JP3466535B2 - Electrochemical device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Electrochemical devices with excellent electrochemical stability, especially
Fuel cells that generate electricity using a chemical reaction
Used for refining equipment, gas sensors for detecting gas, etc.
It relates to a suitable electrochemical device. [0002] 2. Description of the Related Art An electrochemical device is an electrochemical reaction.
To generate electricity and purify gas
This is the device where the basic reaction takes place.
Widely applied to refining equipment, gas sensors, etc. For example
A fuel cell has a fuel cell on one of the electrodes in contact with both sides of the electrolyte body.
The fuel is supplied to the other side with an oxidizer, and the oxidation of the fuel is
Chemical energy can be directly
Converts to electrical energy, but is a solid polymer type
Taking fuel cell as an example, solid polymer as electrolyte
Refers to a membrane and a gas diffusion electrode, or an integrated product
Become. FIG. 16 shows a typical proton-conductive solid.
Electrochemical device 1 constituting a polymer electrolyte fuel cell
FIG. In the figure, 2 is a solid polymer electrolyte membrane
(Hereinafter abbreviated as an electrolyte membrane), 3 is an anode electrode,
Indicates a cathode electrode. The electrolyte membrane 2 is made of perfluorosulfur
Phonic acid film, anode electrode 3 and cathode electrode 4
Used carbon fiber carrying a platinum catalyst.
You. Next, the operation will be described. Hydrogen on anode 3
Supply oxygen to gas and cathode electrode 4 and pass through external circuit
Current from the anode electrode 3 and the cathode electrode 4
Upon release, the following reaction occurs. Anode reaction     H_Two→ 2H⁺+ 2e^-                ・ ・ ・ ・ ・ (1) Cathodic reaction     2H⁺+ 2e^-+ 1 / 2O_Two→ H_TwoO ... (2) At this time, hydrogen becomes a proton on the anode electrode 3,
Moves through the electrolyte membrane 2 to the cathode electrode 4 and
It reacts with oxygen on the cathode electrode 4 to produce water. Therefore,
Of the gas and liquid in the pores of the electrode
Water flows in and out, and electrons flow in the electrode substrate.
Therefore, in order to perform such a reaction smoothly,
Inhibits the movement of reaction active material produced or consumed by
Not to hinder the transfer of electrons
It is necessary to Regarding the movement of the active material
When water is a liquid, the flow of the reaction gas
Access to water is especially important.
You. [0004] To this end, water is applied to a machine such as a pressure or flow path structure.
As a method of promoting movement with a natural force,
JP-A-1-309263, JP-A-2-86071
, JP-A-2-260371, JP-A-3-102
No. 774 has been proposed. Also desiccant and hydrophilic
Means to promote migration by using materials with different affinity for water
JP-A-1-140562 and JP-A-3-13-1
No. 49762, JP-A-3-182205, etc.
Proposed. As for the movement of electrons, a conductive material is used for the electrodes
When using electrodes, and therefore when manufacturing electrodes
Is disclosed in, for example, Japanese Patent Application Laid-Open No. Hei 3-25856.
Kneaded with conductive carbon powder and water repellent material or reinforcing agent
There is a method of binding and metal
As a method, Japanese Patent Laid-Open No. 2-152166 has been proposed.
ing. Also, it is better to support weak electrode materials with rigid structures.
For example, Japanese Patent Application Laid-Open No. 3-149762 proposes
Have been. In addition, electrochemical devices have various applications.
In addition to those listed in the above patents,
Japanese Patent Application Laid-Open No. Sho 62-59184 discloses a gas purifying apparatus.
Japanese Patent Application Laid-Open No. 1-216714 proposes a dehumidifying element and the like.
You. [0005] SUMMARY OF THE INVENTION Problems to be Solved by the Invention
The electrochemical device is constructed as above
Therefore, as described above, the electrodes are mechanically
Brittle, cracks or drops when deformed
There was a problem that there was a possibility of doing. The present invention solves the above problems.
Excellent electrical characteristics and mechanical strength
And mass production while maintaining chemical stability.
The purpose is to obtain a chemical device. [0007] SUMMARY OF THE INVENTION The electrochemical according to the present invention
The device has gas diffusion electrodes on both sides of the solid polymer electrolyte.
At least one of the gas diffusion electrodes is provided with a plurality of through holes.
Through holes are formed, and the through holes are filled with the solid polymer electrolyte.
It is partially infiltrated.[0008] (Action) The electrochemical device according to the present invention includes a gas diffusion electrode.
At least one through-hole formed in one of the
By infiltrating part of the degradation, the gas diffusion electrode and solid
The solid polymer electrolyte has improved adhesion to the solid polymer electrolyte.
Prevent quality deformation.[0009] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of the present invention will be described.
And a reference example will be described. Reference Example 1. FIG. 1 shows an electrochemical device of Reference Example 1 of the present invention.
FIG. 1 is a conceptual cross-sectional view of
Is a metal fiber electrode substrate (gas diffusion electrode), 14 is a solid material
It is a secondary electrolyte membrane. SUS316L as metal fiber
Of a single fiber with a diameter of 12 μm and a length of 50 to 100 mm
400 g / cm of basis weight which was sintered after having been applied to the fiber^Twoof
A cloth was used. Perfluoros on the solid polymer electrolyte membrane 14
Nafion 11 from DuPont, a commercial product of rufonic acid film
7, the electrode substrates 12, 13 and the polymer film 14
50 kg / cm at 190 ° C^TwoHot pressing with surface pressure
When integrated by performing, the fibers of the electrode substrates 12 and 13
However, 50 μm was penetrated into the polymer film 14.[0010] Next, the operation will be described. This electrochemistry
The device 11 is an integrated product having a size of 10 cm square.
When manufactured, hold only one end by hand due to the steel nature of the electrode substrate.
May cause distortion that cannot be separated or reproduced.
There was no. Further, the electrochemical device 11 is
After immersion, repeat the operation of drying in air at 100 ° C three times
However, the electrode substrates 12, 13 and the polymer film 14 were completely separated.
And the shape did not change. This test can be performed with conventional
If the electrode substrate is used, cracks will be formed on the electrode substrate.
In other words, the substrate peeled off. In addition, in this reference example
When the electric resistance between the electrode base materials 12 and 13 was examined, it was found that the electric resistance was low.
