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WO2019082878A1 - Électrode d'électrolyse, et dispositif de génération d'ozone et dispositif électrique équipés de celle-ci - Google Patents

Électrode d'électrolyse, et dispositif de génération d'ozone et dispositif électrique équipés de celle-ci

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Publication number
WO2019082878A1
WO2019082878A1 PCT/JP2018/039308 JP2018039308W WO2019082878A1 WO 2019082878 A1 WO2019082878 A1 WO 2019082878A1 JP 2018039308 W JP2018039308 W JP 2018039308W WO 2019082878 A1 WO2019082878 A1 WO 2019082878A1
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WO
WIPO (PCT)
Prior art keywords
electrode
layer
electrolysis
fluid
reaction layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/039308
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English (en)
Japanese (ja)
Inventor
茂 笹部
藤井　優子
妃代江 郡司
大江　良尚
勤 古田
福田　祐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Intellectual Property Management Co Ltd
Original Assignee
Panasonic Intellectual Property Management Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017207836A external-priority patent/JP2019077936A/ja
Priority claimed from JP2017243399A external-priority patent/JP2019108596A/ja
Priority claimed from JP2018132816A external-priority patent/JP2020012124A/ja
Priority claimed from JP2018132814A external-priority patent/JP2020012122A/ja
Priority claimed from JP2018132815A external-priority patent/JP2020012123A/ja
Priority claimed from JP2018132812A external-priority patent/JP2020012121A/ja
Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Publication of WO2019082878A1 publication Critical patent/WO2019082878A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous

Definitions

  • the present invention relates to an electrode for electrolysis that electrolyzes water to generate an active substance, an ozone generator including the same, and an electrical apparatus.
  • FIG. 15 is a schematic enlarged sectional view of the conventional electrode for electrolysis described in Patent Document 1 in the thickness direction.
  • the conventional electrode for electrolysis 1 is composed of a conductive substrate 2, an intermediate layer 3 and a surface layer 4.
  • the intermediate layer 3 is formed of a noble metal, an alloy containing a noble metal, or a noble metal oxide formed on one surface of the conductive substrate 2.
  • the surface layer 4 is formed on the surface of the intermediate layer 3.
  • the surface layer 4 is formed of a dielectric material made of an oxide.
  • the oxide is obtained by thermal decomposition of a mixture of an alkoxide compound such as tantalum, aluminum, titanium, tungsten, or niobium and a solvent.
  • the surface layer 4 is formed on the surface of the intermediate layer 3 by repeating the steps of coating a dielectric material, drying at normal temperature, drying at 220 ° C., and high-temperature firing at 600 to 700 ° C. several dozen times. .
  • the surface layer 4 is formed in a layered structure having a predetermined thickness. At this time, many cracks are generated in the surface layer 4 in the thickness direction by repeating the above steps. Therefore, in the surface layer 4 formed of a dozen or more layers, the communication path 5 which penetrates the surface layer 4 and reaches the intermediate layer 3 is formed starting from the crack.
  • the electrolysis electrode 1 When the electrolysis electrode 1 is used as an anode electrode and water is electrolyzed using a cathode electrode, water reaches the intermediate layer 3 through the communication passage 5 on the electrolysis electrode 1 side. At this time, an electrode reaction occurs on a small area of the surface portion of the intermediate layer 3 connected to the communication passage 5. As a result, the current density of the intermediate layer 3 connected to the communication passage 5 is increased. As a result, oxygen is oxidized by the catalytic action of the dielectric material around the communication passage 5 of the surface layer 4 to generate ozone.
  • the surface layer 4 is formed on the surface of the intermediate layer 3 by repeating application, drying, and firing ten times. Therefore, the surface layer 4 has a multilayer structure having a nonuniform film thickness. As a result, the branching and coupling of the cracks generated in the surface layer 4 become a complex structure. Therefore, it becomes difficult to form the communication passage 5 starting from the crack with a stable structure. As a result, in the configuration of the electrode 1 for electrolysis, ozone can not be generated stably.
  • the productivity of the electrode 1 for electrolysis is poor.
  • the dielectric of the surface layer 4 is composed only of particles generated by thermal decomposition using a metal alkoxide as a raw material.
  • the surface layer 4 is formed at a low baking temperature of 600 to 700 ° C., bonding between particles of the dielectric and bonding between particles of the dielectric and the intermediate layer 3 are in a semi-sintered state.
  • the adhesion between each layer of the intermediate layer 3 and the surface layer 4 and the surface layer 4 itself becomes weak. Therefore, the surface layer 4 is easily peeled off by the pressure of gas such as oxygen or ozone generated by the electrode reaction. As a result, the durability of the surface layer 4 is reduced.
  • the present invention provides an electrode for electrolysis having excellent productivity, as well as stable generation and durability of ozone, and an ozone generator and an electric apparatus including the electrode.
  • the electrode for electrolysis of the present invention comprises an electrode substrate, an electrode reaction layer formed on the surface of the electrode substrate, at least one of a noble metal, an alloy containing a noble metal, and an oxide containing a noble metal, and a surface of the electrode reaction layer. And a fluid restricting layer which contains a binder as a main component and restricts the contact area between water and the surface of the electrode reaction layer.
  • the electric equipment of this invention is equipped with the said electrode for electrolysis.
  • the ozone generator of this invention is equipped with the said electrode for electrolysis.
  • the electrode for electrolysis is an anode electrode and a voltage or a current is applied between the electrode and the cathode electrode
  • the fluid restriction layer of the anode electrode restricts the contact between water and the electrode reaction layer. Reduce the contact area of the electrode reaction layer. Therefore, in the anode electrode, the voltage of oxygen generation by the electrolysis of water is higher than that of the electrode for electrolysis having a configuration without the fluid restriction layer. Then, when the voltage for oxygen generation reaches a predetermined voltage or more, simultaneously with the generation of oxygen, active species such as oxygen radicals are generated. As a result, the generated active species react with oxygen to generate ozone.
  • the fluid restriction layer suppresses the penetration of water into the electrode reaction layer so that the voltage can be equal to or higher than the voltage at which ozone can be generated, and the water is electrolyzed at a voltage or a current corresponding to the ozone generation amount.
  • ozone water of any concentration can be stably produced with high productivity.
  • the fluid restricting layer is formed mainly of a binder. Thereby, high adhesiveness with the electrode reaction layer is realized. As a result, peeling of the fluid restriction layer can be prevented, and changes in the contact area between the water to be electrolyzed and the electrode reaction layer can be suppressed.
  • the binder etc. which form a fluid restriction layer can prepare concentration etc. easily by using a solvent for exclusive use. Therefore, it is possible to form a fluid restriction layer having a predetermined film thickness by repeating application and baking several times at most.
  • an electrode for electrolysis having excellent productivity, an ozone generator and an electric apparatus equipped with the electrode, which has stable production of ozone and improved durability.
  • FIG. 1 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the first embodiment of the present invention.
  • FIG. 2 is a schematic view of an electrolysis apparatus using the same electrode for electrolysis.
  • FIG. 3 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the second embodiment of the present invention.
  • FIG. 4 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the third embodiment of the present invention.
  • FIG. 5 is a schematic enlarged cross-sectional view in the thickness direction of the fluid restriction layer of the same electrode for electrolysis.
  • FIG. 6 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the fourth embodiment of the present invention.
  • FIG. 1 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the first embodiment of the present invention.
  • FIG. 2 is a schematic view of an electrolysis apparatus using the same electrode for electrolysis.
  • FIG. 7 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the fifth embodiment of the present invention.
  • FIG. 8 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the sixth embodiment of the present invention.
  • FIG. 9 is a schematic enlarged cross-sectional view in the thickness direction of the fluid restricting layer of the electrode for electrolysis in the seventh embodiment of the present invention.
  • FIG. 10 is a schematic enlarged cross-sectional view in the thickness direction of the fluid restriction layer of the same electrode for electrolysis.
  • FIG. 11 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the eighth embodiment of the present invention.
  • FIG. 12 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the ninth embodiment of the present invention.
  • FIG. 13 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the tenth embodiment of the present invention.
  • FIG. 14 is a schematic enlarged cross-sectional view in the thickness direction of the electrode for electrolysis in the eleventh embodiment of the present invention.
  • FIG. 15 is a schematic enlarged sectional view in the thickness direction of the conventional electrode for electrolysis.
  • Embodiment 1 The electrode 11 for electrolysis of Embodiment 1 of the present invention will be described with reference to FIG.
  • FIG. 1 is a schematic enlarged cross-sectional view in the thickness direction of the electrode 11 for electrolysis in the first embodiment.
  • the electrode 11 for electrolysis of Embodiment 1 is formed on the surface of the electrode substrate 12, the electrode reaction layer 13 formed on one surface of the electrode substrate 12, and the electrode reaction layer 13.
  • a fluid restriction layer 14 and the like are included.
  • the electrode substrate 12 is made of, for example, a metal material such as titanium, niobium, tantalum, stainless steel or the like. Among them, titanium is more suitable from the practical viewpoints of corrosion resistance, mechanical strength, processability, cost and the like. Therefore, titanium is used as the electrode base 12 in the present embodiment.
