JPH11131276A - Electrolytic ozone generating element and electrolytic ozone generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the generation of hydrogen in a cathode, a to convert hydrogen to water by oxidation decomposition even if it is generated and to ensure safety by forming platinum catalyst-contg. catalyst layers on both faces of a porous substrate having electronic conductivity and gas permeability to obtain the cathode. SOLUTION: In an electrolytic ozone generating element with an anode 61 and a cathode 62 placed opposite to each other with a solid polyelectrolyte membrane 4 in-between, the cathode 62 is obtd. by forming platinum catalyst- contg. catalyst layers 2, 3 on both faces of a porous substrate 1 having electronic conductivity and gas permeability. Even if hydrogen is generated in the catalyst layer 2 of the cathode kept in contact with the polyelectrolyte membrane 4, the hydrogen is converted to water by oxidation decomposition in the catalyst layer 3 on the rear side of the porous substrate 1. The deterioration of lead dioxide forming the anode 61 due to reduction is prevented by interposing a catalyst layer 6 of α-lead dioxide between the anode 61 and the polyelectrolyte membrane 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical element, in particular, an electrolytic ozone generating element in which an anode and a cathode are opposed to each other with a solid polymer electrolyte membrane interposed therebetween, and a DC voltage is applied to generate ozone from the anode. TECHNICAL FIELD The present invention relates to an electrolytic ozone generator configured by mounting an electrolytic ozone generating element.

[0002]

2. Description of the Related Art As a conventional electrolytic ozone generating element and an electrolytic ozone generating apparatus incorporating the electrolytic ozone generating element, for example, a water supply type as described in Japanese Patent Publication No. 2-44908 is used. In general, practical use of an ozone generating element of a type that supplies air instead of water is also being studied. FIG. 16 is a side view (a) and a plan view (b) of a conventional air supply type electrolytic ozone generating element. In the figure, 61 is the anode of the electrolytic ozone generating element, 62 is the cathode of the electrolytic ozone generating element, 4 is the solid polymer electrolyte membrane, 1 is the base material of the cathode, 2 is the catalyst layer of the cathode, and 7 is the current of the cathode. Terminal 8 is an anode current terminal. For the anode, for example, a titanium mesh plated with platinum and electrodeposited with β-type lead dioxide is used. The solid polymer electrolyte membrane 4 is made of Nafion (DuPont) and an electrolytic ozone generating element. Of carbon paper 1
In this case, a catalyst layer 2 formed of carbon powder carrying platinum is used. It is known that β-type lead dioxide (black) has higher current efficiency of ozone generation than α-type lead dioxide (brown), and β-type lead dioxide is used in a conventional ozone generating element. .

[0003]

The conventional air-supply type electrolytic ozone generating element is constituted as described above. A DC voltage of about 3.5 V is applied to the ozone generating element, Ozone and oxygen are generated, and water is generated on the cathode side. However, at the cathode, not all protons are converted to water, but some are converted to hydrogen. This is because a considerable portion of the voltage applied by the external DC power supply is applied to the cathode side, and the cathode may be placed at a sufficiently low potential for generating hydrogen. In particular, when the voltage is suddenly applied after a high humidity or after a long pause, remarkable hydrogen generation occurs, and there is a risk that the atmosphere on the cathode side may exceed the hydrogen explosion limit. There was a safety problem. In addition, the generated hydrogen gradually reduces the β-type lead dioxide of the anode to lead monoxide and lead ions, which are taken into the solid polymer electrolyte membrane to increase the ionic conduction resistance, resulting in an ozone generating element. There is a problem that the performance decreases with time.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and suppresses the generation of hydrogen at the cathode, and reliably oxidizes and decomposes hydrogen even if hydrogen is generated at the cathode. An object of the present invention is to obtain an ozone generating element having a function of converting water into water and ensuring safety, and an ozone generating apparatus having such an ozone generating element. Another object is to prevent lead dioxide of the anode from being reduced and deteriorated.

[0005]

According to a first aspect of the present invention, there is provided an electrolytic ozone generating element comprising a solid polymer electrolyte membrane sandwiched between an anode and a cathode. A porous substrate having electron conductivity and gas permeability is used, and a catalyst layer containing a platinum catalyst is formed on both surfaces of the porous substrate.

An electrolytic ozone generating element according to a second configuration of the present invention is an electrolytic ozone generating element having an anode and a cathode facing each other with a solid polymer electrolyte membrane interposed therebetween, wherein the cathode has an electron conductive property. In addition, a porous substrate having gas permeability is used, and a catalyst containing a platinum catalyst is contained in the porous substrate.

The electrolytic ozone generating element according to the third structure of the present invention has a catalyst layer made of α-type lead dioxide provided between an anode and a solid polymer electrolyte membrane.

The electrolytic ozone generating element according to a fourth aspect of the present invention uses a titanium porous substrate plated with α-type lead dioxide as an anode, and the porous substrate and the solid polymer electrolyte are used as anodes. A fine particle layer of α-type lead dioxide is sandwiched between the film and the film.

The electrolytic ozone generating element according to a fifth aspect of the present invention has at least one hole penetrating the anode, the solid polymer electrolyte membrane, and the cathode.

[0010] The electrolytic ozone generating element according to a sixth aspect of the present invention has a structure in which at least one of an anode and a cathode is provided on the outside.
A water-repellent and gas-permeable porous membrane is provided.

[0011] In the electrolytic ozone generating element according to a seventh aspect of the present invention, the porous film has a protection means for protecting the element against external force.

An electrolytic ozone generating element according to an eighth aspect of the present invention comprises an anode portion and a cathode portion disposed between the anode and the cathode with the solid polymer electrolyte membrane interposed therebetween, the anode portion and the cathode portion being arranged outside the solid polymer electrolyte membrane. In addition, a plurality of current terminals are formed respectively.

In the electrolytic ozone generating apparatus according to the first aspect of the present invention, the electrolytic ozone generating element is mounted between the socket body and the socket lid, and the cathode current terminal is connected to the cathode connecting portion of the socket body. And the anode current terminal portion comes into contact with the socket lid portion or the anode connection portion of the socket body when the socket lid portion is attached.

In the electrolytic ozone generating apparatus according to the second configuration of the present invention, the space facing the cathode of the socket cover is formed as a closed space, and the vent hole on the socket body side or the electrolytic ozone generating element is provided. Is connected to the space on the anode side through a hole penetrating through.