Resistance could be maintained during this dipping and drying. Polymer electrolysis
Since the membrane 14 itself expands and contracts depending on the water content,
By this test, the adhesion between the polymer film 14 and the substrates 12, 13
Is very strong and, due to the strength of the metal fibers,
It is considered that the deformation of the was prevented. In addition, SUS316
The electric conductivity of L itself is about 10 times that of carbon
Electron transfer in the base material
Voltage loss can be kept low. In addition, metal fiber
Per unit volume when using a smaller diameter than this one
The reaction area increases due to the increase in the surface area of the
Since the overresistance increases, the weight per unit is smaller than this time
It is desirable to use gray cloth. Conversely, the fiber diameter is large
As for the one with large weight, you can use. In addition,
The steel of the electrode base material itself is
If you don't really need it, use felt that doesn't sinter
It is also possible to use.[0011] Reference example 2. Hereinafter, a second embodiment of the present invention will be described.
Will be described. This electrochemical device is the same as the electrode of Reference Example 1.
Gold constituting electrode bases 12 and 13 of electrochemical device 11
Fluorinated metal fiber, shape, mechanical operation
Is the same as that of the electrochemical device 11 of Reference Example 1.
You. The fluoridation of metal fiber cloths involves fluorinating or fluorinating the fibers.
This was performed by placing in hydrogen fluoride gas. Metal fiber board
Since the reaction area is large unlike fluorine or fluorine
Reduce the concentration of hydrogen gas to a few percent or less, or
The same number of moles as the number of moles of the monoatomic layer on the surface of the metal fiber
It is desirable to gradually introduce the reaction gas.[0012] Next, the operation will be described. In this reference example
When water is sprayed on the electrochemical device 11, the water is
It rolls in a spherical shape on the substrates 12 and 13. Therefore, this
Water adheres to the device using the electrochemical device 11
Also, since water does not enter the electrode bases 12 and 13,
The space through which the gas passes is secured, and
Is continuously supplied to the reaction section. Also, depending on the reaction
When water is generated, the electrode substrates 12, 13 are fluorinated.
Water-repellent properties,
The water becomes spherical and moves on the electrode substrates 12 and 13,
A large number of spaces are held in the electrode bases 12 and 13.
Reaction gas can easily flow through it,
Membrane required for the reaction is the reaction part and the electrode substrate 1
The reaction continues smoothly because it is continuously supplied to the interface with 2 and 13.
Done.[0013] Reference example 3. Hereinafter, Reference Example 3 of the present invention will be described.
Will be explained. FIG. 2 shows an electrochemical device 15 of this reference example.
FIG. 2 is a schematic cross-sectional view of FIG.
Materials (gas diffusion electrodes), 21 and 31 are electrode substrates 16 and 17
Metal fibers 22 and 32 in the electrode substrates 16 and 17
1 shows a machine fiber. The organic fibers 22 and 32 are water-repellent
Hair was mixed at a weight ratio of 10% or less using a nitrogen-based fiber.[0014] Next, the operation will be described. In this reference example
Water is sprayed on the electrochemical device 15 in the
Since there is a water-repellent fluorine-based fiber, the electrode substrate 16,
17 and rolls. Therefore, this electrochemical
Even if water adheres to the device using the vise 15, the electrode substrate
Since water does not enter inside 16, 17
The reaction gas and the gas to be detected are
Supplied constantly. If water is generated by the reaction,
Fluorine fiber has the property of repelling water
In addition, water generated by the reaction partially
It becomes spherical and moves on the electrode substrates 16 and 17, and
Is attracted onto the metal fibers, so that the electrode bases 16, 1
Space will be maintained in the whole 7 and react inside it
The gas required for the reaction can be easily
It continues to be supplied to the interface between the electrolyte membrane 14 and the electrode.[0015] Note that electrons do not move through organic fibers.
Therefore, it is not desirable to increase the amount of organic fibers further.
No. For example, even if the weight ratio is 10%, fluorine-based
The specific gravity of the fiber is about 2.1, while the specific gravity of the metal fiber is
Since it is 8.0, the volume ratio is as high as 30%,
An insulating layer may be formed depending on the entanglement method. In that case
In this case, the movement of electrons in the electrode substrate is impeded,
You.[0016] Next, a modified example of the electrochemical device 15
Will be described. Here, the organic fibers 22 and 32 are used.
Use a hydrophilic aramid fiber and mix at a weight ratio of 3% or less.
I had hair.[0017] Next, the operation will be described. In this reference example
Water is sprayed on the electrochemical device 15 in the
Is absorbed by the hydrophilic aramid fiber, and the electrode substrate 16,
17 moves toward the electrolyte membrane 14. Therefore,
When liquid water is supplied to an electrochemical device,
Water can be supplied to the reaction section while securing
You. If water is generated by the reaction,
The water is drawn to the
Gas flow from the vicinity of the interface between the metallic fiber and the electrolyte
Interfering water is removed, and the gas required for the reaction is
Supply to the electrolyte membrane 14 and the electrode interface.[0018] Also here, electrons move through the organic fiber.
It is not desirable to increase the amount of organic fiber
Not good. For example, aramid fiber has a specific gravity as small as 1.5.
Also, because it is covered with moisture and the real volume increases,
It is necessary to minimize the content. In addition, hydrophilic
Other machine fibers include polyester and acrylic.
Natural fibers such as cotton and hemp can be used in addition to synthetic fibers
But not decomposed by the functional groups of the electrolyte membrane 14
Are not appropriate.[0019] Reference example 4. Hereinafter, a fourth embodiment of the present invention will be described.
Will be described. This electrochemical device is the same as the electrode of Reference Example 3.
Fluorine the metal fibers 21 and 31 of the electrochemical device 15
Reference Example 3 for the shape and mechanical operation
The same as the electrochemical device 15 using the hydrophilic fiber of
You. In addition, the fluorination of the metal fiber was performed using the cloth of Reference Example 2.
Same as prime.[0020] Next, the operation will be described. In this reference example
Water is sprayed on the electrochemical device 15 in the
Are the electrode bases 16 and 17 because of the water-repellent metal fibers.
This electrochemical device 15 was used because it rolled over
Even if water adheres to the device, water will be present in the electrode bases 16 and 17.
A space for gas to pass through is secured without entering
The gas to be detected is constantly supplied to the reaction section. Meanwhile, the reaction
Draws water towards the organic fibers
Metal that causes electron transfer and electrochemical reactions
Water that impedes gas flow from near the fiber-electrolyte interface
The gas required for the reaction is removed and the electrolyte membrane 14 serving as a reaction part is removed.