  • the electrode reaction layer 13 is configured using at least one of a noble metal, an alloy containing a noble metal, and an oxide containing a noble metal. Among them, platinum and platinum-containing alloys are more suitable in terms of performance and durability in water electrolysis. In this embodiment, platinum or an alloy containing platinum is used as the electrode reaction layer 13 in order to use the electrolysis electrode 11 for the electrolysis of water.
  • the electrode reaction layer 13 although there exist a baking method, electroplating method etc., for example, it is not limited to this.
  • a commercially available electrode material may be adopted to produce the electrode reaction layer 13.
  • the firing method first, chloroplatinic acid is applied to the surface of the titanium substrate which is the electrode substrate 12. Then, the applied chloroplatinic acid is thermally decomposed by drying and baking to form a layer of platinum particles.
  • the electroplating method also electroplates platinum on a titanium substrate to form a layer of platinum particles.
  • the electrode reaction layer 13 is produced by these production methods.
  • the fluid restricting layer 14 is formed mainly of a binder described below.
  • the fluid restricting layer 14 has the function of limiting the contact area between water and the surface of the electrode reaction layer 13 to the electrode 11 for electrolysis.
  • the fluid restricting layer 14 is formed by applying a coating agent containing a binder as a main component and heat curing.
  • a coating agent such as glass paste, metal alkoxide, alumina sol, colloidal silica or the like, or an organic binder used as a paint such as nylon resin varnish, acrylic resin varnish, silicone resin varnish or the like is applied.
  • glass paste is more preferable as the fluid limiting layer 14 from the viewpoint of the function of limiting the contact area of water and the surface of the electrode reaction layer 13 and durability.
  • Examples of the method of forming the fluid restricting layer 14 include, but are not limited to, spray coating, brush coating or spatula coating, roll coater, spin coater, screen printing and the like.
  • a manufacturing method by sputtering, CVD (Chemical Vapor Deposition), or the like can also be adopted.
  • the electrode 11 for electrolysis of Embodiment 1 is constituted and produced.
  • FIG. 2 is a schematic view showing a flow type electrolytic device 15 showing an example using the electrode 11 for electrolysis.
  • the electrolytic device 15 includes a housing 18, an electrode 11 for electrolysis, a counter electrode 19, a DC power supply 20 and the like.
  • the housing 18 comprises a water inlet 16 and an electrolyzed water outlet 17.
  • the electrode 11 for electrolysis is attached to the inside of the housing 18, and functions as an anode electrode.
  • the counter electrode 19 is disposed to face the electrode 11 for electrolysis, and functions as a cathode electrode.
  • the DC power supply 20 is connected to the electrode 11 for electrolysis and the counter electrode 19 so as to be conductive.
  • the electrode 11 for electrolysis is disposed such that the surface on which the electrode reaction layer 13 and the fluid restriction layer 14 are formed faces the counter electrode 19 in a separated manner. Thus, a flow path through which water flows is formed between the electrode 11 for electrolysis and the counter electrode 19.
  • water is supplied from the inlet 16 of the housing 18 of the electrolytic device 15 at a predetermined flow rate.
  • the supplied water flows through the flow path formed between the electrode 11 for electrolysis and the counter electrode 19, and is discharged from the outlet 17 of the housing 18.
  • a voltage or current is applied from the DC power supply 20 with the electrode 11 for electrolysis as an anode and the counter 19 as a cathode. . Water is thereby electrolyzed.
  • oxygen is generated at the electrode 11 for electrolysis which is an anode electrode, and hydrogen is generated at a counter electrode 19 which is a cathode electrode.
  • a fluid restricting layer 14 made of a dielectric material (binder) is formed on the outermost layer of the electrode 11 for electrolysis in contact with water. Therefore, even if a voltage or current is applied from the DC power supply 20, the fluid limiting layer 14 can not obtain conductivity as an electrode. That is, in the fluid restriction layer 14, the electrolysis reaction of water does not occur. However, water penetrates through the fluid restriction layer 14 through the membrane structure described later. The permeated water reaches the conductive electrode reaction layer 13 formed on the surface of the electrode substrate 12 of the electrode 11 for electrolysis. The water reached is electrolyzed on the surface of the electrode reaction layer 13.
  • the fluid restricting layer 14 is formed of a coating film formed by applying a coating agent containing a binder as a main component and heat curing.
  • the coating film is dense as a film structure, but the density is not uniform. Therefore, water penetrates in the fluid restricting layer 14 through the relatively low density portion of the membrane and reaches the electrode reaction layer 13.
  • the contact area between the water that has reached the electrode reaction layer 13 and the electrode reaction layer 13 is extremely smaller than the area of the entire electrode reaction layer 13. Therefore, the current density of the portion of the electrode reaction layer 13 in contact with water is increased and the voltage of oxygen generation is higher than that of the electrode configuration without the fluid restriction layer 14. In other words, the overvoltage of oxygen generation is high. Then, when the voltage for oxygen generation reaches a predetermined voltage or more, simultaneously with the generation of oxygen, active species such as oxygen radicals are generated. As a result, the generated active species react with oxygen to generate ozone.
  • the electrode 11 for electrolysis of Embodiment 1 is equivalent to the porosity of the fluid restricting layer 14 (corresponding to the portion where the density of the film is small as described above so that the electrode reaction of oxygen generation occurs at a predetermined voltage or more generating ozone. Control).
  • the water is electrolyzed at a voltage or current according to the required ozone production amount.
  • ozone water of a predetermined concentration can be stably produced.
  • the fluid restricting layer 14 is formed of a binder material.
  • the binder inherently has a function as an adhesive. Therefore, the adhesion between the fluid restriction layer 14 and the electrode reaction layer 13 is improved by the fluid restriction layer 14. Thereby, the destruction of the fluid restriction layer 14 due to the pressure of gas such as oxygen generated by the electrolysis, the peeling of the fluid restriction layer 14 due to the erosion of water to the interface between the fluid restriction layer 14 and the electrode reaction layer 13, etc. Can be prevented more reliably. Therefore, the contact area of water and the electrode reaction layer 13 is always maintained constant. As a result, the electrode 11 for electrolysis of the present embodiment can maintain the initial ozone generation performance over a long period of time.
  • the binder can be easily prepared, for example, with a dedicated solvent such as water, alcohol, ether, terpineol, etc. Therefore, unlike the conventional electrode for electrolysis, it is possible to form the electrode 11 for electrolysis having a predetermined film thickness by repeating application and baking several times at most, without requiring coating over a dozen times or more. As a result, the manufacturing steps of the electrode for electrolysis 11 can be simplified and the cost can be reduced by reducing the number of manufacturing steps. As a result, the electrode 11 for electrolysis excellent in productivity can be provided stably.
  • the binder used for the fluid restricting layer 14 of the first embodiment is, for example, an inorganic binder such as glass paste, metal alkoxide, alumina sol, colloidal silica, nylon resin varnish, acrylic resin varnish, silicone resin An organic binder used as a paint such as varnish is applied.
  • inorganic binders are preferably used.
  • the inorganic binder is highly hydrophilic and has good compatibility with water. Therefore, the repelling of the water on the surface of the fluid restriction layer 14 is suppressed, and the water always penetrates into the fluid restriction layer 14 stably. As a result, a high quality electrode 11 for electrolysis with stable ozone generation performance can be realized.
  • the main component is a glass material.
  • the glass material achieves excellent adhesion with the electrode reaction layer 13 and increases the hardness and strength of the fluid restricting layer 14 itself. Therefore, mechanical damage to the fluid restriction layer 14 can be prevented, and excellent durability can be realized.
  • the glass material among the glasses, a glass having a composition which does not contain a compound of an alkali metal and an alkaline earth metal as the main component is more preferable.
  • the fluid restricting layer 14 made of glass containing a compound of an alkali metal and an alkaline earth metal gradually elutes the alkali metal and the alkaline earth metal and becomes porous.
  • the area of contact between water and the electrode reaction layer 13 is increased because the porous fluid restricting layer 14 has many places where water penetrates the electrode reaction layer 13. As a result, the voltage for oxygen generation decreases and the ozone generation performance decreases.
  • the fluid restricting layer 14 of the first embodiment is made of glass which does not contain a compound of an alkali metal and an alkaline earth metal. Thereby, the elution of the glass component from the fluid restriction layer 14 is suppressed. Therefore, it is possible to prevent the fluid restriction layer 14 from being made porous even if it is left for a long time in a state where the electrode 11 for electrolysis is immersed in water. As a result, the initial ozone generation performance can be maintained for a long time.
  • glasses containing no alkali metal or alkaline earth metal generally require a baking temperature of 900 ° C. or more after coating. Therefore, when the electrode substrate 12 is a metal material, oxidation at the metal material proceeds by firing at a high temperature. As a result, peeling of the oxide layer, deformation of the electrode, and the like from the electrode substrate 12 may occur, and the function as the electrode for electrolysis 11 may not be exhibited.
  • the fluid restriction layer 14 in order to solve the above-mentioned problems, it is necessary to fire the fluid restriction layer 14 at a relatively low baking temperature of 700 ° C. or less.