An electrolytic ozone generating apparatus according to a third aspect of the present invention is provided with an electrolytic ozone generating element equipped with an electrolytic ozone generating element and provided with an anode and an ozone generator when no ozone is generated from the apparatus. A lower voltage is applied between the cathodes than when ozone is generated.

An electrolytic ozone generator according to a fourth configuration of the present invention is equipped with an electrolytic ozone generating element, and a current assumed to generate ozone in an electrolytic ozone generator equipped with a DC power supply. A fuse that cuts at a current value higher than the current value is provided in the current circuit.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 FIG. FIG. 1 is a side view (a) and a plan view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 1 of the present invention. In the figure, 1 is a cathode substrate, 2 is a catalyst layer on the front surface of the substrate in contact with the solid polymer electrolyte membrane 4 of the cathode, 3 is a catalyst layer on the back surface of the cathode substrate, 62 is the cathode, 4 is Solid polymer electrolyte membrane, 5 is an anode substrate, 6 is an anode catalyst layer, 61 is an anode, 7a is a cathode current terminal, 7b is a cathode voltage terminal, 8a is an anode current terminal, and 8b is an anode voltage. Terminal.

As the base material 1 of the cathode, fine particles of polytetrafluoroethylene (hereinafter referred to as PTFE) are adhered to carbon paper made of carbon fiber and having a thickness of 0.3 mm, and repelled by heat treatment at 350 ° C. Water-treated one was used. The diameter of the cathode excluding the current and voltage terminals is 22m
m. The catalyst layer 2 on the front face of the cathode is formed by fixing a liquefied solid polymer electrolyte as a binder to a catalyst in which platinum fine particles are supported on carbon powder, and has a thickness of 20 μm.
μm. The catalyst layer 3 on the back surface is obtained by fixing fine particles of PTFE as a binder to a catalyst in which fine platinum particles are supported on carbon powder, and has a thickness of 20 μm. The catalyst layer 2 on the front surface and the catalyst layer 3 on the back surface are formed on the cathode substrate 1 by first applying a screen printing method to one surface of the water-repellent cathode substrate 1 by using a screen printing method. After applying, 35
After heat-treating at 0 ° C., PTFE is fused to the back surface of the cathode substrate 1, and after imparting strong water repellency to the catalyst layer 3 on the back surface, the PTFE is turned over and the front surface is screen-printed. The catalyst layer 2 on the front surface was applied and heat-treated at 150 ° C., and the solid polymer electrolyte added as a binder was fused to the cathode substrate 1 to form a highly hydrophilic catalyst layer 2. That is,
A highly water-repellent catalyst layer 3 was formed on the back surface of the cathode substrate, and a highly hydrophilic catalyst layer 2 was formed on the front surface.

The base material 5 of the anode is made of a thin plate of titanium having a thickness of 50 μm, which is cut and stretched and is slightly plated with platinum, and has a diameter of 20 mm excluding the current and voltage terminals. The anode catalyst layer 6 is made of β-type lead dioxide, is formed by applying the above-mentioned β-type lead dioxide on the solid polymer electrolyte membrane 4, and has a thickness of 20 μm and a diameter of 20 mm. As the solid polymer electrolyte membrane 4, Nafion 115 (about 120 μm in thickness) manufactured by DuPont was punched out with a punch to a diameter of 22 mm. A cathode 62 having two catalyst layers 2 and 3 on the front and back, a solid polymer electrolyte membrane 4 having an anode catalyst layer 6 coated on one side, and an anode substrate 5 are connected to each other by the current and voltage terminals of the anode and the cathode. They were superposed on concentric circles at right angles and hot-pressed at 160 ° C. to produce an ozone generating element.

Next, the operation will be described with reference to FIG.
FIG. 2 is an explanatory diagram showing the operation of the electrolytic ozone generating element of FIG. In the figure, 11 is an external circuit, and 12 is a DC power supply. When a DC voltage of about 3 V is applied between the anode 61 and the cathode 62, moisture in the air is electrolyzed at the anode 61, and ozone and oxygen (by-products) are converted by the reactions shown in Equations 1 and 2. Occur. _{3H 2 O → O 3 + 6H} + + 6e - ··· ( Equation _{1) 2H 2 O → O 2} + 4H + + 4e - ··· ( Equation 2)

Electrons move to the cathode 62 through the external circuit 11 and protons pass through the solid polymer electrolyte membrane 4 to the cathode 1.
It moves to the catalyst layer 2 on the front surface. In the catalyst layer 2 on the front surface of the cathode, oxygen in the air reacts according to the following formula to generate water. Part of the water returns to the anode 61 via the solid polymer electrolyte membrane 4 and is used for the reaction at the anode 61. O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O (formula 3)

If the supply of oxygen to the catalyst layer 2 on the front surface of the cathode is insufficient, hydrogen may be generated by the following equation. 2H ⁺ + 2e ⁻ → H ₂ (Equation 4) However, even when hydrogen is generated in the catalyst layer 2 on the front surface of the cathode, it is oxidized by the catalyst layer 3 on the back surface of the cathode and returned to water. Therefore, no hydrogen is emitted into the atmosphere.

The ozone generating element according to the first embodiment is placed in a stainless steel evaluation box having a capacity of 43 liters.
When 3 V was continuously applied for one week and the ozone concentration and the hydrogen concentration were measured, the ozone concentration was 50 ppm and the hydrogen concentration was 10 ppm.
ppm or less (below the detection limit of the hydrogen sensor used).

In order to compare the effects of the structure of the cathode of the ozone generating element according to the first embodiment, as shown in Table 1, 6
Each type of sample was prepared, placed in a 43-liter evaluation box, and continuously applied with a voltage of 3 V for one week to examine the ozone concentration and the hydrogen concentration. The sample 1 was the same as that of the first embodiment, and the catalyst layer 2 on the front surface of the cathode was hydrophilic because it was manufactured using a liquefied solid polymer electrolyte membrane having a strong hydrophilic property as a binder. The layer 3 is water repellent because PTFE fine particles having strong water repellency are used as a binder. Thus, by changing the type of the binder, it is possible to distinguish between hydrophilicity and water repellency of the catalyst layer. Similarly, in Sample 2, both the front and back surfaces are hydrophilic, and in Sample 3, both the front and back surfaces are water repellent.
In Sample 4, contrary to Sample 1, the front surface was made water-repellent and the back surface was made hydrophilic. In addition, as a conventional electrolytic ozone generating element, Sample 5 had a hydrophilic catalyst layer on the front surface and nothing on the back surface. In sample 6, the front surface was a water-repellent catalyst layer, and nothing was provided on the back surface. The results are summarized in Table 1.