And the electrode substrates 16 and 17 are continuously supplied to the interface. Also,
Again, the electrons do not move through the organic fiber,
It is not desirable to increase the amount more than necessary.[0021] Reference example 5. Hereinafter, a fifth embodiment of the present invention will be described.
Will be described. FIG. 3 shows an electrochemical device 4 of this reference example.
1 is a schematic cross-sectional view of FIG.
Electrodes having catalyst particles supported on each of the electrode substrates 12 and 13 of Example 1
It is an electrode substrate (gas diffusion electrode). Platinum as catalyst particles
Black (platinum fine particles) was used. There are various loading methods
But for a lower alcohol solution containing 5% polymer electrolyte
The suspension containing 30% platinum black in weight by weight
1cm on the substrate^TwoApply 4mg per coat and dry
I let it. Then, the hot press described in Reference Example 1
The polar bases 42 and 43 and the electrolyte membrane 14 were integrated.[0022] Next, the operation will be described. In this reference example
Flowing hydrogen through one electrode substrate 42 of the electrochemical device 41
And the other electrode base 43 is negative with respect to the electrode base 42.
Is applied, the electrochemical device 11 of Reference Example 1
Then, for the first time when the potential between both poles is applied 100 mV or more
The current flowed, and hydrogen was detected from the electrode substrate 13 side,
In this reference example, a current flows at 10 mV or more, and the electrode substrate
It was confirmed that hydrogen was generated from the 43 side. This
The platinum supported on the electrode substrates 42 and 43 serves as a catalyst.
It can be confirmed that the electrochemical reaction is accelerated
Was. As for the catalyst, the same platinum was used as the catalyst.
So-called platinum loaded with platinum supported on carbon fine particles
Carbon catalyst is applied by this method due to its low specific gravity
The amount of catalyst in the applied liquid is about 30% of that of platinum black.
When using a 20% supported catalyst, the amount of platinum is
It is reduced to about 5% compared to the time. Therefore, the amount of platinum is greatly
It can save, but the catalytic effect is somewhat reduced. As a catalyst
Not only platinum but also white metal elements and alloys containing them,
Is a commercially available catalyst
Use other types of catalyst particles
However, if the method of supporting the substrate by coating is adopted,
Need to be adjusted.[0023] Reference example 6. This electrochemical device is for reference
Platinum having a catalytic effect is applied to each of the electrode substrates 12 and 13 of Example 1.
It is plated. To perform platinum plating,
To remove impurities on the surfaces of the electrode substrates 12 and 13,
Wash with grease. In this state, the electrode substrates 12 and 13 are
The electrode substrates 12 and 13 are cleaned
Boil in water for several minutes or immerse in 1N hydrochloric acid for several seconds
You. Then, it moves to a plating process. Plating solutions are generally commercially available
Phosphoric acid-based acid type under standard conditions
Although used, there is no particular problem with other known liquid compositions.
However, unlike plating, the following
There was such a phenomenon. It is the water generated during plating
Elementary bubbles stay in the fiber to make contact between the fiber surface and the plating solution.
Fibers in the plating solution
Need to be vibrated. Further, the electrode substrate 12,
13 is flexible, so buoyancy acts on the part with air bubbles
May be lifted up on the four sides of the substrate or
Jigs that allow current to flow with both ends fixed are required.
Required (not shown). Regarding the plating amount, consider the electrode substrate as a flat plate.
When this was done, the plating amount was adjusted to an amount that resulted in a plating thickness of 1 μm.
Of course, it may be more, but do not consider the catalytic effect.
This amount was sufficient. 0.1A / c depending on application
m^TwoEquipment that operates at low current densities below
The amount of the jack may be extremely reduced. Also, as a catalyst
Even if other elements or alloys are used,
A known plating technique according to the composition may be used.[0024] Next, the operation will be described. Regarding the catalytic effect
Then, it is the same as the electrochemical device 41 of Reference Example 5.
Omitted. The electrode substrate of this reference example was immersed in boiling water for 5 hours.
Even if the process of pickling and drying is repeated, the plating
No screeching occurred. This is similar to fuel cells and electrolyzers
The catalyst drops even when used under conditions where the reactants flow rapidly.
No stable characteristics can be maintained.[0025] Reference example 7. Hereinafter, a seventh embodiment of the present invention will be described.
Will be described. FIG. 4 shows a plurality of electronically independent
It is a top view of the electrochemical device 45 which has an electrode part.
In the figure, 12A, 12B, 12C and 12D are electronic
Are independent electrodes in the same plane. Thickness for electrode material
300 μm carbon paper was used. 10cm square
A 12 cm square electrolyte membrane 14 is placed on the electrode 13.
Furthermore, four independent electrodes 12A to 4 cm in diameter
12D and four independent electrodes 12A to 12D inside
The same 250 µm thick Teflon sheet 46 with holes
Arrange on a plane. Then, hot under the same conditions as in Reference Example 1.
Pressed. The surface pressure is based on the area of four independent electrodes.
I made it. In addition, a gas can flow through the electrode substrate 13.
A gas flow path, a flow path that allows different gases to flow through the four electrodes,
And set up terminals for reading the voltage of each electrode.
(Not shown).[0026] Next, the operation will be described. For electrode 13
Flows pure hydrogen and separate electrodes 12A-12D
Each contains the fuel exhaust gas from the four cells of the fuel cell stack
Shed. Each electrode12A, 12B, 12C, 12
DAnd the voltage generated between the electrodes 13 flows through the respective flow paths.
(3) according to the hydrogen partial pressure of the fuel exhaust gas
Voltage. Therefore, one electrochemical device
Thus, the concentrations of the four gases could be measured simultaneously.[0027] Here, the method to know the hydrogen concentration is explained
I do. Flow pure hydrogen on one pole and hydrogen on the other.
When the gas to be inspected is introduced, the Nernst equation (3)
Is generated between the two poles.