  • a glass component not containing an alkali metal or an alkaline earth metal for example, a glass having a composition containing an oxide of Si, Al, B, or Bi as a main component Be
  • the fluid restriction layer 14 of the electrode 11 for electrolysis of Embodiment 1 is formed of the glass having the above composition. Thereby, maintenance of ozone generation performance and electrode 11 for electrolysis excellent in endurance can be realized.
  • the fluid restricting layer 14 of the first embodiment has a dense structure, water penetration occurs between fine particles of several tens of nano to sub-micron particles or through gaps in the molecular structure of glass. That is, if the film thickness of the fluid restricting layer 14 is large, the barrier property is enhanced and the water permeability is impaired. Therefore, the fluid restricting layer 14 is preferably formed of a thin film having a thickness of 10 ⁇ m or less.
  • the electrode base 12 may be made of a dielectric substrate such as ceramic.
  • the terminal portion of the electrode for electrolysis electrically connected to the power source needs to be provided with a conductive film in the same manner as the electrode reaction layer 13. Thereby, current can be conducted from the end to the electrode reaction layer 13.
  • the electrode base 12 by forming the electrode base 12 with a dielectric substrate such as ceramic, the corrosion of the base can be suppressed, and the durability is improved.
  • FIG. 3 is a schematic enlarged sectional view in the thickness direction of the electrode 21 for electrolysis in the second embodiment.
  • the electrode 21 for electrolysis of the second embodiment is different from that of the first embodiment in the constituent material of the fluid restricting layer 22. Therefore, the same components as those in the first embodiment may be assigned the same reference numerals and descriptions thereof may be omitted.
  • the electrode 21 for electrolysis of Embodiment 2 is formed on the surface of the electrode substrate 12, the electrode reaction layer 13 formed on one surface of the electrode substrate 12, and the electrode reaction layer 13.
  • a fluid restriction layer 22 or the like is included.
  • the fluid restricting layer 22 is composed of particles 23 of the dielectric material (hereinafter sometimes abbreviated as “particles”) and a binder 24.
  • the flow passage 25 communicating with the electrode reaction layer 13 is formed in the fluid restriction layer 22 by the particles 23 and the binder 24.
  • the electrode base 12 and the electrode reaction layer 13 can be made of the same materials as in the first embodiment.
  • the fluid restricting layer 22 is composed of particles 23 of the dielectric material.
  • the particle 23 any compound can be used as long as it is non-conductive and does not elute particle components even when exposed to a water environment.
  • these compounds include metal oxides such as alumina, titania, zirconia and silica, nitrides, and carbides.
  • the above compounds can be used alone, in a mixture, or in the form of a complex. Furthermore, it is also possible to apply particles of semiconductor materials such as gallium phosphide, selenium, and cuprous oxide having high electric resistance, for example. Thereby, the same effect as the case of using the dielectric material is obtained.
  • Embodiment 1 The same material and manufacturing method as Embodiment 1 apply to the binder 24 of the fluid restricting layer 22.
  • the flow passage 25 in the fluid restriction layer 22 is formed by the containing particles 23. That is, when the minute gaps between the particles 23 and the gaps at the interface between the particles 23 and the binder 24 are connected, the flow path 25 communicating with the electrode reaction layer 13 is formed. Thereby, the water which has infiltrated from the surface of the fluid restriction layer 22 passes through the flow passage 25 and comes in contact with the electrode reaction layer 13.
  • the electrode 21 for electrolysis of the second embodiment is configured.
  • the flow path 25 of the fluid restriction layer 22 makes it easy for the water to be electrolyzed to reach the electrode reaction layer 13. Thereby, the contact area of water and the electrode reaction layer 13 can be enlarged. That is, by forming the flow passage 25 by particles, the contact area between water and the electrode reaction layer 13 becomes larger than that in the first embodiment.
  • the width of the voltage at which ozone is generated is narrowed, the current density in the electrode reaction layer 13 can be reduced. That is, as the contact area increases, the current density decreases and the voltage range (voltage width) generated by ozone decreases. Therefore, the elution amount of the noble metal used for the electrode reaction layer 13 is reduced. Thereby, the durability of the electrode 21 for electrolysis is further improved.
  • the flow path 25 of the fluid restricting layer 22 is formed by a series of the gaps between the particles 23 and the gaps at the interface between the particles 23 and the binder 24. Therefore, the contact area of the surface of the electrode reaction layer 13 in contact with the water to be electrolyzed changes depending on the size and the content of the particles 23 contained in the fluid restriction layer 22.
  • the gap between the particles 23 in contact with each other becomes small. Therefore, the flow passage 25 of the fluid restriction layer 22 becomes smaller. Thereby, the contact area of the electrode reaction layer 13 and the water which contacts is small. As a result, since the voltage for oxygen generation increases, the amount of ozone generation increases.
  • the voltage of oxygen generation can be controlled by the size, the content, and the like of the particles 23 contained in the fluid restriction layer 22. That is, even if the fluid limiting layer 22 has the same film thickness, it is possible to control the generation amount of ozone by adjusting the size, the content and the like of the particles 23. Thereby, the freedom degree of design of the electrode 21 for electrolysis is large, and the electrode 21 for electrolysis with high practicability can be provided.
  • the shape of the particles 23 used in Embodiment 2 is preferably spherical.
  • the spherical shape allows the gaps between the particles 23 and the gaps at the interface between the particles 23 and the binder 24 to have a relatively uniform shape and size. As a result, since the flow passage 25 having a stable flow passage resistance can be formed, stable ozone generation performance can be obtained.
  • the ozone generation performance of the electrode 21 for electrolysis prepared using the particle 23 of the fluid restriction layer 22 of alumina spherical particles having a uniform spherical shape and alumina having a polygonal shape and different particle shapes is evaluated. Will be explained.
  • ten glass electrodes were used as the binder 24, and ten electrodes 21 for electrolysis each having the fluid restriction layer 22 formed of spherical alumina beads and polygonal alumina particles were produced.
  • the electrolytic device 15 shown in FIG. 2 was produced by using the produced electrode 21 for electrolysis as an anode electrode and using a commercially available platinum electrode as a cathode electrode.
  • ozone is generated by raising the voltage for oxygen generation.
  • the voltage of oxygen generation at which ozone was generated was evaluated by the following.
  • a sample was prepared using sodium sulfate of 0.1 M concentration (Mol concentration) as an electrolyte, an Ag / AgCl electrode as a reference electrode, platinum as a counter electrode, and the electrolysis electrodes 11 and 21 of this embodiment as a working electrode. . Then, the voltage of oxygen generation was evaluated from the current-voltage characteristics measured by the potentiostat measuring device for the prepared sample.
  • the voltage of the electrolysis electrodes 11 and 21 was in the range of 1.6 to 3 V (relative to the potential of the reference electrode) suitable for the generation of ozone. That is, when the voltage is less than 1.6 V, the amount of generated ozone decreases. On the other hand, when the voltage exceeds 3 V, the current increases. Therefore, the elution amount of the noble metal contained in the electrode reaction layer 13 increases, and the durability of the electrode for electrolysis decreases.
  • the fluid limiting layer 14 of the first embodiment and the fluid limiting layer 22 of the second embodiment do not generate a crack that reaches the electrode reaction layer 13 as in the conventional case. Therefore, it was also found that the water flow passage was not formed due to the crack.
  • the material constituting the fluid restriction layers 14 and 22 does not have the catalytic effect of oxidizing oxygen and generating ozone.
  • FIG. 4 is a schematic enlarged cross-sectional view in the thickness direction of the electrode 11 for electrolysis in the third embodiment.
  • FIG. 5 is a schematic enlarged cross-sectional view of the fluid restricting layer 26 of the electrode 11 for electrolysis.
  • the electrode 11 for electrolysis of the third embodiment is different from that of the first embodiment in the constituent material of the fluid restricting layer 26. Therefore, the same components as in the first embodiment may be assigned the same reference numerals and descriptions thereof may be omitted.
  • the electrode 11 for electrolysis of Embodiment 3 is formed on the surface of the electrode base 12, the electrode reaction layer 13 formed on one surface of the electrode base 12, and the electrode reaction layer 13.
  • a fluid restriction layer 26 and the like are included.
  • the fluid limiting layer 26 is mainly made of an insulating material (or a low conductivity material).
  • the electrode base 12 and the electrode reaction layer 13 can be made of the same materials as in the first embodiment.
  • the fluid restricting layer 26 functions to restrict the contact area between water and the surface of the electrode reaction layer 13.
  • the fluid restricting layer 26 is formed by applying a coating agent based on an organic material and heat curing.
  • the fluid restricting layer 26 is formed of, for example, polyimide.
  • polyamic acid which is a polyimide precursor is applied to the surface of the electrode reaction layer 13 and formed by heat curing.
  • the fluid restricting layer 26 becomes a porous polyimide layer.
  • adjacent porous voids 27 communicate with each other, and a flow passage 28 communicating with the surface of the electrode reaction layer 13 through the fluid restriction layer 26 is formed.