[0025]

[Table 1]

Samples 1 to 4 having the same structure as that of the present embodiment in which the catalyst layers 2 and 3 are provided on both surfaces of the cathode have a large difference in hydrogen concentration as compared with the samples 5 and 6 having the conventional structure. Was seen. In the conventional structure, the hydrogen concentration is 10
Although it exceeded 00 ppm, in the structure of the present embodiment, the hydrogen concentration was kept at 50 ppm or less. This difference is apparently due to the presence or absence of the catalyst layer 3 on the cathode back surface. Since a slight amount of generated hydrogen is oxidized by the catalyst layer 3 on the cathode back surface due to a change in the potential of the cathode, the samples 1 to 4 It is considered that the hydrogen concentration at was kept at 50 ppm or less. Although the hydrogen concentration of about 1000 ppm in the conventional example is considerably lower than the lower limit of hydrogen explosion of 4%, since it is an average hydrogen concentration in a 43-liter container, it is not sufficiently safe even in a local hydrogen concentration. I can not say. Therefore, the effect of this embodiment in which the hydrogen concentration can be kept at 50 ppm or less is great.

Looking at Table 1 in more detail, Samples 1 and 3 in which the catalyst layer 3 on the cathode back surface was made water-repellent were Samples 2 and 4 in which the catalyst layer 3 on the cathode back surface was made hydrophilic.
Hydrogen concentration is significantly lower than 10 ppm. This is because the catalyst layer 3 on the back surface of the cathode is made water repellent,
Since gas diffusibility is secured as compared with the case where the catalyst layer 3 on the cathode rear surface is made hydrophilic, supply of oxygen in the air to the catalyst layer 2 on the cathode front surface becomes easy, and the cathode front This is because the possibility of generating hydrogen in the surface catalyst layer 2 is reduced.

On the other hand, there was a difference in the ozone concentration, and the sample 1 in which the catalyst layer 2 on the cathode front surface was made hydrophilic was used.
And Sample 2 had a higher ozone concentration than Samples 3 and 4 in which the catalyst layer 2 on the cathode front surface was made water-repellent. This is because, when the catalyst layer 2 facing the solid polymer electrolyte membrane 4 is hydrophilic, the utilization rate of the catalyst increases, the polarization of the cathode decreases, and conversely, the polarization of the applied voltage applied to the anode increases. This is because ozone is easily generated. That is, the catalyst layer 2 on the cathode front surface is made hydrophilic,
The sample 1 in which the catalyst layer 3 on the back surface of the cathode is made water-repellent is most effective for lowering the hydrogen concentration and increasing the ozone concentration.

In the above embodiment, the anode catalyst layer 6 is applied to the solid polymer electrolyte
And the solid polymer electrolyte membrane 4 coated on one side with an anode catalyst layer 6 and the anode substrate 5 to form an ozone generating element. The anode catalyst layer is formed by electrodeposition as in the prior art. An ozone generating element may be formed by providing the anode, the solid polymer electrolyte membrane 4, and the cathode 62 having the same structure as in the present embodiment on the entire surface of the anode substrate.

Embodiment 2 FIG. FIG. 3 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 2 of the present invention. In the figure, reference numeral 9 denotes a cathode on which a catalyst containing a platinum catalyst is attached over the entire area in the thickness direction of the porous substrate.

The base material of the cathode 9 is a 0.3 mm-thick carbon paper made of carbon fiber, and is a solid polymer electrolyte obtained by liquefying a catalyst in which platinum particles are supported on carbon powder without performing a water-repellent treatment. Was used as a binder, heat-treated at 150 ° C., fused to the solid polymer electrolyte added as a binder, and adhered so as to coat the fiber surface of the carbon paper. Observation with a scanning electron microscope photograph confirmed that this catalyst coating layer covered the surface of the carbon fiber thinly, had a thickness of 5 μm or less, and did not block the pores of the substrate. As the anode substrate 5, the anode catalyst layer 6, and the solid polymer electrolyte membrane 4, those having the same specifications as in the first embodiment were used. The cathode 9 having the catalyst adhered over the entire surface of the base material, the solid polymer electrolyte membrane 4 having the anode catalyst layer 6 applied on one side, and the anode base material 5 are arranged such that the current and voltage terminals of the anode and the cathode are perpendicular to each other. As described above, the ozone generating element was formed by overlapping the concentric circles and hot pressing at 160 ° C.

One week in a 43 liter evaluation box
When a voltage of V was applied to check the ozone concentration and the hydrogen concentration,
The ozone concentration was 45 ppm and the hydrogen concentration was 15 ppm, and effects such as a higher ozone concentration and a lower hydrogen concentration were obtained as compared with the conventional example shown in Table 1. This is because a sufficient amount of oxygen diffuses into the catalyst existing over the entire base material of the cathode, and the slightly generated hydrogen is quickly oxidized.

Embodiment 3 FIG. 4 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 3 of the present invention. In the figure, reference numeral 13 denotes an anode composed of a titanium porous substrate plated with α-type lead dioxide.

The base material of the anode is used in the first and second embodiments.
This is a slightly expanded platinum metal of the same type as that of the above, except that the catalyst layer of the anode is not coated on the solid polymer electrolyte membrane 4, but α-type lead dioxide is plated on the anode substrate. Configured. The plating of α-type lead dioxide can be easily formed by electrolytic plating of lead ions in an alkaline solution. On the other hand, the plating of β-type lead dioxide can be easily formed by electrolytic plating of lead ions in an acidic solution. That is, the plating can be easily performed by distinguishing between α and β by the acidity of the plating solution. For the cathode 62 and the solid polymer electrolyte membrane 4,
The same specifications as in the first embodiment were used. A cathode 62;
The solid polymer electrolyte membrane 4 and the anode 13 having the above-mentioned configuration were overlapped on a concentric circle so that the current and voltage terminals of the anode and the cathode were perpendicular to each other, and were hot-pressed at 160 ° C. to produce an ozone generating element. .

For three months in a 43 liter evaluation box,
The voltage of 3 V was continuously applied to check the ozone concentration and the hydrogen concentration. For comparison, an electrolytic ozone generating element using a platinum expanded metal made of titanium and a β-type lead dioxide plated as an anode was similarly evaluated. FIG. 5 shows changes in ozone concentration and hydrogen concentration for three months.