Knowing the hydrogen concentration in the gas to be inspected by measuring
Can be.[0028]   E = RT / 2F × 1n (P_H2/ P_R・ ・ ・ ・ ・ ・ ・ ・ (3)[0029] Where R is gas constant and F is Faraday constant
Number, T is absolute temperature, P_H2Is the hydrogen gas content in the test gas
Pressure, P_RIndicates the pressure of pure hydrogen.[0030] In this reference example, 4
Although two electrodes 12A to 12D are arranged, a plurality of electronic
If the electrode is independent of the
It may be as follows. In this reference example, the counter electrode 3 is 1
Although it was composed of12A, 12B, 12C, 12D
Divided into four corresponding to each, four electronically independent
It is also possible to configure a battery that has been used. In that case,
By connecting four batteries in series, on average four times the power
Pressure can be generated.[0031] Reference Example 8. Hereinafter, Reference Example 8 of the present invention will be described.
Will be explained. FIG. 5 shows an electrochemical device 51 of this reference example.
FIG. 3A is a plan view of the same figure.
(B) is a sectional view thereof. In the figure, 12R, 12
W is an electronically independent co-planar electrode, and 52 is
It is a partition (sealing part) that blocks the electrode 12R from the outside air.
For the electrodes 12R and 12W, platinum-plated electrode substrates are used.
The electrode of Example 6 was used. Assembling of 10cm square electrode 13
A 12 cm square electrolyte membrane 14 is placed on top of the
An electrode 12R having a diameter of 1 cm and a hole having a diameter of 1.5 cm
The opened electrodes 12W of 10 cm square are arranged on the same plane.
Then, hot pressing was performed under the same conditions as in Reference Example 1.
The surface pressure was based on the area of the counter electrode 13. And electrode 1
Hole for voltage terminal to prevent outside air from flowing into 2R
Silicon rubber with a thickness of 0.2mm and a radius of 1.2cm
And a hemispherical cap made of rubber (septum 52). Soshi
And a 1 mm thick SUS304 package with a 2 mm hole
Sandwiching the electrode with a punching metal
And a terminal for reading the voltage of the electrode 12R.
(Not shown). At this time, one punching metal is
Electronically connected to pole 12W, the other punch
Metal is electrically connected to the electrode 13,
The electrode 12R is in an electrically insulated state except for the voltage terminal
Has become.[0032] Next, the operation will be described. This electrochemistry
The device 51 is placed in the air, and the electrode 12W-the counter electrode 13
During that time, a potential of 4 V is applied via a punching metal.
The moisture in the air in contact with the electrode 13 is calculated according to Equation 4 described later.
The electrode 12W forms hydrogen ions in the electrolyte membrane 14,
Move to 12R side. At the electrode 12W, the hydrogen ions
The acid in the air immediately after being reduced to hydrogen according to the equation (5)
Reacts with element to form water. On the other hand, the electrode 12R
On turns electrons into hydrogen as shown in equation 7 below.
However, since it is sealed by the rubber cap 52,
Filled with hydrogen gas, excess hydrogen only, rubber cap 5
2 and the membrane 14.[0033] Here, the movement of hydrogen ions will be described.
You. When DC voltage is applied to both electrodes in moist air,
Due to the electrochemical reaction, moisture in the air is charged on the anode side.
Loss of hydrogen and become hydrogen ions, and the cathode in the electrolyte membrane
Moving. 2H_TwoO → 4H⁺+ O_Two+ 4e^-        ・
.... (4) Hydrogen ions obtain electrons on the cathode and become water
It is reduced to hydrogen, but reacts with oxygen in the air to form water.   4H⁺+ O_Two+ 4e^-→ 2H_TwoO ... (5) Eventually, the water on the anode side moves to the cathode side.
This lowers the humidity of the space on the anode side. Ma
For example, when DC voltage is applied to both electrodes in water, electrochemical
Due to the reaction, water loses electrons at the anode and hydrogen ions
And oxygen gas, the oxygen gas is generated as a gas, hydrogen
The ions move to the cathode side in the electrolyte membrane. On the other hand,
In the sword, hydrogen ions generate electrons and generate hydrogen gas
I do.   2H_TwoO → 4H⁺+ O_Two+ 4e^-      ・ ・ ・ ・ ・ (6)   4H⁺+ 4e^-→ 2H_Two                ・ ・ ・ ・ ・ (7)[0034] As described above, the electrode 12R is connected to the hydrogen reference electrode.
The voltage of the electrode 12R and the counter electrode 13 and the electrode 12R
By measuring the voltage of the electrode 12W, this electrochemical
Separate and measure the polarization of each pole in the reaction
Can be. So, between this voltage and 12W-13
Adjusting the applied voltage may cause corrosion of the electrodes.
To avoid the danger of applying abnormal voltage to the electrodes
In both cases, operation is possible with the maximum required voltage
Thus, the device can be made more compact.[0035] Embodiment 1 FIG. Hereinafter, the first embodiment will be described.
This will be described with reference to the drawings. FIG. 6 shows the electrochemistry of the present embodiment.
FIG. 5 is a conceptual cross-sectional view of the device 53, in which FIG.
Reference numerals 4 and 55 denote electrode substrates having through holes 56, and 14 denotes a polymer.
It is an electrolyte membrane. As the electrode substrate, S shown in Reference Example 1 was used.
US316L, diameter 12 μm, length 50-100 mm
Is sintered after passing through a fiber opening machine.
g / cm^TwoCloth was used. Perfluorinated polymer film 14
Nafion 1 of DuPont as a commercial product of sulfonic acid membrane
17, the electrode substrates 54 and 55 and the polymer film 14 are used.
50 kg / cm at 190 ° C^TwoHot pressing with surface pressure
When integrated by performing, the fibers of the electrode substrate
And the electrolyte membrane 14 has a through hole
I was digging in to fill 56.[0036] Next, the operation will be described. 10cm square
When manufacturing an electrochemical device 53 of a size
Even if it is not possible, hold only one end by hand due to the steel nature of the electrode substrate.
Even if you handle it, this unified material will separate and cause unreproducible distortion.
I didn't wake him. In addition, this one
After immersion in water, repeat the operation of drying in air at 100 ° C 10 times
The electrode substrates 54 and 55 and the polymer film 14 were completely separated.
Without releasing, the shape of this integrated product did not change. This trial
When the test is performed using a conventional electrode substrate, the electrode base
Cracks start from the hole made in the material, the base material cracks and peels
I fell down. Further, the electrode substrate 5 of the present embodiment
Examination of the electric resistance between 4, 55 showed that the low resistance
It could be maintained during immersion and drying. Polymer electrolyte membrane 14
The body expands and contracts depending on the moisture content.