  • Examples of the method for applying the polyimide precursor (polyamic acid) include, but are not limited to, spray coating, brush coating and spatula coating, roll coaters, spin coaters, screen printing, and the like. Depending on the material, for example, a manufacturing method such as CVD may be employed.
  • the electrode 11 for electrolysis of Embodiment 3 is comprised and produced.
  • Electrode 11 for electrolysis of Embodiment 3 is mounted
  • water is supplied to the electrolytic device 15 from the inlet 16 of the housing 18.
  • the supplied water flows through the flow path formed between the electrode 11 for electrolysis and the counter electrode 19, and flows out from the outlet 17 of the housing 18.
  • oxygen is generated at the electrode 11 for electrolysis which is an anode electrode, and hydrogen is generated at a counter electrode 19 which is a cathode electrode.
  • a fluid restricting layer 26 made of an insulating material (a low conductive material) is formed on the surface layer of the electrode 11 for electrolysis in contact with water. Therefore, even if electric power is supplied from the DC power supply 20 to the electrode 11 for electrolysis, the electrolysis reaction of water does not occur in the fluid restriction layer 26.
  • the fluid restricting layer 26 is formed of a porous polyimide layer, water penetrates into the voids 27 formed in the fluid restricting layer 26. Then, the water reaches the electrode reaction layer 13 through the flow passage 28 formed by connecting the air gaps 27. Thus, water is electrolyzed on the surface of the electrode reaction layer 13.
  • the contact area between the water that has reached the electrode reaction layer 13 and the electrode reaction layer 13 is extremely smaller than the area of the entire electrode reaction layer 13. Therefore, as compared with the electrode configuration without the fluid restriction layer 26, the current density of the portion of the electrode reaction layer 13 in contact with water is increased, and the voltage for generating oxygen is increased. In other words, the overvoltage of oxygen generation is high. Then, when the voltage for oxygen generation reaches a predetermined voltage or more, simultaneously with the generation of oxygen, active species such as oxygen radicals are generated. As a result, the generated active species react with oxygen to generate ozone.
  • the flow passage 28 through which water reaches the electrode reaction layer 13 is formed such that the voltage for oxygen generation is equal to or higher than a predetermined voltage.
  • the fluid restricting layer 26 can be formed with the size and the number of the air gaps 27 and the flow passages 28 by preparing the concentration, the composition, and the like of the solution of the polyimide precursor (polyamic acid) as the material. That is, the number and area of the flow passages 28 to the electrode reaction layer 13 can be easily adjusted.
  • the fluid restricting layer 26 is formed by applying a solution of a polyimide precursor (polyamic acid) as a material and heat curing it. Therefore, the adhesion between the fluid restricting layer 26 and the electrode reaction layer 13 is improved. Thereby, the destruction of the fluid restriction layer 26 due to the pressure of gas such as oxygen generated by the electrolysis and the peeling of the fluid restriction layer 26 due to the erosion of water at the interface between the fluid restriction layer 26 and the electrode reaction layer 13 It can prevent more reliably. Therefore, the contact area of water and the electrode reaction layer 13 is always maintained constant. As a result, the electrode 11 for electrolysis of Embodiment 3 can maintain the initial ozone generation performance over a long period of time.
  • a polyimide precursor polyamic acid
  • the fluid restricting layer 26 is formed by applying a solution of a polyimide precursor (polyamic acid) and heat curing. Therefore, unlike the conventional electrode for electrolysis, it is possible to form the electrode 11 for electrolysis having a predetermined film thickness by repeating application and baking several times without requiring coating of more than a dozen times or more. As a result, the manufacturing steps can be simplified and the manufacturing cost can be reduced by reducing the number of manufacturing steps. As a result, the electrode 11 for electrolysis excellent in productivity can be provided stably.
  • a polyimide precursor polyamic acid
  • the fluid restricting layer 26 is formed by applying a solution of a polyimide precursor (polyamic acid) and heat curing. Therefore, the fluid restricting layer 26 can be formed by heating at about 300.degree. That is, unlike the conventional electrode for electrolysis, it is not necessary to bake at a high temperature of 600 to 700 ° C. Thereby, the influence of heat on the electrode base 12 and the electrode reaction layer 13 of the electrode 11 for electrolysis can be reduced. As a result, the material selectivity of the fluid restricting layer 26 can be expanded, and the manufacturing cost can be reduced.
  • a polyimide precursor polyamic acid
  • the flow passage 28 penetrates the fluid restriction layer 26 and reaches the electrode reaction layer 13 but does not reach the electrode base 12. Therefore, the occurrence of inconvenience such as erosion of the electrode substrate 12 by electrolysis can be eliminated in advance.
  • the fluid restricting layer 26 can easily adjust the area of the electrode reaction layer 13 in the portion in contact with water by adjusting the number and the area of the flow passages 28. Thereby, the fluid restriction layer 26 can generate ozone at a desired ozone concentration.
  • the fluid restricting layer 26 needs a predetermined film thickness to obtain a high voltage at the electrode reaction layer 13 depending on the desired ozone concentration.
  • the film thickness of the fluid restriction layer 26 is large, the water does not easily pass through the flow passage 28, and the permeability (such as the amount of permeation) of water is impaired. Therefore, the inventors of the present application conducted various experiments on the film thickness of the fluid restriction layer 26. As a result, it has been found that the film thickness of the fluid restricting layer 26 is preferably in the range of 1 to 10 ⁇ m.
  • the flow path 28 of the fluid restricting layer 26 is formed of a coating film capable of forming the flow path 28.
  • the present invention is not limited to this.
  • the film may be machined or etched to form the flow passage.
  • a film having the flow passage 28 may be separately formed, and the film may be adhered to the electrode reaction layer 13 with an adhesive or the like. Thereby, the same effect as the case of applying a coating is acquired.
  • the configuration using a metal material as the electrode substrate 12 has been described as an example, but the electrode substrate 12 may be made of a dielectric substrate such as ceramic as exemplified in the second embodiment. .
  • a ceramic substrate is used as the electrode substrate 12, it is necessary to form a terminal for connection to a power supply at the end of the electrode substrate 12.
  • the terminal portion is configured by forming a conductive film electrically connected across part or the entire width of the electrode reaction layer 13. At this time, there is a possibility that electrolysis of water may occur due to the conductive film. Therefore, it is preferable to use a material having no catalytic action, such as platinum, as the conductive film.
  • the electrolytic device 15 was produced using the electrode 11 for electrolysis demonstrated above, and the following methods evaluated.
  • the fluid restriction layer 14 generates ozone by raising the voltage of oxygen generation.
  • a sample was prepared using 0.1 M sodium sulfate as an electrolyte, an Ag / AgC electrode as a reference electrode, platinum as a counter electrode, and the electrode 11 for electrolysis of the present invention as a working electrode. And the voltage of oxygen production was evaluated from the current-voltage characteristic measured with a potentiostat measuring device for the produced sample.
  • the voltage of the electrode for electrolysis 11 in the range of 1.6 to 3 V is suitable for the generation of ozone. That is, when the voltage is less than 1.6 V, the amount of generated ozone decreases. On the other hand, when the voltage exceeds 3 V, the current increases. Therefore, the elution amount of the noble metal contained in the electrode reaction layer 13 increases, and the durability of the electrode 11 for electrolysis decreases.
  • Embodiment 3 the electrode 11 for electrolysis which changed the porosity of the fluid restriction layer 26 was produced, and the voltage was measured.
  • the inventors of the present application confirmed that if the porosity (porosity) of the fluid limiting layer 26 is in the range of 10 to 50%, the voltage of the electrode 11 for electrolysis can be in the above voltage range. That is, when the porosity is less than 10%, the voltage of the electrode 11 for electrolysis exceeds 3V. In addition, since the gas leakage through the air gap of the fluid restricting layer 26 is deteriorated, the electrodes are easily peeled off and the durability is lowered. On the other hand, when the porosity exceeds 50%, the voltage of the electrode 11 for electrolysis is less than 1.6V. Therefore, it becomes difficult to generate ozone.
  • Porosity (%) (M0-M1) / M0 x 100
  • M0 is the mass of the fluid restriction layer when there is no air gap 27 or flow passage 28.
  • M1 is a mass of the fluid restriction layer in the case where there are the air gap 27 and the flow passage 28.
  • the fluid restricting layer 26 of the third embodiment is formed by applying a solution of a polyimide precursor (polyamic acid) and heat curing it, so that there is no catalytic effect to generate ozone.
  • a polyimide precursor polyamic acid
  • FIG. 6 is a schematic cross-sectional view of the electrode 11 for electrolysis in the fourth embodiment.
  • the electrode 11 for electrolysis of the fourth embodiment is different from that of the first embodiment in that a terminal portion 29 constituting an electric bonding layer for electrically connecting to the DC power supply 20 is provided on the surface of the electrode reaction layer 13. .
  • the same components as in the first embodiment may be assigned the same reference numerals and descriptions thereof may be omitted.
  • the electrode 11 for electrolysis of Embodiment 4 is formed on the surface of the electrode substrate 12, the electrode reaction layer 13 formed on one surface of the electrode substrate 12, and the electrode reaction layer 13.