FIG. 5 is a graph showing the change over time in the performance of the electrolytic ozone generating element according to the third embodiment. In the figure, 14 is a change in ozone concentration when α-type lead dioxide is used as a catalyst layer of the anode, 15 is a change in ozone concentration when β-type lead dioxide is used as a catalyst layer of the anode, 16
Represents a change in hydrogen concentration when α-type lead dioxide is used as the anode catalyst layer, and 17 represents a change in hydrogen concentration when β-type lead dioxide is used as the anode catalyst layer.

In the case of α-type lead dioxide, the ozone concentration in the initial stage of operation is low, but gradually increases to 50% after 100 hours.
ppm, and no degradation was observed until 1500 hours thereafter. On the other hand, in the case of β-type lead dioxide, the initial ozone concentration was high, but gradually decreased over 1500 hours. Since the current value during this period was almost constant,
It is considered that the current efficiency of ozone generation gradually decreased due to an increase in the generation rate of oxygen. Also, hydrogen gradually increases,
After 1500 hours, it reached 500 ppm. After operation, the anode was disassembled and the anode was examined. As a result, in the case of α-type lead dioxide, the color was brown at first, but changed to black after operation. Observation with a scanning electron microscope showed that α
No abnormalities such as cracks were found in the lead dioxide plating layer of the mold. On the other hand, in the case of β-type lead dioxide, observation with a scanning electron microscope revealed that numerous cracks were formed in the β-type lead dioxide plating layer.

Based on the results of observation with a scanning electron microscope,
FIG. 6 schematically shows the cross section of the α-type lead dioxide plating layer (a) and the β-type lead dioxide plating layer (b) after operation. In the drawing, 18 is an expanded metal made of titanium, 19 is a platinum plating layer on the surface of titanium, 20 is a plating layer of α-type lead dioxide, and 21 is a β-type plating layer formed on the surface of an α-type lead dioxide plating layer. A thin layer of lead dioxide, 22 is a plated layer of β-type lead dioxide, and 23 is a crack formed in the plated layer of β-type lead dioxide in large numbers. α-type lead dioxide is brown and alkaline and stable, and β-type lead dioxide is black, which is acidic and stable, contrary to α-type lead dioxide. It is considered that the sulfonic acid group of the solid polymer electrolyte is a strong acid, and the surface of the α-type lead dioxide plating layer has undergone a phase change to have been changed to an acidic and stable β-type. The α-type lead dioxide plating layer is a tough film, while the β-type lead dioxide plating layer is a very brittle layer, is weak to stress and easily cracks. FIG.
It is considered that the crack in (b) was caused by the internal stress existing in the plating layer of β-type lead dioxide.
If a crack occurs in the β-type lead dioxide plating layer, moisture will enter the platinum plating layer on the titanium surface. Then, the plated platinum serves as a catalyst for oxygen generation, and oxygen generation takes precedence over ozone generation. It is considered that the reason why the ozone concentration was reduced without decreasing the current value in the time-dependent change 15 in FIG. 5 is that moisture began to enter such cracks and oxygen generation began to occur. The increase in hydrogen concentration is because oxygen generation (1.2 V) occurs at a potential lower than the ozone generation potential (1.5 V), so that the potential on the cathode side decreases and the probability of hydrogen generation increases. . On the other hand, for a thin layer of β-type lead dioxide generated on the surface of α-type lead dioxide, cracks are unlikely to occur due to its thinness,
Even if a crack occurs, there is no crack that reaches the platinum plating layer or titanium because there is a tough α-type lead dioxide plating layer. That is, if the anode structure according to the third embodiment of the present invention is adopted, an electrolytic ozone generating element having excellent life stability can be obtained.

In the above embodiment, the anode 13 is formed by plating α-type lead dioxide on the anode substrate. However, α-type lead dioxide is applied to the solid polymer electrolyte membrane 4 as a catalyst layer of the anode. The surface may be turned black as in the case of the third embodiment, and the same effects as in the case of the third embodiment can be obtained with respect to the ozone generation ability and the service life.

Embodiment 4 FIG. FIG. 7 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 4 of the present invention. In the figure, reference numeral 24 denotes a titanium porous substrate plated with α-type lead dioxide, and 25 denotes a thin film sheet in which α-type lead dioxide fine powder is applied to a stretched PTFE thin film. An anode is constituted by the material 24 and the thin film sheet 25.

As the anode substrate 24, one having the same specifications as those used for the anode of the third embodiment was used. Further, a thin film sheet 25 obtained by applying a fine powder of α-type lead dioxide to a stretched PTFE thin film is coated on the PTFE thin film using a roller as described in, for example, JP-A-8-2130270. Is a soft, flexible brown film with a thickness of 1
0 μm. As the cathode 62 and the solid polymer electrolyte membrane 4, those having the same specifications as in the first embodiment were used. Cathode 6
2, the polymer electrolyte membrane 4, and the anode 61 were concentrically overlapped so that the current and voltage terminals of the anode and the cathode were perpendicular to each other, and were hot-pressed at 160 ° C. to produce an ozone generating element. .

As in the case of the third embodiment, the ozone concentration and the hydrogen concentration were examined by applying a voltage of 3 V for 3 months in a 43 liter evaluation box, and the ozone concentration was found to be 100 hours in the initial period. Gradually increased to 80 ppm, 1500
The ozone concentration was kept stable over time. Also, hydrogen was kept below the detection limit of 10 ppm. Furthermore, as a result of disassembly after the operation, the surface of the thin film sheet 25 in contact with the solid polymer electrolyte membrane 4 and the surface of the porous substrate 24 made of titanium plated with α-type lead dioxide turned black. It is considered that the ozone concentration increased due to the change to β-type lead dioxide. Further, the ozone concentration was higher than that in the third embodiment because of the effect that the α-type lead dioxide fine particles significantly increased the reaction area of the anode.

In the fourth embodiment, the expanded PTF
Although a thin film sheet 25 in which α-type lead dioxide fine particles are applied to a thin film made of E was used, as a fluorine-based porous thin film,
Other than PTFE, other FEP, PFA, and the like can be used, and similarly, α-type lead dioxide fine particles can be formed into a sheet. Also, the thin film sheet 25 of α-type lead dioxide fine particles can be manufactured by kneading and rolling PTFE fine particles and α-type lead dioxide fine particles.
Further, instead of using a sheet, α-type lead dioxide fine particles and a liquefied solid polymer electrolyte (Nafion liquid, manufactured by Aldrich) are mixed and pasted, and the solid polymer electrolyte membrane 4 is directly anode-coated by brushing or the like. Even when the catalyst layer was formed, the surface turned black as in the case of the fourth embodiment, and the same effects as those of the fourth embodiment were obtained with respect to the ozone generation ability and the life.

