuel Cell A 6 cm square stainless steel foil with an insulating lead wire was laid on the bottom of an acrylic container of 6 cm square and 2 cm deep, and its upper part 1 c
The thickness is 2 mm and the hole diameter is 50 pp, which is the counter electrode in parallel with the position of m.
A foamed nickel cathode of i was installed. 30w in this container
2.5 g of t% platinum-supported hydrophilic carbon black (AB-12; manufactured by Denki Kagaku Kogyo Co., Ltd.) and 1 g of low molecular weight PTFE (Rubron; manufactured by Daikin Industries, Ltd.) were added to ethanol 100.
The mixture was filled with an electrophoretic solution for forming a reaction layer, in which 25 ml of a dispersion obtained by ultrasonic dispersion in addition to 25 ml of a solid polymer electrolyte solution (manufactured by Aldrich; Nafion, 5 wt% solution) was mixed. After applying a voltage of 30 V for 15 seconds to form a reaction layer on a stainless steel foil, the electrophoresis liquid was quickly removed, and a solution containing a solid polymer electrolyte (Aldrich; Nafion, 5 wt% solution) was foamed with nickel foam. When the cathode was filled until it was immersed and a voltage of 30 V was applied for 30 seconds, a 40-micron solid polymer electrolyte (Nafion) membrane was formed on the stainless steel foil. This reaction layer and a solid polymer electrolyte (Nafion) membrane electrodeposited
100 kg / cm ² at the time of fresh drying, temperature 1
After the two pieces were heated and pressed under the condition of 35 ° C. for 1 minute, the stainless steel foil was peeled off to produce a reaction layer / electrolyte membrane assembly. Water-repellent carbon paper cut to 5 cm square as a gas diffusion layer is arranged on both sides, and is sandwiched between metal end plates provided with gas supply passages, to produce a solid polymer electrolyte fuel cell according to the present invention. did.

Comparative Example 1 Preparation of Solid Polymer Electrolyte Fuel Cell A dispersion for forming a reaction layer was applied to a solid polymer electrolyte (Nafion 115 manufactured by DuPont) and dried to prepare a reaction layer / electrolyte membrane assembly. did. The content of the platinum catalyst in this reaction layer was 0.3 mg / cm ² . Similarly, a water-repellent carbon paper cut into 5 cm squares as a gas diffusion layer was placed on both sides, and 100 kg / cm ^{2 at} a temperature of 135 ° C.
The joined body obtained by heating and pressure-contacting under the condition of 2 minutes was sandwiched between metal end plates provided with gas supply passages to produce a solid polymer electrolyte fuel cell.

Evaluation of Solid Polymer Electrolyte Fuel Cell Each of the fabricated solid polymer electrolyte fuel cells was operated under the following conditions, and the current-voltage characteristics were measured. Pure hydrogen and pure oxygen were humidified by a humidifier (glass bubbler) set at a temperature of 83 ° C., and then supplied to the battery at atmospheric pressure. As a result, in the fuel cell of the present invention, at a current density of 0.3 A / cm ² , 0.73 V
Was obtained. On the other hand, in the fuel cell of the comparative example, the 0.1.
Only an output of 0.67 V was obtained at a current density of 3 A / cm ² .

Example 3 Preparation of Solid Polymer Electrolyte Fuel Cell A 10 cm square, 1.5 cm thick acrylic plate 2, 3 shown in FIG. 1 was dug into a 6 cm square, 5 mm deep recess, and an insulation was placed on the bottom of the recess. Platinum nets 4 and 5 of 6 cm square with a lead wire were provided. An acrylic cell 1 was formed by sandwiching a solid polymer electrolyte membrane (Nafion 115 manufactured by DuPont) 6 swelled with ethanol, fixing the four corners with screws, and preventing the electrodeposition liquid 7 from leaking. Solid polymer electrolyte solution (manufactured by Aldrich;
Nafion 5 wt% solution) 80 ml, ethanol 200
ml, 30 wt% platinum-supported hydrophilic carbon black (A
B-12; manufactured by Denki Kagaku Kogyo Co., Ltd.) 3.6 g, low molecular weight P
2.7 g of TFE (Rubron; manufactured by Daikin Industries, Ltd.) was added, and the mixture was ultrasonically dispersed to prepare an electrodeposition solution. This electrodeposition liquid was filled in the acrylic cell 1, a voltage of 20 V was applied for 30 seconds, and the reaction layer was formed on one side (the cathode chamber side) of the solid polymer electrolyte membrane.
Formed. While the formed reaction layer was in a dry state, it was heated and pressed at 100 kg / cm ^{2 at} a temperature of 135 ° C. for 1 minute, whereby the solid polymer electrolyte membrane and the reaction layer were firmly bonded. The thickness of the reaction layer is approximately 0.1 mm
Met. Acrylic cell 1 is prepared and electrodeposited in the same manner as described above, with a solid polymer electrolyte membrane having a reaction layer firmly bonded to the anode chamber side on the side where the reaction layer is attached. A molecular electrolyte membrane was obtained. Again, in a dry state, it was heated and pressed under the conditions of 100 kg / cm ² , 135 ° C. for 1 minute, and the solid polymer electrolyte membrane and the reaction layer were firmly bonded. According to the present invention, the obtained solid polymer electrolyte membrane having a reaction layer formed on both surfaces thereof is sandwiched by a metal end plate provided with a gas supply passage through water-repellent carbon paper. A solid polymer electrolyte fuel cell was fabricated. At this time, the amount of supported platinum was 0.4 to 0.6 mg / cm ² . When the manufactured solid polymer electrolyte fuel cell was operated at a temperature of 80 ° C. in the same manner as described above, the cell voltage was 0.72 V at a current density of 0.3 A / cm ² .

[0036]

According to the solid polymer electrolyte fuel cell of the present invention, a thin ion exchange membrane can be easily manufactured by using electrophoresis, and a reaction layer in which polymer electrolyte molecules are dispersed around a catalyst-supporting carbon black can be easily formed. Since the reaction layer and the solid polymer electrolyte layer can maintain the continuity of the proton path, a battery with good performance can be obtained.

Further, since the solid polymer electrolyte fuel cell and the solid polymer electrolyte membrane of the present invention can be obtained by electrophoresis, the manufacturing apparatus can be simplified and the cost required for equipment cost can be reduced. Can be.

Also, because of the electrophoresis, almost no current flows between the two electrodes, so that the power consumption is small and a uniform electric field is formed between the two electrodes. A polymer electrolyte membrane, a reaction layer or a gas supply layer can be formed, and the fine particles of the gas diffusion electrode material adhere to the electrode surface with the power of electricity, so-called Coulomb force. It has the effect that a layer and / or a reaction layer can be formed, and further, it is possible to form a gas supply layer and / or a reaction layer by continuously attaching fine particles to the metal net surface of the current collector. Therefore, it has effects such as excellent mass productivity.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an acrylic cell used in Embodiment 3 of the present invention.

[Explanation of symbols]

 1 Acrylic cell 2, 3 Acrylic plate 4, 5 Platinum net 6 Solid polymer electrolyte membrane 7 Electrodeposition liquid

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H018 AA06 AS02 AS03 BB00 BB01 BB03 EE03 EE05 EE18 5H026 AA06 BB00 BB01 BB02 BB04 BB08 CX05 EE02 EE05 EE18

Claims (11)

[Claims] 1. A solid polymer electrolyte fuel cell, wherein all or any of the solid polymer electrolyte membrane, the reaction layer and the gas supply layer forming the battery is formed by electrophoresis. 2. The solid polymer electrolyte membrane, wherein the solid polymer electrolyte is formed by electrodeposition by electrophoresis on an anode in a solid polymer electrolyte solution or on a porous body provided near the anode. The polymer electrolyte fuel cell according to claim 1, wherein: 3. The solid polymer electrolyte fuel cell according to claim 1, wherein the reaction layer is formed by electrophoresis on a solid polymer electrolyte membrane. 4. The solid polymer electrolyte membrane, wherein the solid polymer electrolyte is formed by electrodeposition by electrophoresis on an anode in a solid polymer electrolyte solution or on a porous body placed near the anode. The polymer electrolyte fuel cell according to claim 3, wherein: 5. The solid polymer electrolyte fuel cell according to claim 1, wherein the reaction layer formed by the electrophoresis is formed by thermocompression bonding on a solid polymer electrolyte membrane. 6. The solid polymer electrolyte fuel cell according to claim 1, wherein the reaction layer and the gas supply layer are formed by electrophoresis on a solid polymer electrolyte membrane. 7. The solid polymer electrolyte membrane in which the solid polymer electrolyte is formed by electrophoresis on a porous body provided on or near the anode in the solid polymer electrolyte solution by electrophoresis. The solid polymer electrolyte fuel cell according to claim 6, wherein: 8. The solid polymer electrolyte fuel cell according to claim 1, wherein the reaction layer and the gas supply layer are formed by electrophoresis on both surfaces of a solid polymer electrolyte membrane. 9. The solid polymer electrolyte membrane, wherein the solid polymer electrolyte is formed by electrodeposition by electrophoresis on a porous body provided on or near an anode in the solid polymer electrolyte solution. The solid polymer electrolyte fuel cell according to claim 8, wherein: 10. A solid polymer electrolyte, wherein a solid polymer electrolyte is electrodeposited by electrophoresis on an anode in a solid polymer electrolyte solution or on a porous body placed near the anode to form a film. Molecular electrolyte membrane. 11. The solid polymer electrolyte solution in which fine particles are dispersed in the liquid, and the obtained solid polymer electrolyte membrane contains fine particles.
3. The solid polymer electrolyte membrane according to item 1.