  • a fluid restriction layer 14 and the like are included.
  • the terminal portion 29 is provided on a part of the surface of the electrode reaction layer 13 in which the fluid restriction layer 14 is not formed.
  • the terminal portion 29 is formed of, for example, a conductive film such as platinum.
  • FIG. 7 is a schematic cross-sectional view of the electrode 11 for electrolysis in the fifth embodiment.
  • the electrode 11 for electrolysis of the fifth embodiment is different from that of the fourth embodiment in that the electrode substrate 12 is composed of a metal substrate 12 b and an insulating film 12 a provided on the surface of the metal substrate 12 b.
  • the same components as in the fourth embodiment may be assigned the same reference numerals and descriptions thereof may be omitted.
  • the electrode 11 for electrolysis of the fifth embodiment is formed on the surface of the electrode base 12, the electrode reaction layer 13 formed on one surface of the electrode base 12, and the electrode reaction layer 13.
  • a fluid restriction layer 14 and the like are included.
  • the electrode substrate 12 includes an insulating film 12a formed on the surface of the metal substrate 12b.
  • a terminal portion 29 constituting an electric bonding layer for electrically connecting to the DC power supply 20 is formed on a part of the surface of the electrode reaction layer 13 where the fluid restriction layer 14 is not formed.
  • the terminal portion 29 is formed of, for example, a conductive film such as platinum.
  • FIG. 8 is a schematic enlarged sectional view in the thickness direction of the electrode 11 for electrolysis in the sixth embodiment.
  • the material for the fluid restricting layer 30 of the electrolysis electrode 11 of the sixth embodiment is different from that of the first embodiment.
  • the electrode 11 for electrolysis of the sixth embodiment is formed on the surface of the electrode substrate 12, the electrode reaction layer 13 formed on one surface of the electrode substrate 12, and the electrode reaction layer 13.
  • a fluid restriction layer 30 and the like are included.
  • the fluid restricting layer 30 is made of a material including metal oxide derived from metal alkoxide and metal oxide fine particles.
  • the electrode base 12 and the electrode reaction layer 13 can be made of the same materials as in the first embodiment.
  • the fluid restriction layer 30 is formed by the following method.
  • a coating agent composed mainly of metal alkoxide and metal oxide fine particles or metal oxide precursor fine particles is applied to the surface of the electrode reaction layer 13. Then, the applied coating agent is cured by hydrolysis and dehydration reaction. Thereby, the fluid restriction layer 30 is formed.
  • the metal alkoxide is selected from, for example, metal alkoxide containing one or more elements from tantalum, titanium, aluminum, silicone, tungsten, niobium and the like.
  • the fluid restriction layer 30 is not particularly limited to the degree of polymerization of the metal alkoxide used.
  • the metal oxide fine particles are selected, for example, from tantalum oxide, titanium oxide, aluminum oxide, silicon oxide, tungsten oxide, niobium oxide and the like from metal oxide fine particles containing one or more elements.
  • fine-particles as a substitute of metal oxide microparticles
  • aluminum hydroxide or boehmite can be applied as an aluminum oxide precursor.
  • the particle size of these metal oxide fine particles or metal oxide precursor fine particles is not particularly limited. However, from the viewpoint of controlling the occurrence of cracks, the particle size is preferably submicron size.
  • a noble metal such as platinum, gold, or iridium may be partially added to the fluid restricting layer 30. Thereby, the conductivity of the fluid restriction layer 30 can be controlled.
  • the fluid restriction layer 30 for example, spray coating, brush or spatula coating, roll coater, spin coater, screen printing and the like can be mentioned, but it is not limited thereto.
  • a manufacturing method by sputtering, CVD or the like can be adopted.
  • the electrode 11 for electrolysis of the sixth embodiment is configured and manufactured.
  • Electrode 11 for electrolysis of Embodiment 6 is mounted
  • water is supplied to the electrolytic device 15 from the inlet 16 of the housing 18.
  • the supplied water flows through the flow path formed between the electrode 11 for electrolysis and the counter electrode 19, and flows out from the outlet 17 of the housing 18.
  • the fluid restricting layer 30 made of a dielectric material is formed on the outermost layer of the electrode 11 for electrolysis in contact with water.
  • the fluid limiting layer 14 can not obtain conductivity as an electrode. That is, in the fluid restriction layer 30, the electrolysis reaction of water does not occur. However, water permeates through the fluid restriction layer 30 via the communication passage 31. The permeated water reaches the conductive electrode reaction layer 13 formed on the surface of the electrode substrate 12 of the electrode 11 for electrolysis. The water reached is electrolyzed on the surface of the electrode reaction layer 13. This produces ozone as described above.
  • FIG. 9 is a schematic enlarged cross-sectional view of the fluid restricting layer 30 in the seventh embodiment.
  • FIG. 10 is a schematic enlarged cross-sectional view of the fluid restriction layer 30. As shown in FIG.
  • the fluid restricting layer 30 of the sixth embodiment is described in more detail.
  • the fluid restricting layer 30 of the seventh embodiment is made of a material including the metal oxide 32 derived from the metal alkoxide and the metal oxide fine particles 33.
  • the metal oxide 32 and the metal oxide fine particles 33 are chemically bonded. Thereby, the strength of the dielectric film forming the fluid restricting layer 30 is enhanced. As a result, destruction of the fluid restriction layer 30 due to the pressure of a gas such as oxygen generated by electrolysis, peeling of the fluid restriction layer 30 due to erosion of water at the interface between the fluid restriction layer 30 and the electrode reaction layer 13, It can prevent.
  • the contact area of water and the electrode reaction layer 13 can always be maintained constant.
  • the electrode 11 for electrolysis of Embodiment 7 can maintain the initial ozone generation performance over a long period of time.
  • the fluid restricting layer 30 is formed of a film containing the metal oxide fine particles 33. Therefore, the metal oxide fine particles 33 have an effect of controlling the progress of the crack generated in the metal oxide 32. Thereby, the cracks 34 can be uniformly distributed in the fluid restriction layer 30. Then, starting from the crack 34, the plurality of cracks 34 are fused and connected. Thus, the communication passage 31 is formed in the fluid restriction layer 30.
  • the communication passage due to the occurrence of the crack is increased as the ratio of the metal oxide fine particles 33 occupied in the fluid restricting layer 30 is increased.
  • the distribution frequency of 31 decreases.
  • the diameter of the communication passage 31 tends to decrease.
  • the contact area between the water that has reached the electrode reaction layer 13 and the electrode reaction layer 13 is extremely smaller than the area of the entire electrode reaction layer 13. Therefore, the current density of the portion of the electrode reaction layer 13 in contact with water is increased and the voltage of oxygen generation is higher than that of the electrode structure without the fluid restriction layer 30. Then, when the voltage for oxygen generation reaches a predetermined voltage or more, simultaneously with the generation of oxygen, active species such as oxygen radicals are generated. As a result, the generated active species react with oxygen to generate ozone.
  • the electrode 11 for electrolysis of the seventh embodiment has the porosity of the fluid restricting layer 30 by adjusting the ratio of the metal oxide fine particles 33 or the like so that the electrode reaction of oxygen generation occurs above the voltage generating ozone. Control.
  • the water is electrolyzed at a voltage or current according to the required ozone production amount.
  • ozone water of a predetermined concentration can be stably produced.
  • a material that is excellent in acid resistance and alkali resistance may be added to the fluid restriction layer 30. ,preferable. This makes it possible to secure acid resistance and alkali resistance as well as dielectric properties. As a result, the durability of the fluid restriction layer 30 is improved.
  • an alkaline aqueous solution is used as the electrolytic solution is described below as an example.
  • M 1 corresponding to the metal oxide 32 derived from the metal alkoxide shown in FIG. 10 for example, silicon, which is inferior in alkali resistance, is used.
  • aluminum which has excellent alkali resistance, is used as M 2 corresponding to the metal oxide fine particles 33.
  • FIG. 11 is a schematic enlarged sectional view in the thickness direction of the electrode 11 for electrolysis in the eighth embodiment.
  • the electrode 11 for electrolysis of the eighth embodiment differs from that of the first embodiment in the configuration of the fluid restricting layer 35.
  • the electrode 11 for electrolysis of the eighth embodiment is formed on the surface of the electrode base 12, the electrode reaction layer 13 formed on one surface of the electrode base 12, and the electrode reaction layer 13.
  • the fluid restriction layer 35 is included.
  • the fluid restricting layer 35 is composed of a glass composition whose main component is silicon dioxide.
  • the electrode base 12 and the electrode reaction layer 13 can be made of the same materials as in the first embodiment.
  • the fluid restricting layer 35 is formed of a glass layer and is formed by the following method.
  • a glass paste prepared by mixing a glass frit of a main component of silicon dioxide, a resin, and a solvent is applied to the electrode substrate 12. Then, the applied glass paste is fired. Thereby, the fluid restriction layer 35 is formed. At this time, when the glass paste is fired, pin holes penetrating through the fluid restriction layer 35 are generated in the fluid restriction layer 35.
  • the communication holes 36 formed in the fluid restriction layer 35 are configured by the pinholes.