Embodiment 5 FIG. FIG. 8 is a side view (a) and a plan view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 5 of the present invention. In the figure, reference numeral 26 denotes a hole passing through the anode 61, the solid polymer electrolyte membrane 4, and the cathode 62.

The structure and material are the same as those of the first embodiment. Finally, a punch having a diameter of 5 mm
Was opened. Newspaper was placed on each of the cathodes of the electrolytic ozone generating element having the structure of the first embodiment and the electrolytic ozone generating element of the fifth embodiment, and 3 V was applied thereto. One hour later, in the configuration of Embodiment 1, the hydrogen concentration increased to 8000 ppm,
In the fifth embodiment, it was 25 ppm. In the configuration of the first embodiment, the reason why the hydrogen concentration increased when the cathode was covered was that oxygen in the air near the cathode was reduced. On the other hand, the reason why the hydrogen concentration hardly increased in the fifth embodiment is that oxygen is supplied to the cathode side through the through hole. Therefore, according to the configuration of the fifth embodiment, even when the cathode side is covered, generation of hydrogen is suppressed, and an effect of maintaining high safety can be obtained.

In the fifth embodiment, the case where one through-hole 26 is provided in the center is shown, but a plurality of through-holes may be provided or may be provided at the end. Also, a small hole may be provided over the entire surface.

Embodiment 6 FIG. FIG. 9 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 6 of the present invention. In the figure, reference numeral 27 denotes a water-repellent and gas-permeable porous film, which is a porous thin film made of PTFE.

A comparison test was conducted between the case where the porous thin film 27 made of PTFE was provided on the outside of the electrolytic ozone generating element having the same specification as that of the embodiment 5 and the case where the element was not provided with water. went. As a result, even when water was applied to the device provided with the porous thin film 27, the water tumbled down like a ball, and almost no change was observed in the current flowing through the element, but the porous thin film 27 was not provided. It was found that when water was applied to the object, more than three times the current flowed, and a large amount of hydrogen was generated temporarily. This is due to the direct supply of water
The supply rate of water, which is the reaction product of the electrolysis, was rate-limiting and the reaction rate, which was constant, was accelerated all at once, and the ionic conduction resistance of the solid polymer electrolyte membrane decreased, causing a large current to flow. It is considered that hydrogen was generated due to lack of oxygen. Therefore, according to the configuration of the sixth embodiment, even when water is directly applied to the ozone generating element, generation of hydrogen is prevented, and high safety is ensured.

Further, in the ozone generating element of the present embodiment, by providing the porous thin film 27, it is possible to prevent the entry of metal ions from dust and the like and the attachment of organic substances, and have the effect of maintaining the performance for a long time. In addition, the porous thin film 27 made of PTFE is insulative and does not cause a short circuit.

In the sixth embodiment, the porous thin film 27 is used.
Was made of PTFE, but PFA or FEP
A similar effect may be obtained. Alternatively, the porous thin film 27 may be provided only on the side of the cathode or anode where water may be directly applied. further,
The porous thin film 27 does not have to be a thin film, and may be formed in a sheet shape or a plate shape.

Embodiment 7 FIG. FIG. 10 is a side view (a) and a plan view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 7 of the present invention. In the figure, 28 is a stainless steel plate with a plurality of holes subjected to a water-repellent treatment,
Reference numeral 29 denotes a hole passing through the stainless steel thin plate 28.

In the seventh embodiment, a stainless steel thin plate having a plurality of holes, which has been subjected to a water-repellent treatment on the outside of the anode side in the structure of the sixth embodiment, is used to protect the element against external force. It is arranged as a means. In this configuration, it was confirmed that a sufficient amount of ozone was generated and almost no hydrogen was generated. When the metal penetrates the ozone generating element, a trouble such as a short circuit between the anode and the cathode, a large current flows and heat is expected. However, according to the seventh embodiment, the ozone generation is stopped due to the sharp metal or the like. Even when the element is about to break through, the thin plate 28 made of stainless steel does not easily penetrate the element, and the element can be prevented from being broken. Further, in the configuration of FIG. 10, the porous thin film 27 is disposed between the anode 61 and the metal thin plate 28, and the electrical insulation between the anode 61 and the metal thin plate 28 is ensured. Current is prevented from flowing from the thin plate 28 to the outside, and air permeability between the anode 61 and the outside air is secured.

In the seventh embodiment, the case where a plurality of holes 29 are formed in the stainless steel thin plate 28 is shown. However, a titanium or nickel thin plate having a plurality of holes may be used. It has the same ozone resistance as a thin plate, and can be water-repellent with a fluororesin. Further, since the resistance to ozone is enhanced by coating with a fluororesin, a metal oxidized by ozone can be used. Further, foamed metal, punching metal, or the like can be used. Also, on the cathode side, a stainless steel plate having a plurality of holes and subjected to a water-repellent treatment may be arranged outside the cathode side.

Embodiment 8 FIG. FIG. 11 is a plan view (a) and a side view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 8 of the present invention. In the figure, 30 is an elliptical anode, 31 is an elliptical cathode, 32 is an anode current terminal A, 33 is an anode current terminal B, 34 is a cathode current terminal C, and 35 is a cathode current terminal D. It is.

In the ozone generating element according to the present embodiment, the anode 30 and the cathode 31 are formed in a slender shape resembling an ellipse, and the axes of the slender shapes of the anode and the cathode are shifted with the solid polymer electrolyte membrane 4 interposed therebetween. Since they face each other, four peripheral portions where the anode and the cathode do not directly face each other are formed. In the four peripheral portions where the anode and the cathode do not directly face each other, two portions at both ends on the anode side can be effectively used as anode current terminal portions, and two portions at both ends on the cathode side can be effectively used as cathode current terminal portions. Since the reaction is near the center of the overlap of the two ellipses, for example, if the anode current terminal portion A32 and the cathode current terminal portion C34 are used as the current terminals, the reaction will be the anode current terminal portion A32 and the cathode current terminal portion C34. To a position close to However, the reaction is made uniform by using both ends of the anode current terminal portion A32 and the anode current terminal portion B33 and the cathode current terminal portion C34 and the cathode current terminal portion D35 as the current collecting ends as in the eighth embodiment. , The most ideal current collection.

As shown in FIG. 11 (b), if an electronic insulating material such as a porous thin film 27 made of PTFE is disposed outside the anode and the cathode, and the portion other than the current terminal portion is covered,
The danger of short circuit and grounding is reduced.