Adhesion between the electrode base polymer film 14 and the bases 54 and 55
Is very strong and the strength of the metal fibers
It is thought that the movement of was able to be restricted.[0037] The electric conductivity of SUS316L itself is
Since it is about 10 times the electric conductivity of carbon,
Electron transfer is smooth and keeps voltage loss low
be able to. Also, when the electrolyte membrane enters the through hole,
So that the water that has entered the liquid directly touches the electrolyte membrane
This facilitated the supply of water to the membrane. In addition, gold
If the fiber diameter is smaller than this one,
Although the surface area around the volume increases, the reaction area increases,
In this case, the gas permeation resistance increases.
It is desirable to use a cloth with a small basis weight. Conversely, the fiber diameter
For large ones, those with a large basis weight can also be used. Fret
The base material of the electrode itself
When sintering is not so necessary
It is also possible to use[0038] Reference Example 9. Hereinafter, Reference Example 9 will be described.
You. FIG. 7 is a schematic cross-sectional view of the electrochemical device 58 of this reference example.
FIG. Reference numeral 59 denotes a layer made of hydrophilic fibers. This
Here, a polyester fiber diameter of 1 μm and a thickness of 2 mm
Woven fabric was used.[0039] Next, the operation will be described. This electrochemistry
When water is sprayed on the device 58, the water is applied to the hydrophilic layer 59.
After being substantially uniformly distributed in the spread surface,
It reaches the electrolyte membrane 14. On the other hand, water is electrolyzed by the reaction
Excess water at the interface between the membrane 14 and the electrode 12
It is absorbed by the aqueous layer 59, spreads over the entire surface, and is removed.
It is. Space will be maintained throughout the substrate,
The reaction gas can easily flow through
Is supplied to the interface between the electrolyte membrane 14 as a reaction part and the electrode.
I can. However, since electrons do not move through organic fibers,
The exchange of electrons between the polar base material 12 and the outside is performed by the hydrophilic layer 59.
A terminal is taken out from between the electrolyte membranes 14 or hydrophilic.
It is necessary to make a hole in a part of the layer 59 so that only the terminal passes
Therefore, it is not suitable for operation in which a large current flows. Hydrophilic
Other fibers such as polyamide and polyethylene
In addition to synthetic fibers, natural fibers such as cotton and hemp can be considered.
Synthetic fibers that can freely control the pore size of are preferred. In addition,
In the above reference example, the one having a thickness of 2 mm was used.
If it is applied to the side that discharges water, thicker
Operating at room temperature without any problems and without directly touching the electrolyte membrane 14.
Restrictions on material selection, besides hydrophilicity
There is no need to do it. In addition, from inside the hydrophilic layer, further outside
It is also possible to carry a known water supply polymer.Reference Example 10 . Less thanReference example 10About
I do. FIG. 8 shows a bent electrode and an electrolyte membrane according to this embodiment.
Is an electrochemical device 61 in which
The gas diffusion electrodes 62 and 63 are bent, and the gas diffusion electrode 64 is bent.
Electrolyte membrane (solid polymer electrolyte). Also, 65
A gas flow path formed by the electrode 62, 66 is an electrode 63
It is a gas flow path formed by. Also, 68, 69
Is the conductive separator that forms the other end of this gas flow path.
It is a tar plate. 70 is an insulating spacer film.
A Teflon sheet having a thickness of 250 μm was used. Gas expansion
No special technique is required for bending the electrode
Can be carried out in the same manner as the sheet metal press. In addition,
When integrating the electrodes 62 and 63 and the electrolyte membrane 64,
For example, JP-A-3-84866, JP-A-3-2082
No. 61, JP-A-3-208262 and the like.
If the method is adopted, the film is formed into the shape of the bent electrode substrate.
Is easy to follow. Here, SUS316
A gas flow path having a width of 2 mm is formed from a sintered electrode substrate of L fiber.
Was.[0041] Next, the operation will be described. This electrochemistry
In the device 61, hydrogen gas which is one of electrochemical reactions
Perform a purification reaction. Hydrogen gas containing carbon dioxide as impurities
Is introduced into the gas passage 65 and the separator plate 68 is separated.
When a voltage of 0.5 V is applied to the heater plate 69, the electrode 6
2, a reaction of the formula 8 described below occurs, and only hydrogen gas is
And move in the electrolyte 64 toward the electrode 63
Then, the flow path 2 returns to the hydrogen gas by the reaction of Equation 9 described later.
3 will be introduced.[0042] Here, hydrogen containing impurities on the anode side
When flowing gas and applying voltage, only hydrogen gas reacts
It becomes hydrogen ions and moves to the cathode side in the electrolyte membrane.
You.   H_Two→ 2H⁺+ 2e^-                ・ ・ ・ ・ ・ (8)   2H⁺+ 2e^-→ H_Two                  ・ ・ ・ ・ ・ (9) On the cathode side, hydrogen ions obtain electrons and reduce them to hydrogen gas
Is done. Only hydrogen ions can move in the electrolyte membrane
Thus, pure hydrogen can be obtained on the cathode side.[0043] Therefore, electrons are separated from the electrode 62 by separation.
Through an external circuit through a separator plate 69,
It flows to the electrode 63. The thickness of the electrode substrate is about 0.3 mm
Although the metal fiber is highly conductive,
Separator from the top of the long flow path 65TBoard
There is almost no voltage loss even with the movement of electrons up to 68,
The reaction proceeds. At this time, the electrolysis per simple flat area
The reaction area is large because the interface area between the material and the electrode is doubled and wide.
It was secured tightly and it became possible to purify a large amount of gas. Further
While keeping the thickness of the electrode thin,
The thickness of the unit battery is very
Thinner, making the battery stack very compact
Can be configured. Regarding contact resistance between separator and electrode
Can maintain the contact pressure by utilizing the elasticity of metal fiber
Therefore, the voltage loss can be kept low.Reference Example 11 . Less thanReference Example 11About
I do. FIG. 9 shows an embodiment of the present invention,
Electrochemical device 71, and 72 is an elastic current collector.
, 73 is a current collector of a counter electrode, and 70 is an insulating spacer.
You. The material of the elastic current collector 72 is austenitic
Other than stainless steel and martensitic stainless steel,
It is possible to use metals and alloys with spring properties
Both use a plastic film coated with a conductive layer
It is possible, but it should be selected in consideration of corrosion resistance depending on operating conditions.