  • fluid restriction layer 35 for example, spray coating, brush or spatula coating, roll coater, spin coater, screen printing, etc. may be mentioned, but it is not limited thereto. Furthermore, sputtering, CVD, or the like may be employed.
  • the electrode 11 for electrolysis of the eighth embodiment is configured and manufactured.
  • Electrode 11 for electrolysis of Embodiment 8 is mounted
  • the counter electrode 19 is described using platinum, but the present invention is not limited to this.
  • water is supplied to the electrolytic device 15 from the inlet 16 of the housing 18.
  • the supplied water flows through the flow path formed between the electrode 11 for electrolysis and the counter electrode 19, and flows out from the outlet 17 of the housing 18.
  • oxygen is generated at the electrode 11 for electrolysis which is an anode electrode, and hydrogen is generated at a counter electrode 19 which is a cathode electrode.
  • the fluid restricting layer 35 formed of a glass layer having no conductivity is formed on the outermost layer of the electrode 11 for electrolysis in contact with water.
  • communication holes 36 are formed in the fluid restriction layer 35 by pin holes.
  • the water passes through the communication holes 36 and reaches the conductive electrode reaction layer 13 formed on the surface of the electrode base 12.
  • the water reaching the electrode reaction layer 13 is electrolyzed on the surface of the electrode reaction layer 13.
  • the area in which the water reaching the electrode reaction layer 13 contacts the electrode reaction layer 13 is extremely smaller than the area of the electrode reaction layer 13. Therefore, the current flowing due to the electrode reaction is concentrated at the portion where the water and the electrode reaction layer 13 are in contact, and the current density becomes high. Thereby, the voltage applied to the electrode 11 for electrolysis becomes high, and the voltage of oxygen generation becomes high. In other words, the overvoltage of oxygen generation is high. Then, when the voltage for generating oxygen becomes equal to or higher than a predetermined voltage, the generation of oxygen and the active species such as oxygen radicals are simultaneously generated, whereby the generated active species react with oxygen, and ozone is generated. Is generated.
  • the number (quantity) of the communication holes 36 formed in the fluid restriction layer 35 is controlled so that the electrode reaction of oxygen generation occurs above the voltage at which ozone is generated. Thereby, ozone water of a predetermined concentration can be obtained.
  • the porosity of the communication hole 36 formed in the fluid restricting layer 35 can be controlled by the film thickness of the fluid restricting layer 35. That is, when the film thickness of the fluid restriction layer 35 is thin, the number of pinholes formed is increased. Therefore, the number of the communication holes 36 increases, and the voltage for generating oxygen decreases. On the other hand, if the film thickness of the fluid restricting layer 35 is large, the number of pinholes formed is reduced. Therefore, the number of communication holes 36 is also reduced, and the voltage for generating oxygen is increased.
  • the voltage for oxygen generation is lower, oxygen is generated but the amount of active species generated is smaller. Therefore, the amount of ozone generation is reduced.
  • the voltage for generating oxygen increases, the amount of generated ozone increases, but the voltage applied as the electrolytic device 15 increases. Therefore, the power supply circuit of the electrolytic device 15 becomes complicated, and the power consumption increases.
  • the film thickness of the fluid restricting layer 35 is set to 5 to 15 ⁇ m.
  • both of the practical applied voltage and the ozone generation amount can be established.
  • the range of the film thickness of the fluid restricting layer 35 has been found by intensive studies of the present inventors.
  • the communication holes 36 of the fluid restricting layer 35 are formed of pinholes generated by applying and firing a glass paste.
  • the fluid restricting layer 35 is composed only of the glass composition free of other non-compound particles. Therefore, if the fluid restriction layer 35 is formed to have the same film thickness, the number of pinholes generated becomes stable. That is, by adjusting the film thickness of the fluid restriction layer 35, stable porosity (number) of the communication holes 36 can be obtained. As a result, the ozone generation performance can be stabilized.
  • the fluid restricting layer 35 of the eighth embodiment is adhered to the electrode reaction layer 13 with high adhesion. Furthermore, the glass component of the fluid restricting layer 35 adheres the fluid restricting layer 35 to the electrode substrate 12 through the holes formed when the electrode reaction layer 13 is fired. Thereby, breakage or peeling of the fluid restriction layer 35 due to the pressure of a gas such as oxygen generated by the electrolysis of water can be more reliably prevented.
  • the electrode 11 for electrolysis of the eighth embodiment is used as an anode electrode in order to generate target ozone.
  • an electrode reaction of oxygen generation occurs on the anode electrode side. Therefore, the fluid restricting layer 35 and the electrode reaction layer 13 which constitute the electrode 11 for electrolysis are exposed to a strong acidic environment with low pH.
  • metal ions such as calcium ions contained in water are reduced and attached as a scale component.
  • the polarity of the applied voltage or current is reversed and applied to the anode electrode and the cathode electrode to remove the scale, that is, polarity inversion is performed.
  • the electrode 11 for electrolysis serves as a cathode electrode. Therefore, the surface of the electrode 11 for electrolysis becomes a strong basic environment with high pH.
  • the fluid restricting layer 35 is formed using a glass composition whose main component is silicon dioxide. Silicon dioxide glass is excellent in acid resistance and base resistance. Therefore, in the fluid restriction layer 35, the elution of the components of the fluid restriction layer 35 is suppressed even in a strongly acidic or strongly basic environment, and peeling and dissolution of the fluid restriction layer 35 can be prevented. Thus, it is possible to realize the fluid restriction layer 35 capable of maintaining stable ozone generation performance over a long period of time.
  • the content of silicon dioxide in the fluid restriction layer 35 is less than 60% by weight, dissolution of the fluid restriction layer 35 occurs because the elution of other glass components in the fluid restriction layer 35 increases.
  • the content of silicon dioxide is 60% by weight or more, the elution of other glass components in the fluid restriction layer 35 can be prevented.
  • the content of silicon dioxide is increased, the firing temperature is increased, so that the electrode substrate 12 is deformed by oxidation. Therefore, in order to satisfy both the acid resistance and the base resistance, the content of silicon dioxide in the fluid restricting layer 35 is preferably in the range of 60 to 90% by weight.
  • the fluid restricting layer 35 is more preferably a glass having a composition not containing a compound of an alkali metal and an alkaline earth metal.
  • the fluid restriction layer 35 containing the compound of the alkali metal and the alkaline earth metal gradually elutes the alkali metal and the alkaline earth metal and becomes porous.
  • the fluid restricting layer 35 is made porous, the area of the electrode reaction layer 13 in contact with water is increased, so that the voltage for oxygen generation is reduced and the ozone generation performance is reduced.
  • the fluid restricting layer 35 of the eighth embodiment is made of a glass composition in which the main component made of glass not containing a compound of an alkali metal and an alkaline earth metal is silicon dioxide.
  • the fluid restriction layer 35 can suppress the elution of the glass component. Therefore, even if the electrolysis electrode 11 is left immersed in water for a long period of time, the fluid restriction layer 35 can be prevented from being made porous. As a result, it is possible to realize the fluid restriction layer 35 capable of maintaining the initial ozone generation performance over a long period of time.
  • the electrode reaction layer 13 is preferably made of a material that enhances the electrode reaction for electrolytically decomposing water.
  • Materials that activate the electrode reaction include materials containing noble metals. Among them, noble metals of platinum, palladium, rhodium, ruthenium, indium, alloys containing these noble metals, and oxides containing noble metals are more preferable. Thereby, since the electrolysis performance of water can be made high, the production amount of ozone can be increased. Moreover, since the said material is chemically stable, durability of the electrode reaction layer 13 can be further improved.
  • the fluid restricting layer 35 according to the eighth embodiment does not require coating of more than a dozen times as in the conventional electrode for electrolysis, and the predetermined film thickness is obtained by repeating application and baking several times at most. You can get As a result, cost reduction can be achieved by simplifying the manufacturing steps and reducing the number of manufacturing steps of the fluid restriction layer 35. As a result, the electrode 11 for electrolysis excellent in productivity can be provided.
  • FIG. 12 is a schematic enlarged sectional view in the thickness direction of the electrode 11 for electrolysis in the ninth embodiment.
  • the electrode 11 for electrolysis of the ninth embodiment is different from that of the eighth embodiment in the constituent material of the electrode reaction layer 37.
  • the same constituent materials as in Embodiment 8 may be assigned the same reference numerals and descriptions thereof may be omitted.
  • the electrode 11 for electrolysis includes an electrode substrate 12, an electrode reaction layer 37 formed on one surface of the electrode substrate 12, and a fluid restriction layer 35 formed on the surface of the electrode reaction layer 37.
  • the fluid restricting layer 35 is composed of a glass layer whose main component is silicon dioxide. Therefore, the fluid restricting layer 35 has a communicating hole 36 which is formed at the time of firing and communicates with the electrode reaction layer 37.
  • the electrode base 12 and the fluid restricting layer 35 can be made of the same materials as in the eighth embodiment.
  • the electrode reaction layer 37 is made of a noble metal, an alloy containing a noble metal, or a noble metal oxide, and a glass composition whose main component is silicon dioxide. At this time, the electrode reaction layer 37 is formed by the following method in a state where at least one kind of noble metal particles 39 of the noble metal, the alloy containing the noble metal, and the oxide containing the noble metal are dispersed in the glass composition 38 Be done.
  • a conductive paste is prepared by mixing noble metal particles 39, a glass frit whose main component is silicon dioxide, a resin, and a solvent. Then, the produced conductive paste is applied to the electrode substrate 12 and fired. Thereby, the electrode reaction layer 37 is formed.
  • the water having passed through the communication hole 36 of the fluid restriction layer 35 is electrolyzed on the surface of the electrode reaction layer 37.
  • the electrode reaction layer 37 is made of a glass composition having the same composition as the fluid restricting layer 35. Therefore, the adhesion between the fluid restricting layer 35 and the electrode reaction layer 37 is further improved. Thereby, destruction or peeling of the fluid restriction layer 35 due to the gas generated by the electrode reaction can be further reliably prevented.
  • the electrode reaction layer 37 contains the glass composition which is a silicon dioxide as a main component, adhesiveness with the electrode base 12 improves. Therefore, it is possible to more reliably prevent the delamination due to the erosion of water at the interface between the electrode reaction layer 37 and the electrode base 12 as well as the fluid restriction layer 35 and the electrode reaction layer 37 described above. Thereby, the area of the electrode reaction layer 13 in contact with water can be stably maintained. As a result, the electrode 11 for electrolysis which can maintain the initial ozone generation performance over a long period of time can be realized.
  • the electrode 11 for electrolysis produced in the following shape was evaluated by the durability using the electrolysis device 15 shown in FIG.
  • the electrode 11 for electrolysis was produced with an effective electrode area of 9 cm 2 .
  • the test conditions were a current density of 20 mA / cm 2 and a water flow rate of 90 ml / min.
  • a repeated test of the driving operation of 30 minutes as the anode electrode for electrolysis and 30 minutes as the cathode electrode was performed to evaluate the durability.
  • the commercial platinum electrode was used for the electrode used as a counter electrode. At this time, the operation operation time as an anode electrode was repeatedly tested until it became 200 hours, for example.
  • an electrode for electrolysis using bismuth-based glass was evaluated as the fluid restricting layer 35 of the eighth embodiment. Furthermore, the same test was performed also for the electrode for electrolysis which used the conventional dielectric material layer.
  • the electrode 11 for electrolysis according to Embodiment 8 and Embodiment 9 exhibits higher ozone generation performance than that of the conventional electrode for electrolysis, and the effect of the present embodiment is confirmed.
  • the main component of the fluid restricting layer 35 of the eighth embodiment is replaced with a glass composition which is silicon dioxide, and the electrode for electrolysis using a bismuth-based glass composition has both the electrode reaction layer 13 and the fluid restricting layer 35. Dissolved, peeled off, and the ability to generate ozone was lost.
  • the electrode 11 for electrolysis of Embodiment 8, 9 is excellent in durability.
  • the fluid restricting layer 35 in the eighth embodiment and the ninth embodiment generates ozone by raising the voltage of oxygen generation.
  • the electrode for electrolysis 11 according to Embodiment 8 and Embodiment 9 was used to evaluate from the current-voltage characteristics.
  • the voltage of the electrode for electrolysis 11 is preferably in the range of 1.6 to 3 V (relative to the potential of the reference electrode) for the generation of ozone. That is, when the voltage was less than 1.6 V, the amount of generated ozone decreased. On the other hand, in the case of a voltage exceeding 3 V, the current flowed due to the generation of ozone. As a result, it was found that the elution amount of the noble metal contained in the electrode reaction layer 13 increased, and the durability of the electrode 11 for electrolysis decreased.
  • the fluid restriction layer 35 of the eighth and ninth embodiments did not generate a crack reaching the electrode reaction layers 13 and 37 as in the prior art. That is, it was found that the fluid restriction layer 35 of the eighth and ninth embodiments is not configured to use the crack as the water flow passage as in the conventional case.
  • the glass composition used for the fluid restricting layer 35 has no catalytic effect of oxidizing oxygen and generating ozone.
  • FIG. 13 is a schematic enlarged cross-sectional view in the thickness direction of the electrode 11 for electrolysis in the tenth embodiment.
  • the electrode 11 for electrolysis of the tenth embodiment is different from that of the first embodiment in the constituent material of the fluid restricting layer 40.
  • the electrode 11 for electrolysis of Embodiment 10 is formed on the surface of the electrode base 12, the electrode reaction layer 13 formed on one surface of the electrode base 12, and the electrode reaction layer 13.
  • a fluid restriction layer 40 and the like are included.
  • the same material as that of the first embodiment can be used for the electrode substrate 12 and the electrode reaction layer 13.
  • the fluid restricting layer 40 is formed of a glass layer. Specifically, first, dielectric particles 42 are mixed with glass frit, resin, and solvent of the main component silicon dioxide, which is a starting material of the glass composition 41, to prepare a glass paste. The produced glass paste is applied to the electrode reaction layer 13 and fired. Thereby, the fluid restriction layer 40 is formed. At this time, at the time of firing, a flow passage 43 through which water flows is formed in the fluid restriction layer 40 through the gap at the interface between the glass composition 41 and the dielectric particles 42 and the gap between the dielectric particles 42. Ru.
  • fluid restriction layer 40 for example, spray coating, brush or spatula coating, roll coater, spin coater, screen printing, etc. may be mentioned, but it is not limited thereto.
  • the electrode 11 for electrolysis of the tenth embodiment is configured and manufactured.
  • the electrode 11 for electrolysis of Embodiment 10 is mounted
  • the counter electrode 19 is described using platinum, but is not limited thereto.
  • water is supplied to the electrolytic device 15 from the inlet 16 of the housing 18.
  • the supplied water flows through the flow path formed between the electrode 11 for electrolysis and the counter electrode 19, and flows out from the outlet 17 of the housing 18.
  • the fluid restricting layer 40 of the tenth embodiment is formed of the glass composition 41 and the dielectric particles 42, it has no conductivity. Therefore, even if a voltage or current is applied to the fluid restriction layer 40 from the DC power supply 20, no electrolysis reaction of water occurs on the surface of the fluid restriction layer 40.
  • the flow passage 43 is formed. Therefore, the water passes through the flow passage 43 and reaches the conductive electrode reaction layer 13 formed on the surface of the electrode substrate 12. Then, the reached water is electrolyzed on the surface of the electrode reaction layer 13.
  • the fluid restricting layer 40 of the tenth embodiment is composed of a glass composition 41 whose main component is silicon dioxide and dielectric particles 42.
  • the fluid restricting layer 40 is in a state in which the dielectric particles 42 are dispersed in the glass composition 41.
  • the glass composition 41 and the dielectric particles 42 are not in a state of being in close contact with each other.
  • the contact portion between the dielectric particles 42 is also point contact. Therefore, a minute gap is formed around the dielectric particles 42.
  • the flow path 43 of the fluid restricting layer 40 of the tenth embodiment is formed by utilizing the gap between the glass composition 41 and the dielectric particles 42 and the gap between the dielectric particles 42. Therefore, the area of the electrode reaction layer 13 in contact with water changes depending on the size and number (quantity) of the flow passage 43. Furthermore, the size and number (quantity) of the flow path 43 change depending on the film thickness of the fluid restriction layer 40, the size and content of the dielectric particles 42 contained in the fluid restriction layer 40, and the like.
  • the voltage for oxygen generation is relatively lower than the voltage before increasing the particle size of the dielectric particles and increasing the content of the number of dielectric particles.
  • the film thickness of the fluid restriction layer 40 is thick, the particle diameter of the dielectric particles 42 is small, and the content of the dielectric particles 42 is small, the area of the electrode reaction layer 13 in contact with water flowing through the flow passage 43 is It becomes smaller. Therefore, the voltage for oxygen generation is relatively higher than the voltage before the particle size of the dielectric particles is reduced and the content of the dielectric particles is reduced.
  • the generation of ozone changes depending on the film thickness of the fluid restricting layer 40 and the particle diameter and content of the dielectric particles 42 contained in the fluid restricting layer 40. Therefore, the range of the film thickness, the particle diameter, and the content can be appropriately selected as long as a predetermined ozone generation amount can be obtained, and is not particularly limited.
  • FIG. 14 is a schematic enlarged cross-sectional view in the thickness direction of the electrode 11 for electrolysis in the eleventh embodiment.
  • the electrode 11 for electrolysis of the tenth embodiment is different from that of the tenth embodiment in the constituent material of the electrode reaction layer 44.
  • the same components as in Embodiment 10 may be assigned the same reference numerals and descriptions thereof may be omitted.
  • the electrode 11 for electrolysis of Embodiment 11 is formed on the surface of the electrode substrate 12, the electrode reaction layer 44 formed on one surface of the electrode substrate 12, and the electrode reaction layer 44.
  • a fluid restriction layer 40 and the like are included.
  • the electrode base 12 and the fluid restricting layer 40 can be made of the same materials as in the tenth embodiment.