Further, if the length of the ellipse is changed between the anode and the cathode, the possibility of connecting the anode and the cathode and making a mistake is reduced. Titanium is generally used for the anode of the electrolytic ozone generating element, and carbon paper or carbon cloth is generally used for the cathode. The carbon material has higher electric resistance than the titanium material. Therefore, when the current collection distance on the anode side is longer than that on the cathode side, the resistance required for current collection can be reduced and the performance can be improved.

In the embodiment shown in FIG. 11, the anode and the cathode are elliptical. However, the anode and the cathode are not necessarily elliptical. A plurality of current terminals may be provided on the outer peripheral portion of each electrode, that is, on the outer portion of the solid polymer electrolyte membrane, by disposing spacers around the electrolyte membrane to face each other.

Embodiment 9 FIG. 12 is a plan view (a) showing a configuration of a socket body of an electrolytic ozone generating apparatus according to Embodiment 9 of the present invention, and a cross-sectional view (b) along line AA. FIG. It is the top view (a) which shows the structure of the socket cover part of a generator, and sectional drawing (b) along AA. In the figure, 36 is a socket body,
37 is a socket cover, 38 is an anode connection A of the socket cover, 39 is an anode connection B of the socket cover, 40 is a cathode connection C of the socket body, 41 is a cathode connection D of the socket body, 44 is an anode connection part A of the socket body part, 45
Is a wiring connecting the cathode connection parts C and D, 47 is a wiring connecting the anode connection parts A and B, 48 is a positive current terminal to a DC power supply, and 49 is a DC power supply. A negative current terminal, 53 a hole penetrating the socket body, 54 a hole penetrating the socket lid, 55
Is a socket body mounting bolt hole, 56 is a recess provided on the cathode side, and 57 is a recess provided on the anode side.

The electrolytic ozone generating element shown in FIG. 11 is mounted with the cathode part facing the socket body shown in FIG. The cathode-side installation recess 56 is deeper than the anode-side installation recess 57, and has a shape that matches the shape and thickness of the element. The mounting of the electrolytic ozone generating element is completed simply by placing the cathode side in the recess 56 on the cathode side of the socket body and fitting the socket lid. Although the socket body and the socket lid are not easily detached by using irregularities, such a structure can be easily configured by using a well-known technique as a fitting type structure. . The cathode connection portions 40 and 41 of the socket body are
The device is connected to the current terminal portions 34 and 35 of the cathode of the device, and is connected to the negative current terminal 49 by a wiring 46.
On the other hand, the inside of the anode connection portions 38 and 39 of the socket lid portion is electrically connected to the current terminal portions 32 and 33 of the anode of the element, and the outside of the anode connection portions 38 and 39 of the socket lid portion is the socket body portion. Connected to the anode connection portions 44 and 45 of the
7 is connected to a positive current terminal 48. Therefore, the minus current terminal 49 and the plus current terminal 48
When a DC voltage of about V is applied, current can flow between the cathode and the anode of the electrolytic ozone generating element, and ozone is generated. In addition, when the lid is detached, power is not supplied, and there is no danger of electric shock during mounting. The socket body and the socket lid are made of an electronically insulating plastic material that is durable to ozone.
12 and 13 by extrusion molding.
Can be manufactured. As mentioned above,
According to the configuration of FIGS. 12 and 13, the electrolytic ozone generating element can be mounted with one touch, and there is no need to perform wiring of the anode and the cathode.

Embodiment 10 FIG. FIG. 14 is a plan view (a) showing a configuration of a socket body of an electrolytic ozone generator according to Embodiment 10 of the present invention, and a cross-sectional view (b) taken along line AA. In the figure, 58 is a closed space on the cathode side,
Reference numeral 59 denotes a ventilation hole in the socket body, and 63 denotes a communication hole between the closed space and the ventilation hole, which is an air communication passage to the anode side.

In the ozone generator according to the present embodiment,
Although the cathode side space is a closed space, the air is in communication with the cathode side, so that the danger of generating hydrogen on the cathode side is reduced. In addition, since it is not necessary to expose the cathode side to air, the socket body can be easily attached to a wall or the like using the attachment hole 55 or adhered using a double-sided tape or the like. The degree of freedom of the installation location of the generator is increased.

Embodiment 11 FIG. FIG. 15 is a configuration diagram showing a circuit configuration of an electrolytic ozone generator according to Embodiment 11 of the present invention. In the figure, 50 is a dry battery, 51 is a current circuit changeover switch, 52 is a fuse, and 10 is an electrolytic ozone generating element.

When the ozone is generated by mounting the electrolytic ozone generating element 10, two dry cells are connected in series and 3 V
When no ozone is generated from the apparatus by applying a direct current voltage of only one of the two batteries in series or the two batteries are electrically connected in parallel by the current circuit changeover switch 51, and between the anode and the cathode. And a voltage 1.5 V lower than that in the case of generating ozone. by this,
Deterioration due to reduction of the anode can be prevented.

With the electrolytic ozone generator of Embodiment 11 shown in FIG.
In order to compare the life of each ozone generating element in the electrolytic ozone generating apparatus without applying a voltage, ON-OF was used.
F was repeated every two hours. After one month, the ozone generation performance of the electrolytic ozone generator of the eleventh embodiment shown in FIG. In an electrolytic ozone generator in which no voltage is applied when ozone is not generated from the apparatus, the amount of ozone generated has been reduced by half. This is because when no voltage was applied, the potential of the anode was reduced and reduced to lead ions, which were taken into the solid polymer electrolyte membrane, and the resistance was increased. According to the eleventh embodiment, it is possible to prevent the anode from being at a low potential even during stoppage, and
An electrolytic ozone generator having a long repetition life of F can be obtained.

On the other hand, the fuse 52 in FIG. 15 is cut off when a current larger than usual flows, and it is possible to prevent the current from flowing any more. In a case where the element is damaged and short-circuited, abnormal heat generation of the element and generation of hydrogen can be prevented, and the safety in the event of an emergency can be kept high.

In the above embodiment, the case where a dry battery is used has been described. However, any DC voltage may be used. A DC / DC converter may be used to set the voltage to 3 V or 1.5 V from a household 100 V power supply. Is also good. Further, a solar cell can also be used.