Need to be Here, dehumidification operated at room temperature and air
SUS316L thickness 0.05m for use in a container
A plate provided with holes for gas permeation was used. The hole is
Known, eg punching, etching or machining
Can be created. The size of the elastic current collector 72 is 10 cm square.
And is machined into an arc with a radius of 10 cm. Moth
SUS fiber felt is platinum plated
The electrode of Reference Example 6 is used. Assembling the current collector 73
The electrode 12, the electrolyte membrane 14, and the electrode 13 are stacked on the
Current collector 72 such that the center of the arc faces outward from above.
And sandwich it between frames 74. Frame 74 is 3m thick
m, made of hard polyethylene, using current collector 73 with screws, etc.
Fixed. The elastic current collector 72 has an end through which a current flows.
A child is attached (not shown).[0045] Next, the operation will be described. Current collection in the atmosphere
When a voltage of 4 V is applied to the current collector 73 on the body 72,
The reaction of the above-described formula 4 occurs on the pole 12, and the current collector 73 side
The water in the air is decomposed, and protons flow through the electrolyte 14.
Moving toward pole 13 and reacting in air
Combines with oxygen and comes out as water. At this time, the electrons are
12, the current collector 72 through an external circuit through the current collector 73,
It flows to the electrode 13. The contact resistance between the current collector 72 and the electrode 13
The resistance uses the elasticity of the current collector 72 to maintain the contact surface pressure.
As a result, the voltage loss could be kept low. Also one
Unintegrated electrodes and electrolyte membranes can also be used with this method.
Therefore, the integration step could be omitted. In addition,
In the present embodiment, the electrode substrate itself has a catalytic function.
Used, but the dissolution medium must be integrated with the electrode
Is not particularly specified, for example, as disclosed in JP-A-3-46764.
Insert a catalyst sheet between the electrode substrate and the electrolyte membrane
May be. The total thickness is very thin, 0.7mm
And compact when attached to various devices
Can be configured.[0046] Embodiment2. The following embodiment2about
explain. FIG. 10 shows an embodiment of the present invention.2Electrochemistry
Conceptual diagram of fuel cell 81 using device 53 (FIG. 6)
54 is a cross-sectional view, in which 54 is a cathode having a through hole 56, 55
Is an anode also having a through hole 56, and 68, 69
Is a separator plate having a gas passage made of carbon.
You. Effective surface of each electrode 54, 55 of the electrochemical device 81
The product is 100cm^TwoWas used. In addition, the electrolyte membrane 14
Used was Nafion 115 manufactured by DuPont.[0047] Next, the operation will be described. Fuel cell 81
Is heated to 80 ° C. by an external heater (not shown),
Hydrogen gas humidified at 95 ° C.
Air humidified to 50 ° C. was introduced into the flow path 65. Sepa
Connecting the radiator plates 69-68 to an external circuit
On the gate 55, hydrogen emits an electron by the reaction of the equation (10).
To move to the cathode 54 through the membrane 14 with water.
You.   2H_Two→ 4H⁺+ 4e^-              ・ ・ ・ ・ ・ (10) At the cathode 54, hydrogen ions and oxygen combine to generate electrons.
The resulting water is produced.   4H⁺+ O_Two+ 4e^-→ 2H_TwoO ... (11) At this time, the temperature of the cell depends on the dew point of the anode gas (95 ° C).
Is excessively low, so that excessive moisture
Condense. Although the droplets are carried in the flow path 66 by the dynamic pressure of the gas,
Touch the electrolyte membrane 14 filling the through hole 56 in the electrode.
And partly absorbed, and partly the electrolyte in the through-hole 56.
It flows into the electrolyte membrane 14 along the membrane 14. On the other hand Caso
Although there is excess water in the wire 54, the through hole 56 is filled.
The electrolyte membrane 14 is more hydrophilic than the electrode 54
The water moves along the through hole 56 into the flow path 65 and circulates.
Evaporates on contact with air. This makes it necessary for electrochemical reactions.
The supply of necessary water becomes possible, and the cathode electrode 54
Since the water inside can be quickly drained, supply oxygen necessary for the reaction.
Supply, and maintain high characteristics even when the current density is increased.
Can be.Reference Example 12 . Less thanReference Example 12About
I do. FIG.Reference Example 12The electrochemical debye
Is a dehumidifier 91 using a stiffener 71, and 72 is elastic.CollectionElectric
Body, 92 is a DC power supply, 93 is a housing to be dehumidified, 94 is a housing 9
3 is a window for dehumidification opened in the side wall, and the hole is a known example.
Such as punching, etching or machining
It may be a metal plate joined together. Here, the thickness is 0.
A 5 mm SUS304 punching metal was used.
Since the window 94 functions as a current collector, the insulating layer
It was unpainted so that it would not occur, but it was insulated from the enclosure 93
Fixed. Also, on the outside of the housing 93, there is a fixing device for fixing the dehumidifying element.
A frame 74 is provided. Frame 74 is welded to the same steel plate as the housing
And is attached to the housing. The outside is the same paint as the case
However, the inside is unpainted to conduct with the current collector 72.
did. The size of the current collector 72 is 10 cm square.
And is bent into an arc having a radius of 10 cm. Electrical
Chemical device 71 is used for gas diffusion electrode
Electrode of Reference Example 6 obtained by plating platinum on
117 film at 150 ° C, surface pressure 50 kg / cm^TwoAnd unite with
Was used. The lower heating temperature is due to the electrode film
And the substantial thickness of the electrolyte membrane 14 is reduced.
This is to prevent backflow of water by keeping it thick.
The integration is somewhat poor, but it is pressed by the current collector 72.
There is no problem. The electrode 12 has a thickness of 400
μm 400g / cm^TwoFelt, weight of electrode 13
Is 200 g / cm with a thickness of 200 μm^TwoSet of Fell
Is used. The electrode 13 is assembled along the frame 74 during assembly.
Insert the electrochemical device so that it faces the body and
Insert the current collector 72 so that the center of the arc faces the outside of the housing.
Entered. The window 94 is connected to the + terminal of the DC power supply.
The negative terminal was grounded to the housing 93.[0049] Next, the operation will be described. Start the DC power supply
When it moves, a voltage of 4V is applied to the window 94 with respect to the housing 93.
You. The window 94 is electrically connected to the electrode 13, and the housing 93 is connected to the frame 7.
Since it is electrically connected to the electrode 12 through the four current collectors 72,
A voltage of 4 V is applied to the electrode 13 with respect to the electrode 12. Do
And the reaction of the formula 3 occurs on the electrode 13, and the air in the housing 93 is
The water inside is decomposed, and the protons pass through the electrolyte 14 in the electrode 1
2 to the oxygen in the outside air according to the reaction of Equation 4.
And come out as water. At this time, the electrons
Through the window 94, through the DC power supply 92, the enclosure 93, the frame 7
4. The current flows to the current collector 72 and the electrode 12. Current collector 72 and electricity
The contact resistance between the poles 12 is obtained by utilizing the elasticity of the current collector 72.
Since contact surface pressure can be maintained, voltage loss can be kept low
it can. In this method, the electrochemical device is a current collector
It is only fixed by the elasticity of the
It can be easily replaced simply by pulling out the chemical device 71.
When the volume of the housing 93 is about 10 liters,
Relative humidity should be about 40-50% lower than the atmosphere
did it. Further, the electrochemical device of Embodiment 2 was used.
In such cases, a large amount of gas can be dehumidified.
Prevents condensation inside the fins if placed on the windward side of the cooling fins
And oxygen enrichment is possible.Reference Example 13 . Less than,Reference Example 13About
I will tell. FIG. 12 shows a plurality of electronically independent electrodes in a plane.
Having a partReference Example 13Using the electrochemical device 45
FIG. 2 is a conceptual sectional view of a gas concentration sensor 101. In the figure
12A, 12B, 12C, and 12D are electronically independent.
The electrodes stand in the same plane. 30 for electrode material
0 μm carbon paper was used. 10cm square electrode
13cm, 12cm square over the circumference of 1cm
Is placed. In addition, 16 2
FIG. 13 shows a cm-cm independent electrode in a range where the electrode 13 is below.
As shown, the electrodes are arranged at intervals of 6 mm. Andthree
ExampleHot pressing was performed under the same conditions as in Example 1. In addition, surface pressure
Is an area of 64 independent electrodes 64cm^TwoBased. Ma
In addition, a gas flow path 102 through which gas can flow through the counter electrode 13
And flow channels 103A to 103A through which different gases can flow through the 16 electrodes.
103P (103A to 103D in the figure) was provided.
A voltage terminal 104 is connected to the electrode 13 via a current collector (not shown).
And connected. The voltage terminals 105 are also provided on the electrodes 12A to 12P.
A to 105P were connected. In addition, the end plates 106 and 107
Polycarbonate was used. End plate 106 is a conductive metal
Although it is possible to use a material,
Since it is necessary to electrically insulate the poles 12A to 12P,
When using conductive materials such as metal or carbon
It is necessary to prevent the conductive portion from touching the electrode.[0051] Next, the operation will be described. In the flow path 102
Flow pure hydrogen, and each of the independent electrodes
The fuel exhaust gas from 16 cells of the pond stack was flushed. Each
The voltage generated between the electrodes 12A to 12P and the electrode 13 is
Depending on the hydrogen partial pressure of the fuel exhaust gas flowing through each flow path
It becomes the voltage shown by Formula 3. Each voltage 104-1
Monitor the voltage between 05A and 104-105P
And the exhaust gas of the 16 cells of the fuel cell stack
The hydrogen concentration could be measured at the same time. In this exam
Methane reforming simulation gas (hydrogen 80
%, Residual carbon dioxide). Each cell voltage in the stack
There was variation due to measurement, but what is this variation?
I didn't know if it was based. However, this concentration sensor
Is installed, the exhaust gas from the cell with low cell voltage is
The electrode voltage is higher than the other cells, and the hydrogen concentration
Was found to be extremely low. Fuel cell star
Since the current flowing through each cell is the same in
The same applies to the amount of hydrogen gas. Nevertheless hydrogen concentration
Low indicates that less fuel is flowing into the cell.
Problem with the distribution of gas in the stack
Understand that this voltage can be monitored by optimizing the flow path structure and gas flow rate.
Can be performed by
Tack characteristics have been greatly improved.[0052] BookReference exampleThen the electrode 13 with pure hydrogen flowing
Was measured and the gas concentration was measured.
If only the variation in concentration is measured as in
Neglecting the potential of the reference electrode 13, the potentials of 12A to 12P
The concentration distribution by monitoring only the
It is also possible to know. For example, the number of divided electrodes is limited to 2 cells.
The cells at both ends where gas distribution is most likely to be uneven.
The gas is introduced into the flow paths 103A and 103B to
When the exhaust gas is introduced into the flow path 102, the flow path 103A-1
If the voltage between 03B exceeds a certain value, the total gas flow rate
Driving method that keeps stack operation normal by increasing
It is also possible to adopt a law.Reference Example 14 . Less thanReference Example 14About
I do. FIG.Reference Example 14Using the electrochemical device 51
Is an electrolytic cell 111 used, 112 is an electrolytic cell container, 13
Is anode, 12W is cathode, 12R is independent cathode
113, an anode current collector 113, a cathode current collector 114,
52 is a silicone rubber cap, 115 is a water supply port, 1
16 is an oxygen outlet, 117 is a hydrogen outlet, 118 is an electrode
Current (voltage) terminal to 12R. The thickness of the electrode
0.1mm basis weight 100g / cm^TwoStainless steel fiber baked
Electrodes 12W and 12R were plated with platinum using a tie.
The electrode 13 is made of iridium plating.
Was. The electrolyte membrane 14 is a perfluorosulfonic acid membrane
A Nafion membrane was used.[0054] Next, the operation will be described. Electrode 12W-
When a DC voltage is applied across the anode 13, 6
Water is decomposed by the reaction of the formula and oxygen is generated.
At 12 W, hydrogen gas is generated in accordance with equation (7). Also,
When the terminal 118 is short-circuited with the cathode, hydrogen is also
Occurs, the inside of the rubber cap 52 is filled with hydrogen, and
Overflowed from the gap between the membrane cap 52 and the membrane 14. Current
Density of 500mA / cm^TwoWhen the current flows about 2
Although it was about V, operation was continued for a while at this current density.
Then, the voltage increased and the current stopped flowing. Terminal 11
8 and the terminal and anode when the cathode is disconnected
Measured the voltage between the terminal and the cathode.
When the voltage rises, the voltage between the terminal 118 and the anode 13 changes.
However, the voltage between the cathode and the terminal 118 almost changed.
Did not convert. Therefore, the characteristics of the electrolytic cell 111 deteriorate.
Because I could guess that there was a problem on the anode side
When the test is performed with attention to the anode, it occurs on the anode
It turns out that the supply of water was dripping with the bubble of oxygen
Was. Therefore, make the anode electrode base material half the thickness
The voltage did not rise. This
Thus, the circuit of the terminal 118 is cut off at regular intervals during operation.
When the voltage between the electrode 13 and the electrode 13 is measured,
If there is a problem with the
Or just before it breaks down
The problematic part can be repaired.Reference Example 15 . Less thanReference Example 15About
I do. FIG.Reference Example 15Using electrochemical device 61
It is the gas purification device 121 which was used. Electrochemical device (one
The lower part is the anode 62 and the upper part is
Is a cathode 63. The electrode substrate has a basis weight of 300 g /
cm^TwoOf SUS316L fiber with thickness of 250 μm
A gas flow path with a width of 2 mm and a height of 2 mm is formed with the polar substrate
Was. 65 is a gas flow path formed by the electrode 62, 66
Is a gas flow path formed by the electrode 63. 68,
69 is a conductive end forming the other end of the gas flow path.
Plate, 122 is a conductive separator plate, whereby
Electrically, four purification units were connected in series.
You. The four devices are labeled A to D respectively.
Was. Each separator plate 122 is made of SUS304.
It is composed of a plate, gas seal with electrolyte membrane and bent
The manifold to the gas flow path with electrodes is made of Teflon resin
(Not shown). Finally, the laminate is
0.2kg / cm^TwoEnd plate with surface pressure68-69Hold the gap
I'm wearing it.[0056] Next, the operation will be described. Diacid to impurities
Hydrogen gas containing activated carbon is introduced into gas flow paths 65A to 65D
Then, when a voltage of 2 V is applied to the end plate 68 with respect to the end plate 69,
The reaction of Formula 8 occurs on the electrodes 62A to 62D,
Only protons become protons in the electrolytes 14A to 14D.
Moving toward 3A-63D, depending on the reaction of Eq.
The raw gas is returned and introduced into the flow paths 66A to 66D. Ma
At this time, the interface area between the electrolyte and the electrode per simple flat area
Has been doubled, which is almost double that of a flat-plate electrode.
Was able to flow. This is the same gas area
This means that twice the gas amount could be processed with respect to the production equipment. Sa
Furthermore, while keeping the thickness of the electrode thin,
Since the flow path was constituted by 61 itself, the flow path was formed on the separator plate.
30% smaller per sheet than when digging
Therefore, the height became about 2/3. For this reason,
Size for gas purification unit of the same size is reduced to about 1/3
As a result, remarkable miniaturization has become possible. Also, separator
Since it is not necessary to dig a groove in the hole, as in this embodiment,
Commercially available thin plates can be used, significantly reducing costs
did it.[0057] According to the present invention, the number of gas diffusion electrodes is small.
At least on one side, a plurality of through holes are formed and these
The solid polymer electrolyte is configured to penetrate a part thereof.
The adhesion between the gas diffusion electrode and the solid polymer electrolyte
And prevents deformation of the solid polymer electrolyte.
There is an effect that can be stopped.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a configuration of an electrochemical device according to Embodiment 1 of the present invention. FIG. 2 is a cross-sectional view illustrating a configuration of an electrochemical device according to a third embodiment of the present invention. FIG. 3 is a cross-sectional view illustrating a configuration of an electrochemical device according to Reference Example 5 of the present invention. FIG. 4 is a plan view showing a configuration of an electrochemical device according to Reference Example 7 of the present invention. FIG. 5 is a plan view and a cross-sectional view illustrating a configuration of an electrochemical device according to Reference Example 8 of the present invention. FIG. 6 is a cross-sectional view illustrating a configuration of the electrochemical device according to Embodiment 1 of the present invention. FIG. 7 is a cross-sectional view illustrating a configuration of an electrochemical device according to Reference Example 9 of the present invention. FIG. 8 is a cross-sectional view illustrating a configuration of an electrochemical device according to Reference Example 10 of the present invention. FIG. 9 is a cross-sectional view illustrating a configuration of an electrochemical device according to Reference Example 11 of the present invention. FIG. 10 is a sectional view showing a fuel cell using the electrochemical device according to Embodiment 2 of the present invention. FIG. 11 is a cross-sectional view illustrating a dehumidifier using the electrochemical device of Reference Example 12 of the present invention. FIG. 12 is a cross-sectional view showing a gas concentration sensor using the electrochemical device of Embodiment 13 of the present invention. FIG. 13 is a plan view showing a configuration of an electrode of a gas concentration sensor using the electrochemical device of Embodiment 13 of the present invention. FIG. 14 is a sectional view showing an electrolytic cell using the electrochemical device of Reference Example 14 of the present invention. FIG. 15 is a cross-sectional view showing a gas purification apparatus using the electrochemical device of Reference Example 15 of the present invention. FIG. 16 is a sectional view showing a conventional electrochemical device. [Description of Signs] 11 Electrochemical device, 12, 13 Metal fiber electrode base material (gas diffusion electrode), 14 Solid polymer electrolyte membrane, 15
Electrochemical device, 16, 17 Electrode substrate (gas diffusion electrode), 21, 31 Metal fiber, 22, 32 Organic fiber, 41 Electrochemical device, 42, 43 Electrode substrate (gas diffusion electrode), 45 Electrochemical device, 51 electrochemical device, 52 partition (sealing part), 53 electrochemical device, 54, 55 electrode base material, 56 through hole, 5
8 electrochemical device, 59 layer made of hydrophilic fiber, 61 electrochemical device, 62, 63 gas diffusion electrode, 64 electrolyte membrane (solid polymer electrolyte), 71 electrochemical device, 72 elastic current collector, 73 Electric body.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-262954 (JP, A) JP-A-63-82355 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 4/86 H01M 8/02 H01M 8/10 G01N 27/26 C25B 11/00

Claims (1)

(57) [Claim 1] In an electrochemical device having gas diffusion electrodes provided on both sides of a solid polymer electrolyte, a plurality of through holes are formed in at least one of the gas diffusion electrodes. An electrochemical device wherein a part of the solid polymer electrolyte is penetrated into these through holes.