  • At least one kind of noble metal particles 46 of a noble metal, an alloy containing a noble metal, and an oxide containing a noble metal are dispersed in a glass composition 45 whose main component is silicon dioxide. Composed of states.
  • the electrode reaction layer 44 is a conductive mixture of a noble metal particle 46 and a glass frit of main component silicon dioxide, which is a starting material of the glass composition of main component silicon dioxide, and a resin and a solvent. Make a paste. The produced conductive paste is applied to the electrode substrate 12 and fired. Thereby, the electrode reaction layer 44 is formed.
  • the electrode 11 for electrolysis including the electrode reaction layer 44 is configured and manufactured.
  • a glass composition having the same composition as the fluid restricting layer 40 is used for the electrode reaction layer 44. Therefore, the adhesion between the fluid restricting layer 40 and the electrode reaction layer 44 is further improved. Thereby, destruction or peeling of the fluid restriction layer 40 due to a gas generated when water is electrolyzed by the electrode reaction can be more reliably prevented.
  • the electrode reaction layer 44 of Embodiment 11 contains the glass composition whose main component is silicon dioxide. Therefore, the adhesion between the electrode reaction layer 44 and the electrode base 12 is further improved than in the ninth embodiment. Thus, it is possible to more reliably prevent delamination due to water erosion not only at the interface between the fluid limiting layer 40 and the electrode reaction layer 44 but also at the interface between the electrode reaction layer 44 and the electrode substrate 12. As a result, since the area of the electrode reaction layer 44 in contact with water can be stably maintained, the electrode 11 for electrolysis which can maintain the initial ozone generation performance over a long period of time can be realized.
  • the electrode 11 for electrolysis produced in the following shape was evaluated by the durability using the electrolysis device 15 shown in FIG.
  • the electrode 1 for electrolysis was produced with an effective electrode area of 9 cm 2 .
  • the test conditions were a current density of 20 mA / cm 2 and a water flow rate of 90 ml / min.
  • a repeated test of operation operation of 30 minutes as the anode electrode for electrolysis and 30 minutes as the cathode electrode for electrolysis was performed to evaluate the durability.
  • the commercial platinum electrode was used for the electrode used as a counter electrode. At this time, the operation operation time as an anode electrode was repeatedly tested until it became 200 hours, for example.
  • an electrode for electrolysis using bismuth-based glass was evaluated as the fluid restricting layer 40 of the tenth embodiment. Furthermore, the same test was performed also for the electrode for electrolysis which used the conventional dielectric material layer.
  • the electrode 11 for electrolysis according to Embodiment 10 and Embodiment 11 has higher ozone generation performance than that of the conventional electrode for electrolysis, and the effect of this embodiment was confirmed.
  • the electrode 11 for electrolysis of Embodiment 10 and 11 is excellent in durability.
  • the fluid limiting layer 40 in the tenth and eleventh embodiments generates ozone by raising the voltage for oxygen generation.
  • the electrode for electrolysis 11 according to Embodiment 8 and Embodiment 9 was used to evaluate from the current-voltage characteristics.
  • the voltage of the electrode for electrolysis 11 is preferably in the range of 1.6 to 3 V (relative to the potential of the reference electrode) for the generation of ozone. That is, when the voltage is less than 1.6 V, the amount of generated ozone decreases. On the other hand, in the case of a voltage exceeding 3 V, the current flowed due to the generation of ozone. As a result, the elution amount of the noble metal contained in the electrode reaction layer 44 increases, and the durability of the electrode 11 for electrolysis decreases.
  • the electrode for electrolysis can control the voltage at which ozone is generated by the fluid restriction layer. Therefore, by controlling the voltage, ozone water of any concentration can be produced. In addition, since the adhesion between the fluid restriction layer and the electrode reaction layer is high, peeling of the fluid restriction layer can be prevented. Therefore, water having excellent durability and stable ozone concentration can be obtained over a long period of time. Furthermore, the fluid restriction layer is excellent in productivity because it can be easily formed in a simple step.
  • the electrolysis apparatus which has an electrode for electrolysis in embodiment of this invention in various electric equipment or an ozone generator.
  • the ozone generated by the electrolytic device having the electrode for electrolysis causes sterilization of water and food, deodorization of the room by decomposition of odorous components, purification of bath water, and prevention of contamination of the bath in various electric devices and ozone generators. Can be realized.
  • the electrode for electrolysis of the present invention improves stable production and durability of ozone, and is excellent in productivity. Therefore, the present invention can be applied to an electric device, an ozone generator, and the like equipped with an electrolytic device having functions such as sterilization of water and food with ozone, deodorization of a room by decomposition of odor components, purification of bath water, and contamination prevention of a bath.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

La présente invention concerne une électrode d'électrolyse (11) qui est configurée à partir : d'un substrat d'électrode (12) ; d'une couche de réaction d'électrode (13) qui est formée sur la surface du substrat d'électrode (12) et comprend un ou plusieurs types parmi un métal précieux, un alliage contenant un métal précieux, et un oxyde contenant un métal précieux ; et d'une couche de restriction de fluide (14) qui est formée sur la surface de la couche de réaction d'électrode (13), a un liant en tant que composant principal de celui-ci, et limite la surface de contact entre l'eau et la couche de réaction d'électrode (13). Par conséquent, la couche de restriction de fluide (14) augmente la tension de génération d'oxygène en limitant le contact entre l'eau et la couche de réaction d'électrode (13), ce qui entraîne la production d'ozone. En outre, la couche de restriction de fluide (14) est formée à partir d'un matériau liant. Par conséquent, l'électrode d'électrolyse (11) fournie présente une durabilité améliorée et empêche la couche de restriction de fluide (14) de celle-ci de se séparer de celle-ci.
PCT/JP2018/039308 2017-10-27 2018-10-23 Électrode d'électrolyse, et dispositif de génération d'ozone et dispositif électrique équipés de celle-ci Ceased WO2019082878A1 (fr)

Applications Claiming Priority (12)

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JP2017207836A JP2019077936A (ja) 2017-10-27 2017-10-27 電解用電極およびそれを備えた電気機器
JP2017-207836 2017-10-27
JP2017243399A JP2019108596A (ja) 2017-12-20 2017-12-20 電解用電極、オゾン発生装置およびそれを備えた電気機器
JP2017-243399 2017-12-20
JP2018132816A JP2020012124A (ja) 2018-07-13 2018-07-13 電解用電極およびそれを備えた電気機器
JP2018132814A JP2020012122A (ja) 2018-07-13 2018-07-13 電解用電極およびそれを備えた電気機器
JP2018132815A JP2020012123A (ja) 2018-07-13 2018-07-13 電解用電極およびそれを備えた電気機器
JP2018-132815 2018-07-13
JP2018-132812 2018-07-13
JP2018-132816 2018-07-13
JP2018132812A JP2020012121A (ja) 2018-07-13 2018-07-13 電解用電極およびそれを備えた電気機器
JP2018-132814 2018-07-13

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0417689A (ja) * 1990-05-11 1992-01-22 Permelec Electrode Ltd 水電解用電極及びその製造方法
JPH0841673A (ja) * 1994-08-02 1996-02-13 Mitsubishi Materials Corp 電気泳動法の電極
JP2006097122A (ja) * 2004-08-31 2006-04-13 Sanyo Electric Co Ltd 電解用電極及び電解用電極の製造方法
JP2007046129A (ja) * 2005-08-11 2007-02-22 Sanyo Electric Co Ltd 電解用電極及び電解用電極の製造方法
WO2012115180A1 (fr) * 2011-02-25 2012-08-30 クロリンエンジニアズ株式会社 Catalyseur d'anode et son procédé de fabrication
JP2015120962A (ja) * 2013-12-24 2015-07-02 三菱マテリアル株式会社 多孔質体及び水酸化ナトリウムの製造装置
JP2017160524A (ja) * 2016-03-11 2017-09-14 富士通株式会社 光化学電極、及びその製造方法
JP2017172001A (ja) * 2016-03-24 2017-09-28 石福金属興業株式会社 オゾン生成用電極及びその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0417689A (ja) * 1990-05-11 1992-01-22 Permelec Electrode Ltd 水電解用電極及びその製造方法
JPH0841673A (ja) * 1994-08-02 1996-02-13 Mitsubishi Materials Corp 電気泳動法の電極
JP2006097122A (ja) * 2004-08-31 2006-04-13 Sanyo Electric Co Ltd 電解用電極及び電解用電極の製造方法
JP2007046129A (ja) * 2005-08-11 2007-02-22 Sanyo Electric Co Ltd 電解用電極及び電解用電極の製造方法
WO2012115180A1 (fr) * 2011-02-25 2012-08-30 クロリンエンジニアズ株式会社 Catalyseur d'anode et son procédé de fabrication
JP2015120962A (ja) * 2013-12-24 2015-07-02 三菱マテリアル株式会社 多孔質体及び水酸化ナトリウムの製造装置
JP2017160524A (ja) * 2016-03-11 2017-09-14 富士通株式会社 光化学電極、及びその製造方法
JP2017172001A (ja) * 2016-03-24 2017-09-28 石福金属興業株式会社 オゾン生成用電極及びその製造方法

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