In the above-described embodiment, the voltage applied to the element when generating ozone is 3 V. However, the appropriate applied voltage may be the ionic conduction resistance of the solid polymer electrolyte membrane, the electric circuit, or the like. It depends on the electronic conduction resistance at the current collector. For example, when a solid polymer electrolyte membrane having high ionic conduction resistance is used, it is necessary to increase the applied voltage, and a value such as 3.5 V or 4 V is used. Conversely, when a solid polymer electrolyte membrane having a low ionic conduction resistance is used, a lower applied voltage such as 2.5 V or 2 V can be applied instead of 3 V. Accordingly, the applied voltage when ozone is not generated from the element is also 1.5 V
Is not an optimal value, and an easy-to-use voltage may be selected from voltages lower than the voltage at which ozone is generated. The lower the applied voltage, the lower the power consumption. However, in consideration of the power loss at the time of voltage transformation, the voltage that can be easily used differs depending on the case where the electrolytic ozone generator is used.

[0069]

As described above, according to the electrolytic ozone generating element of the first configuration of the present invention, in the electrolytic ozone generating element in which the anode and the cathode face each other with the solid polymer electrolyte membrane interposed therebetween, As the cathode, an electron-conductive, gas-permeable porous substrate is used, on both surfaces of the porous substrate,
Since a catalyst layer containing a platinum catalyst was formed, even if hydrogen was generated in the catalyst layer in contact with the solid polymer electrolyte membrane of the cathode,
Hydrogen is reduced to water in the catalyst layer on the back surface of the porous substrate of the cathode, and there is an effect that safety is maintained.

According to the electrolytic ozone generating element of the second configuration of the present invention, in the electrolytic ozone generating element in which the anode and the cathode are opposed to each other with the solid polymer electrolyte membrane interposed therebetween, Since a conductive and gas-permeable porous substrate was used, and a catalyst containing a platinum catalyst was contained inside the porous substrate, hydrogen was applied to the catalyst in contact with the solid polymer electrolyte membrane of the cathode. In the case where hydrogen is generated, hydrogen is reduced to water by the platinum catalyst contained in the porous base material of the cathode, and the safety is enhanced.

Further, according to the electrolytic ozone generating element of the third configuration of the present invention, since the catalyst layer made of α-type lead dioxide is provided between the anode and the solid polymer electrolyte membrane, the surface becomes Converts to β-type lead dioxide and provides the same current efficiency of ozone generation as when β-type lead dioxide is plated, and the tough α-type lead dioxide layer prevents cracking of the lead dioxide layer The effect is that the performance is kept stable for a long time.

According to the electrolytic ozone generating element of the fourth configuration of the present invention, a titanium porous substrate plated with α-type lead dioxide is used as an anode, and the porous substrate and the solid Since the α-type lead dioxide fine particle layer is sandwiched between the polymer electrolyte membrane, the surface of the α-type lead dioxide fine particles changes to β-type, which has high current efficiency of ozone generation, while maintaining the strength against stress. , A large reaction surface area can be maintained. In addition, the tough α-type lead dioxide plating layer has the effect of preventing the lead dioxide layer from cracking and maintaining its role as a current collector for a long time.

Further, according to the electrolytic ozone generating element of the fifth configuration of the present invention, since at least one hole penetrating the anode, the solid polymer electrolyte membrane and the cathode is provided, the hole is sufficiently connected to the cathode. Even if a large amount of oxygen or moisture is supplied and the space on the cathode side is closed, a large amount of hydrogen is not likely to be generated, and there is an effect that safety is maintained.

According to the electrolytic ozone generating element of the sixth configuration of the present invention, a water-repellent and gas-permeable porous membrane is disposed outside at least one of the anode and the cathode. The ozone generating element is waterproofed, and furthermore, metal ions and organic substances from dust and the like are prevented from adhering, and the performance is maintained for a long time.

Further, according to the electrolytic ozone generating element of the seventh configuration of the present invention, since the porous film has a protection means for protecting the element against external force, the element is destroyed by an external force. Can be prevented.

According to the electrolytic ozone generating element of the eighth configuration of the present invention, the anode part disposed between the anode and the cathode sandwiching the solid polymer electrolyte membrane is disposed outside the solid polymer electrolyte membrane. In addition, since a plurality of current terminals are respectively formed in the cathode portion, there is an effect that effective current collection is performed.

Further, according to the electrolytic ozone generating device of the first configuration of the present invention, the electrolytic ozone generating element is mounted between the socket body and the socket lid, and the cathode current terminal is connected to the socket main body. The anode current terminal comes in contact with the socket lid or the anode connection of the socket body when the socket lid is attached, when it comes into contact with the cathode connection, so that the element can be easily mounted. .

Further, according to the electrolytic ozone generator of the second configuration of the present invention, the space facing the cathode of the socket lid is configured as a closed space, and the vent hole on the socket body side or the electrolytic Ozone is generated without generating hydrogen in the cathode-side space even when the electrolytic ozone generator is mounted on a surface such as a wall because it communicates with the space on the anode side through a hole that penetrates the ozone generating element. There is an effect that can be made.

Further, according to the electrolytic ozone generator of the third configuration of the present invention, when ozone is not generated from the device, a lower voltage is applied between the anode and the cathode than when ozone is generated. Thus, there is an effect that the reduction of the anode can be prevented with little power consumption.

Further, according to the electrolytic ozone generator of the fourth configuration of the present invention, the current circuit is provided with a fuse which can be cut at a current value higher than the current value expected when ozone is generated. However, even when a large current flows directly to the ozone generating element, or when the element is damaged by an external force and short-circuited, the fuse cuts and no current flows, preventing generation of hydrogen at the cathode and excessive heat generation. effective.

[Brief description of the drawings]

FIG. 1 is a side view (a) and a plan view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 1 of the present invention.

FIG. 2 is an explanatory diagram showing an operation of the electrolytic ozone generating element according to the first embodiment of the present invention.

FIG. 3 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 2 of the present invention.

FIG. 4 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 3 of the present invention.

FIG. 5 is a graph showing a change over time in performance of an electrolytic ozone generating element according to Embodiment 3 of the present invention.

FIG. 6 shows a plated layer of α-type lead dioxide after operation and β
It is a figure which shows typically the mode of the cross section of the plating layer of the type | mold lead dioxide.

FIG. 7 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 4 of the present invention.

8A and 8B are a side view and a plan view showing a configuration of an electrolytic ozone generating element according to Embodiment 5 of the present invention.

FIG. 9 is a side view showing a configuration of an electrolytic ozone generating element according to Embodiment 6 of the present invention.

FIG. 10 is a side view (a) and a plan view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 7 of the present invention.

FIG. 11 is a plan view (a) and a side view (b) showing a configuration of an electrolytic ozone generating element according to Embodiment 8 of the present invention.

FIG. 12 (a) is a plan view showing a configuration of a socket body of an electrolytic ozone generator according to Embodiment 9 of the present invention.
FIG. 2B is a cross-sectional view taken along line AA.

FIGS. 13A and 13B are a plan view and a cross-sectional view taken along line AA, respectively, showing a configuration of a socket lid of an electrolytic ozone generator according to Embodiment 9 of the present invention.

FIGS. 14A and 14B are a plan view and a cross-sectional view taken along line AA, respectively, showing a configuration of a socket body of an electrolytic ozone generator according to Embodiment 10 of the present invention.

FIG. 15 is a configuration diagram showing a circuit configuration of an electrolytic ozone generator according to Embodiment 11 of the present invention.

FIG. 16 is a side view (a) and a plan view (b) showing the configuration of a conventional electrolytic ozone generating element.

[Description of Signs] 1 Cathode base material, 2 Catalytic layer on front surface of cathode base material,
3 Catalytic layer on the back of the base material of the cathode, 4 Solid polymer electrolyte membrane, 5 Base material of the anode, 6 Catalytic layer of the anode, 7a Cathode current terminal, 7b Cathode voltage terminal, 8a Anode current terminal, 8b anode Voltage terminal, 9 cathode, 10 electrolytic ozone generating element, 11 external circuit, 12 DC power supply, 13
Anode, change in ozone concentration in case of 14α type lead dioxide, change in ozone concentration in case of 15β type lead dioxide, 1
6 Change in hydrogen concentration in the case of α-type lead dioxide, 17 β
Change of hydrogen concentration in case of type lead dioxide, 18 titanium expanded metal, 19 titanium surface platinum plating layer, 20 α type lead dioxide plating layer, 21 β type lead dioxide thin layer, 22 β type Lead dioxide plating layer, 2
3 Crack, porous substrate made of titanium plated with 24α-type lead dioxide, thin-film sheet mainly composed of fine particles of 25α-type lead dioxide, 26 holes, 27 porous thin film, 28
Metal plate, 29 holes, 30 anodes, 31 cathodes,
32 Anode current terminal A, 33 Anode current terminal B, 3
4 Cathode current terminal C, 35 Cathode current terminal D, 36
Socket body part, 37 Socket cover part, 38 Anode connection part A of socket cover part, 39 Anode connection part B of socket cover part, 40 Cathode connection part C of socket body part, 41 Cathode connection part D of socket body part, 44 Anode connection part A of the socket body part, 45 Anode connection part B of the socket body part,
46 wiring, 47 wiring, 48 plus current terminal to DC power supply, 49 minus current terminal to DC power supply, 50
Dry cell, 51 current circuit changeover switch, 52 fuse, 53 hole, 54 hole, 55 bolt hole, 56 cathode side recess, 57 anode side recess, 58 cathode side closed space, 59 socket body part vent hole, 61
Anode, 62 cathode, 63 connecting hole.

Continued on the front page (72) Inventor Makoto Sorimachi 2-6-4 Kitaueno, Taito-ku, Tokyo Inside Toyo Takasago Dry Battery Co., Ltd. (72) Inventor Tetsuya Abe 8-1-1 Honcho Tsukaguchi, Amagasaki City, Hyogo Pref. Within the company (72) Inventor Koji Hatanaka 2-6-1, Miwa, Mita-shi, Hyogo Ryoden Kasei Co., Ltd. (72) Inventor Takeshi Aizawa 2-14-10 Kugahara, Ota-ku, Tokyo Optec Didi Melco Co., Ltd. In the laboratory

Claims (12)

[Claims] 1. An electrolytic ozone generating element in which an anode and a cathode are opposed to each other with a solid polymer electrolyte membrane interposed therebetween, wherein an electron conductive and gas-permeable porous base material is used as the cathode. An electrolytic ozone generating element, wherein a catalyst layer containing a platinum catalyst is formed on both surfaces of the porous substrate. 2. An electrolytic ozone generating element in which an anode and a cathode are opposed to each other with a solid polymer electrolyte membrane interposed therebetween, wherein an electron conductive and gas-permeable porous base material is used as the cathode. An electrolytic ozone generating element, wherein a catalyst containing a platinum catalyst is contained in the porous substrate. 3. The method according to claim 1, wherein α is between the anode and the solid polymer electrolyte membrane.
The electrolytic ozone generating element according to claim 1 or 2, further comprising a catalyst layer made of a type of lead dioxide. 4. A titanium porous substrate plated with α-type lead dioxide is used as an anode, and a fine particle layer of α-type lead dioxide is provided between the porous substrate and the solid polymer electrolyte membrane. The electrolytic ozone generating element according to claim 1 or 2, wherein the element is sandwiched. 5. The electrolytic ozone generating element according to claim 1, wherein at least one hole penetrating the anode, the solid polymer electrolyte membrane, and the cathode is provided. 6. The electrolytic ozone according to claim 1, wherein a water-repellent and gas-permeable porous membrane is disposed outside at least one of the anode and the cathode. Generating element. 7. The electrolytic ozone generating element according to claim 6, wherein the porous film has a protection means for protecting the element against an external force. 8. A method in which a plurality of current terminals are respectively formed on an anode portion and a cathode portion of the anode and the cathode disposed with the solid polymer electrolyte membrane interposed therebetween, which are located outside the solid polymer electrolyte membrane. The electrolytic ozone generating element according to any one of claims 1 to 7, wherein: 9. An electrolytic ozone generating element is mounted between the socket body and the socket lid, and the cathode current terminal contacts the cathode connection of the socket body, and the anodic current flows when the socket lid is mounted. An electrolytic ozone generator characterized in that a terminal portion is brought into contact with a socket lid portion or an anode connection portion of a socket body portion. 10. A space facing the cathode of the socket lid portion is configured as a closed space, and is connected to a space on the anode side through a vent hole on the socket body side or a hole penetrating the electrolytic ozone generating element. The electrolytic ozone generator according to claim 9, characterized in that: 11. In an electrolytic ozone generator equipped with an electrolytic ozone generating element and provided with a DC power supply, when no ozone is generated from the device, a lower voltage is applied between the anode and the cathode than when ozone is generated. The electrolytic ozone generator according to claim 9 or 10, wherein the voltage is applied. 12. In an electrolytic ozone generator equipped with an electrolytic ozone generating element and provided with a DC power supply, a fuse that cuts at a current value higher than a current value expected when generating ozone is provided in a current circuit. The electrolytic ozone generator according to any one of claims 9 to 11, wherein: