US20160186335A1 - Electrode unit, electrolytic cell comprising electrode unit, electrolytic device and method of manufacturing electrode of electrode unit - Google Patents

Electrode unit, electrolytic cell comprising electrode unit, electrolytic device and method of manufacturing electrode of electrode unit Download PDF

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US20160186335A1
US20160186335A1 US15/065,170 US201615065170A US2016186335A1 US 20160186335 A1 US20160186335 A1 US 20160186335A1 US 201615065170 A US201615065170 A US 201615065170A US 2016186335 A1 US2016186335 A1 US 2016186335A1
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Prior art keywords
electrode
holes
electrode unit
porous membrane
electrolytic
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US15/065,170
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Inventor
Katsuyuki Naito
Norihiro Yoshinaga
Wu Mei
Norihiro Tomimatsu
Ryosuke YAGI
Masahiro Yokota
Hideo Oota
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Toshiba Corp
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Toshiba Corp
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Assigned to KABUSHIKI KAISHA TOSHIBA reassignment KABUSHIKI KAISHA TOSHIBA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAGI, RYOSUKE, OOTA, HIDEO, YOKOTA, MASAHIRO, MEI, WU, NAITO, KATSUYUKI, TOMIMATSU, NORIHIRO, YOSHINAGA, NORIHIRO
Publication of US20160186335A1 publication Critical patent/US20160186335A1/en
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    • C25B9/08—
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25B11/0405—
    • C25B11/0415—
    • C25B11/0452—
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms

Definitions

  • Embodiments described herein relate generally to an electrode unit, an electrolytic cell comprising an electrode unit, an electrolytic device and a method of manufacturing an electrode for an electrode unit.
  • an electrolytic device for electrolyzing water and producing an electrolyzed aqueous solution which has various functions, such as an ionized alkaline solution, an ozone solution or aqueous hypochlorous acid has been provided.
  • This electrolytic device comprises an electrolytic cell, and an electrode unit provided in the electrolytic cell.
  • an electrolytic device comprising a three-chamber electrolytic cell.
  • the electrolytic cell is divided into three chambers, specifically, an intermediate chamber and anode and cathode chambers located on both sides of the intermediate chamber, by cation- and anion-exchange membranes included in an electrode unit.
  • the electrode unit comprises an anode and a cathode.
  • the anode and the cathode of the electrode unit are provided in the anode and cathode chambers, respectively.
  • an electrode having a porous configuration is used as the electrodes. A large number of through-holes are formed on the matrix made of a metal plate by applying expanding, etching or punching.
  • a salt water is supplied to the intermediate chamber, and water is supplied to the anode and cathode chambers.
  • the salt water in the intermediate chamber is electrolyzed by the cathode and the anode.
  • aqueous hypochlorous acid is produced from the gaseous chlorine produced by the anode.
  • Aqueous sodium hydroxide is produced in the cathode chamber.
  • the produced aqueous hypochlorous acid is used as a disinfectant.
  • the aqueous sodium hydroxide is used as a cleaning solution.
  • the anion-exchange membrane is degraded easily by chlorine or hypochlorous acid.
  • an electrode having a porous configuration adheres tightly to an ion-exchange membrane (electrolyte membrane), stress is easily concentrated on the edge portion of the pores of the electrode.
  • Nonwoven fabric having overlaps or slits is inserted between an electrode having a porous configuration and an electrolyte membrane to reduce the degradation of the electrode by chlorine.
  • An electrode unit in which a porous inorganic oxide membrane is formed in a flat valve electrode by sol-gel is known.
  • the electrolytic device having the above structure cannot avoid degradation of the electrode unit when operated for a very long time.
  • Embodiments described herein aim to provide an electrode unit, an electrolytic device and a method of manufacturing an electrode for an electrode unit, enabling the electrolytic performance to be maintained for a long time and allowing long-life operation.
  • FIG. 1 is a cross-sectional view showing an electrolytic device according to a first embodiment.
  • FIG. 2 is an exploded perspective view showing an electrode unit of the electrolytic device according to the first embodiment.
  • FIG. 3A is a cross-sectional view in which an electrode and a porous membrane of the electrode unit are enlarged.
  • FIG. 3B is a cross-sectional view in which the electrode and the porous membrane of the electrode unit are enlarged.
  • FIG. 3C is a cross-sectional view schematically showing the porous membrane formed by a multilayer film.
  • FIG. 3D is a cross-sectional view schematically showing the porous membrane formed by an inorganic oxide film having irregular pores in a plane or in a three-dimensional manner.
  • FIG. 4 is a cross-sectional view showing the electrode unit according to a first modification example.
  • FIG. 5 is a cross-sectional view showing the electrode and the porous membrane of the electrode unit according to a second modification example.
  • FIG. 6 is a perspective view showing an electrolytic device according to a second embodiment.
  • FIG. 7 is an exploded perspective view showing an electrode unit of the electrolytic device according to the second embodiment.
  • FIG. 8 is a cross-sectional view showing the electrode unit according to the second embodiment.
  • FIG. 9 is a cross-sectional view showing a process for manufacturing an electrode for the electrode unit according to the second embodiment.
  • FIG. 10 is a cross-sectional view showing a process for manufacturing the electrode and a porous membrane.
  • FIG. 11 is a cross-sectional view showing the electrode unit according to a third modification example.
  • FIG. 12 is a cross-sectional view of an electrolytic device according to a third embodiment.
  • FIG. 13 is a cross-sectional view of an electrolytic device according to a fourth embodiment.
  • FIG. 14 is a cross-sectional view showing an electrode unit according to a fourth modification example.
  • an electrolytic device comprises an electrode unit.
  • the electrode unit comprises: a first electrode comprising a first surface, a second surface located on a side opposite to the first surface, and a plurality of through-holes opening on the first surface and the second surface; a second electrode opposed to the first surface of the first electrode; and a porous membrane containing inorganic oxide, provided on the first surface of the first electrode to cover the first surface and the through-holes.
  • FIG. 1 schematically shows an electrolytic device according to a first embodiment.
  • An electrolytic device 10 comprises, for example, a two-chamber electrolytic cell 11 comprising an electrode unit 12 .
  • the electrolytic cell 11 is formed in the shape of a flat and rectangular box.
  • the electrolytic cell 11 is divided into two chambers, specifically, an anode chamber 16 and a cathode chamber 18 , by a diving wall 14 and the electrode unit 12 .
  • the electrode unit 12 comprises a first electrode (anode) 20 located in the anode chamber 16 , a second electrode (a counterelectrode, a cathode) 22 located in the cathode chamber 18 , and a porous membrane 24 provided between the first and second electrodes.
  • the electrolytic device 10 comprises a power supply 30 which applies voltage to the first and second electrodes 20 and 22 of the electrode unit 12 , ammeter 32 , a voltmeter 34 and a control device 36 which controls these elements.
  • a flow channel for liquid may be provided in the anode chamber 16 and the cathode chamber 18 .
  • a pipe or a pump for supplying liquid from outside or discharging liquid may be connected to the anode chamber 16 and the cathode chamber 18 .
  • a porous spacer may be provided between the electrode unit 12 and the anode chamber 16 or the cathode chamber 18 .
  • FIG. 2 is an exploded perspective view of the electrode unit.
  • the first electrode 20 has a porous configuration in which a large number of through-holes 13 are formed on a matrix 21 made of, for example, a rectangular metal plate.
  • the plate-like matrix 21 comprises a first surface 21 a, and a second surface 21 b facing and substantially parallel to the first surface 21 a.
  • the interval between the first surface 21 a and the second surface 21 b, in other words, the thickness of the plate, is defined as T 1 .
  • the first surface 21 a faces the porous membrane 24 .
  • the second surface 21 b faces the anode chamber 16 .
  • a large number of through-holes 13 are formed on the whole surface of the first electrode 20 .
  • the through-holes 13 open on the first surface 21 a and the second surface 21 b.
  • each through-hole 13 is formed by a tapered wall surface or a curved wall surface such that the opening dimension on the first surface 21 a side is greater than that on the second surface 21 b side.
  • Each through-hole 13 may take a variety of forms such as a square, a rectangle, a rhomboid, a circle or an ellipse. The vertexes of a square, a rectangle or a rhomboid may be rounded.
  • the through-holes 13 need not be aligned regularly and may be arranged randomly.
  • valve metal such as titanium, chromium, aluminum or an alloy thereof, or conductive metal may be used. Of these materials, titanium is preferable.
  • An electrocatalyst (catalytic layer) is preferably formed on the first and second surfaces 21 a and 21 b of the first electrode 20 depending on the electrolytic reaction.
  • a noble metal catalyst such as platinum or an oxide catalyst such as iridium oxide is preferably used.
  • the amount of electrocatalyst per unit area on one surface of the first electrode may differ from that on the other surface of the first electrode. In this manner, for example, a side reaction may be prevented.
  • the surface roughness of the matrix 21 is preferably 0.01 to 3 ⁇ m.
  • the surface roughness of the matrix 21 is more preferably 0.02 to 2 ⁇ m, and is further preferably 0.03 to 1 ⁇ m.
  • the second electrode (counterelectrode) 22 is structured in the same manner as the first electrode 20 .
  • the second electrode 22 has a porous configuration in which a large number of through-holes 15 are formed on a matrix 23 made of, for example, a rectangular metal plate.
  • the matrix 23 comprises a first surface 23 a, and a second surface 23 b facing and substantially parallel to the first surface 23 a.
  • the first surface 23 a faces the porous membrane 24 .
  • the second surface 23 b faces the cathode chamber 18 .
  • the continuous porous membrane 24 is formed on the first surface 21 a of the first electrode 20 and covers the whole first surface 21 a and the through holes 13 .
  • the porous membrane 24 is formed in a rectangular shape so as to have dimensions substantially equal to those of the first electrode 20 .
  • the porous membrane 24 is interposed between the first surface 21 a of the first electrode 20 and the first surface 23 a of the second electrode 22 .
  • the second electrode 22 may not come into direct contact with the porous membrane 24 .
  • another structure may be provided between the second electrode 22 and the porous membrane 24 .
  • the porous membrane 24 a uniform inorganic oxide porous membrane containing an inorganic oxide which is chemically stable is used.
  • Various materials may be used for the inorganic oxide.
  • titanium oxide, silicon oxide, aluminum oxide, niobium oxide, zirconium oxide, tantalum oxide, nickel oxide, tungsten oxide, zircon or zeolite may be used.
  • titanium oxide, zirconium oxide, silicon oxide and aluminum oxide are preferably used.
  • Hydroxide, alkoxide, oxyhalide or hydrate may be contained in the inorganic oxide.
  • titanium oxide, aluminum oxide, zirconium oxide and zircon are preferable as the inorganic oxide for the porous membrane 24 , since these materials easily have a positive zeta potential in an acidic region and therefore exhibit an anion-exchange function.
  • titanium oxide, aluminum oxide, zirconium oxide, silicon oxide, tungsten oxide, zircon and zeolite are preferable as the inorganic oxide for the porous membrane 24 , since these materials easily have a negative zeta potential in an alkaline region and therefore exhibit a cation-exchange function.
  • the porous membrane 24 containing an inorganic oxide may be formed to have irregular pores in a plane and in a three-dimensional manner through application of nanoparticles or sol-gel.
  • the porous membrane 24 is resistant to bending, etc.
  • the porous membrane 24 may contain polymers in addition to the inorganic oxide. Polymers add flexibility to the membrane.
  • a halogen atom may be preferably substituted on a main chain which is chemically stable.
  • polyvinylidene chloride, polyvinylidene fluoride and Teflon (registered trademark) are preferable. Of these materials, Teflon is particularly preferable.
  • polyethylene and an engineering plastics such as polyimide or polyphenylenesulfide may be employed.
  • the pore dimension of the porous membrane 24 may be formed such that the opening dimension on the first electrode 20 side is different from that on the second electrode 22 side.
  • the opening dimension of each pore on the second electrode 22 side is made greater than that on the first electrode 20 side, ion transfer can be further facilitated, and moreover, the concentration of stress applied by the through-hole 13 of the first electrode 20 can be reduced.
  • the structure in which the opening dimension on the second electrode 22 side is great facilitates ion transfer caused by diffusion.
  • the first electrode 20 is used for the anode, a positive potential is applied. Therefore, even when the opening dimension on the first electrode 20 side is less, anions are easily drawn to the first electrode 20 . If the pore dimension on the first electrode 20 side is great, the produced chlorine or hypochlorous acid is easily diffused to the porous membrane 24 side.
  • the pore dimension on the surface of the porous membrane 24 can be measured by a high-resolution scanning electron microscope (SEM).
  • the pores inside the porous membrane can be measured by cross-sectional SEM observation.
  • the porous membrane 24 comprises a first area 24 a which covers the portion of the first surface 21 a of the first electrode 20 , and a second area 24 b which covers the opening of the through-hole 13 .
  • the electrode unit 12 is easily degraded.
  • the pores on the surface of the first area 24 a may be eliminated, in other words, no pore may be formed.
  • the dimension of each pore on the surface of the first area 24 a may be made less than that on the second area 24 b.
  • This structure inhibits an electrolytic reaction in an area which is in contact with the first area 24 a.
  • the degradation of the electrode unit 12 can be prevented.
  • a thin imperforate membrane 29 a or a porous membrane 29 b having a less pore-dimension may be formed on the first surface 21 a of the first electrode 20 by screen printing, etc. It should be noted that, in this case, the reactive area of the first electrode 20 is small. Therefore, it is necessary to cause a sufficient reaction in an electrode area where gas is easily discharged.
  • a side reaction can be reduced by covering the surface (second surface 21 b ) opposite to the porous membrane 24 of the first electrode 20 with an electrical insulating membrane.
  • a multilayer film including a plurality of porous membranes 28 a and 28 b having different pore-dimensions may be used for the porous membrane 24 .
  • the pore dimension of the porous membrane 28 b located on the second electrode 22 side may be made greater than that of the porous membrane 28 a located on the first electrode 20 side.
  • the first electrode 20 , the porous membrane 24 and the second electrode 22 having the above structures are brought into contact with each other by pressing them in a state where the porous membrane 24 is interposed between the first electrode 20 and the second electrode 22 . In this manner, the electrode unit 12 is obtained.
  • the electrode unit 12 is provided in the electrolytic cell 11 and is attached to the dividing wall 14 .
  • the electrolytic cell 11 is divided into the anode chamber 16 and the cathode chamber 18 by the dividing wall 14 and the electrode unit 12 .
  • the electrode unit 12 is provided in the electrolytic cell 11 such that the alignment direction of the structural members is, for example, the horizontal direction.
  • the first electrode 20 of the electrode unit 12 faces the anode chamber 16 .
  • the second electrode 22 faces the cathode chamber 18 .
  • the two poles of the power supply 30 are electrically connected to the first electrode 20 and the second electrode 22 .
  • the power supply 30 applies voltage to the first and second electrodes 20 and 22 under control of the control device 36 .
  • the voltmeter 34 is electrically connected to the first electrode 20 and the second electrode 22 and detects the voltage applied to the electrode unit 12 .
  • the detected data is supplied to the control device 36 .
  • the ammeter 32 is connected to the voltage application circuit of the electrode unit 12 and detects the current flowing in the electrode unit 12 .
  • the detected data is supplied to the control device 36 .
  • the control device 36 controls the application of voltage or load for the electrode unit 12 by the power supply 30 based on the detected data in accordance with the program stored in the memory.
  • the electrolytic device 10 applies voltage or load between the first electrode 20 and the second electrode 22 in a state where the substance for reaction is supplied to the anode chamber 16 and the cathode chamber 18 . In this manner, the electrochemical reaction for electrolysis is advanced.
  • the electrolytic device 10 of the present embodiment preferably electrolyzes an electrolyte containing chloride ions.
  • the porous membrane 24 containing an inorganic oxide which is chemically stable is formed to cover the first surface of the first electrode 20 and the through-holes.
  • the distance between the first electrode 20 and the second electrode 22 can be maintained as constant as possible.
  • the flow of liquid can be uniform.
  • the electrolytic reaction can occur uniformly at the interfaces between electrodes. Because of the uniform electrolytic reaction, the catalysts and the electrode metals deteriorate uniformly.
  • an inorganic oxide which is chemically stable is used. Thus, the life duration of the electrode unit can be significantly prolonged. Since the electrolytic reaction occurs uniformly, the reaction efficiency of the electrolytic device can be improved, and further, the deterioration of the electrodes can be inhibited.
  • the through-holes are formed with a tapered or curved surface which enlarges towards the first surface side.
  • the contact angle between the opening of each through-hole and the porous membrane 24 is made as an obtuse angle, thereby reducing the concentration of stress on the porous membrane 24 .
  • the second electrode 22 has a porous configuration with a large number of through-holes.
  • the second electrode 22 is not limited to this configuration.
  • a plate-like electrode without a through-hole may be employed.
  • FIG. 4 shows the electrode unit according to a first modification example.
  • the electrode unit 12 may comprise a diaphragm 26 which transmits at least one of ions and liquid.
  • the diaphragm 26 is formed in a rectangular shape so as to have dimensions substantially equal to those of the first electrode 20 , and is interposed between the porous membrane 24 and the first surface 23 a of the second electrode 22 .
  • the diaphragm 26 adheres tightly to the porous membrane 24 , and further adheres tightly to the whole first surface 23 a of the second electrode 22 .
  • electrolyte membranes and porous membranes having nano-pores may be used.
  • a usable example of the electrolyte membranes is a polyelectrolyte membrane such as a cation-exchange solid polyelectrolyte membrane, more specifically, a cation-exchange membrane, or an anion-exchange membrane, or a hydrocarbon-series membrane.
  • Usable examples of the cation-exchange membrane are Nafion (registered trademark of E. I.
  • a usable example of the anion-exchange membrane is A201 manufactured by Tokuyama Corporation.
  • the porous membranes having nano-pores are porous ceramic such as porous glass, porous alumina, porous titania and porous zeolite, and porous polymers such as porous polyethylen, porous propylene and porous teflon.
  • FIG. 5 shows a part of the electrode unit according to a second modification example.
  • the porous membrane 24 of the electrode unit 12 may be present on the wall surface defining the through-holes 15 of the first electrode 20 (in other words, on the sidewall surface of the through-holes).
  • the porous membrane 24 may be formed so as to cover the first surface 21 a of the first electrode 20 and a part of or the entire part of the wall surface of at least one through-hole 15 .
  • the porous membrane 24 is formed in this manner, the bond between the first electrode 20 and the porous membrane 24 is strengthened.
  • the porous membrane 24 is difficult to remove even with a thermal cycle, etc.
  • FIG. 6 is a cross-sectional view schematically showing an electrolytic device according to a second embodiment.
  • FIG. 7 is an exploded perspective view of an electrode unit.
  • FIG. 8 is a cross-sectional view of the electrode unit.
  • a first electrode 20 of an electrode unit 12 has a porous configuration, and through-holes are formed such that the opening dimension on the first surface 21 a side differs from that on the second surface 21 b side.
  • the first electrode 20 has a porous configuration in which a large number of through-holes are formed on a matrix 21 made of, for example, a rectangular metal plate.
  • the matrix 21 comprises the first surface 21 a, and the second surface 21 b facing and substantially parallel to the first surface 21 a.
  • the interval between the first surface 21 a and the second surface 21 b, in other words, the thickness of the plate, is defined as T 1 .
  • the first surface 21 a faces a porous membrane 24 .
  • the second surface 21 b faces an anode chamber 16 .
  • a plurality of first holes 40 are formed on the first surface 21 a of the matrix 21 and open on the first surface 21 a. Moreover, a plurality of second holes 42 are formed on the second surface 21 b and open on the second surface 21 b. Each first hole 40 communicates with the second hole 42 facing the first hole 40 . Thus, a through-hole penetrating the matrix 21 is formed.
  • the first holes 40 made on the porous membrane 24 side have an opening dimension (R 1 ) which is less than the opening dimension (R 2 ) of the second holes 42 . Further, the first holes 40 are greater in number than the second holes 42 .
  • the opening area of the second holes 42 is greater than that of the first holes 40 .
  • the depth of the first holes 40 is T 2
  • the depth of the second holes 42 is T 3 .
  • the second holes 42 are formed in, for example, a rectangular shape and are arranged in a matrix on the second surface 21 b.
  • the circumferential wall which defines each second hole 42 may be formed to have a tapered surface 42 a or a curved surface so that the dimension enlarges from the bottom of the hole to the opening, in other words, to the second surface side.
  • the interval between adjacent second holes 42 that is, the width of a linear portion of the electrode, is set to W 2 .
  • the second holes 42 are not limited to a rectangular shape, and may take various other forms. Moreover, the second holes 42 need not be aligned regularly and may be arranged randomly.
  • the first holes 40 are formed in, for example, a rectangular shape and are arranged in a matrix on the first surface 21 a.
  • the circumferential wall which defines each first hole 40 may be formed to have a tapered or curved surface so that the dimension enlarges from the bottom of the hole to the opening, in other words, to the first surface 21 a.
  • a plurality of, for example, nine first holes 40 are provided to face one second hole 42 .
  • the nine first holes 40 communicate with the second hole 42 and form the through-holes penetrating the matrix 21 together with the second hole 42 .
  • Interval W 1 between adjacent first holes 40 is set so as to be less than interval W 2 between second holes 42 .
  • the number density of the first holes 40 on the first surface 21 a is sufficiently greater than that of the second holes 42 on the second surface 21 b.
  • Other elements such as the matrix 21 and the catalytic layer of the first electrode 20 have the same structures as the first embodiment.
  • the opening dimension of the first holes 40 is preferably less in order to make the pressure uniform. However, the first holes 40 need to be large to the extent that substance diffusion can be prevented.
  • the dimension of each side of the opening is preferably 0.1 to 2 mm, and is more preferably 0.3 to 1 mm.
  • the opening may take a variety of forms such as a square, a rectangle, a rhomboid, a circle and an ellipse, while the opening area is preferably 0.01 to 4 mm 2 in the same manner as the above square.
  • the opening area is more preferably 0.1 to 1.5 mm 2 .
  • the opening area is further preferably 0.2 to 1 mm 2 .
  • the ratio of the opening area to the electrode area including the opening is preferably 0.05 to 0.5, and is more preferably 0.1 to 0.4, and is further preferably 0.15 to 0.3. If the opening ratio is excessively less, outgassing is difficult. If the opening ratio is excessively great, electrode reaction is inhibited.
  • first holes 40 are not limited to a rectangular shape, and may take other forms. Moreover, the first holes 40 need not be aligned regularly and may be arranged randomly. Furthermore, all the first holes 40 may not necessarily communicate with the second holes 42 . Some first holes 40 may not communicate with second holes 42 . Thus, some first holes 40 may not communicate with the anode chamber 16 .
  • the first holes 40 may be formed in a rectangular shape extending from the vicinity of one end of the electrode to the vicinity of the other end of the electrode. In these first holes 40 , a plurality of opening portions communicating with the second holes 42 may be arranged at intervals. Only a part of each first hole 40 may communicate with the second holes. The first holes which do not communicate with the second holes can increase the electrode area.
  • 85% or more of all of the first holes 40 have an opening area of 0.01 to 4 mm 2 . More preferably, 90% or more, and further preferably, 95% ore more of all of the first holes 40 have an opening area of 0.01 to 4 mm 2 .
  • each second hole 42 may be employed for each second hole 42 , such as a square, a rectangle, a rhomboid, a circle or an ellipse.
  • the opening dimension of each second hole 42 is preferably great in order to facilitate outgassing. However, if the opening dimension is great, the electrical resistance is increased. Therefore, the second holes 42 cannot be significantly enlarged.
  • the dimension of each side of the opening is preferably 1 to 40 mm, and is more preferably 2 to 20 mm.
  • the opening may take a variety of forms such as a square, a rectangle, a rhomboid, a circle and an ellipse, while the opening area is preferably 1 to 1600 mm 2 in the same manner as the above square.
  • the opening area of the second holes 42 is more preferably 4 to 900 mm 2 , and is further preferably 9 to 400 mm 2 .
  • the opening may be shaped in a rectangle or an ellipse which is long in one direction so as to connect an end and the other end of the electrode.
  • the porous membrane 24 containing an inorganic oxide is formed on the first surface 21 a of the first electrode 20 so as to cover the whole first surface 21 a and the first holes 40 .
  • the porous membrane 24 employs the same porous membrane as the first embodiment described above.
  • a second electrode (counterelectrode) 22 is structured in the same manner as the first electrode 20 .
  • the second electrode 22 has a porous configuration in which a large number of through-holes are formed on a matrix 23 made of, for example, a rectangular metal plate.
  • the matrix 23 comprises a first surface 23 a, and a second surface 23 b facing and substantially parallel to the first surface 23 a.
  • the first surface 23 a faces a diaphragm 26 .
  • the second surface 23 b faces a cathode chamber 18 .
  • a plurality of first holes 44 are formed on the first surface 23 a of the matrix 23 and open on the first surface 23 a. Further, a plurality of second holes 46 are formed on the second surface 23 b and open on the second surface 23 b. The opening dimension of the first holes 44 made on the diaphragm 26 side is less than that of the second holes 46 . Further, the first holes 44 are greater in number than the second holes 46 . The depth of the first holes 44 is less than that of the second holes 46 .
  • a plurality of, for example, nine first holes 44 are provided to face one second hole 46 .
  • the nine first holes 44 communicate with the second hole 46 and form the through-holes penetrating the matrix 23 together with the second hole 46 .
  • the interval between adjacent first holes 44 is set so as to be less than the interval between the second holes 46 .
  • an electrolytic device 10 preferably electrolyzes an electrolyte containing chloride ions.
  • the first electrode 20 can be manufactured by, for example, an etching method using a mask.
  • the flat matrix 21 is prepared.
  • Resist films 50 a and 50 b are applied to the first and second surfaces 21 a and 21 b of the matrix 21 .
  • the resist films 50 a and 50 b are exposed, using an optical mask (not shown).
  • masks 52 a and 52 b for etching are prepared.
  • wet etching is applied to the first and second surfaces 21 a and 21 b of the matrix 21 via the masks 52 a and 52 b with solution. In this manner, a plurality of first holes 40 and a plurality of second holes 42 are formed. Subsequently, the first electrode 20 is obtained by removing the masks 52 a and 52 b.
  • the shape of the tapered or curved surface of the first and second holes 40 and 42 can be controlled based on the material of the matrix 21 and etching conditions.
  • the depth of the first holes 40 is T 2
  • the depth of the second holes 42 is T 3 .
  • the first and second holes are formed such that T 2 ⁇ T 3 .
  • both surfaces of the matrix 21 may be etched at the same time, or may be etched separately.
  • the type of etching is not limited to wet etching. For example, dry etching may be employed.
  • the first electrode 20 may be manufactured by, for example, an expanding method, a punching method or a processing method using a laser or precision cutting.
  • the porous membrane 24 is formed on the first surface 21 a of the first electrode 20 .
  • a preprocessing film 24 c is manufactured by applying a solution containing inorganic oxide particles and/or inorganic oxide precursors to the first surface 21 a.
  • the preprocessing film 24 c is subjected to sintering to manufacture the porous membrane 24 having a large number of pores.
  • the solution containing inorganic oxide precursors is prepared by dissolving metal alkoxide in alcohol, adding a solvent having a high boiling point such as glycerin to achieve a porous configuration, or blending an organic substance such as fatty acid which is easily oxidized to be carbon dioxide at the time of sintering.
  • a solvent having a high boiling point such as glycerin
  • an organic substance such as fatty acid which is easily oxidized to be carbon dioxide at the time of sintering.
  • the viscosity of the solution is preferably increased by adding a small amount of water and partially hydrolyzing metal alkoxide.
  • a dispersion liquid containing inorganic oxide particles may be applied. Alternatively, they may be combined with each other.
  • the sintering temperature is preferably 150 to 600° C.
  • the first and second holes 40 and 42 of the first electrode 20 may be covered by an organic substance 55 before preparing the preprocessing film.
  • the preprocessing film 24 c may be formed on the first surface 21 a of the first electrode 20 as shown in FIG. 10( b ) .
  • the organic substance 55 is removed, and the preprocessing film 24 c is burned.
  • the porous membrane 24 is formed.
  • the preprocessing film 24 c may be burned while the organic substance 55 is left.
  • the through-holes of the electrode can be covered certainly when the solution containing inorganic oxide particles and/or inorganic oxide precursors is applied. Further, the film thickness of the inorganic oxide can be made constant such that the film can be flat.
  • the other structures of the electrode unit 12 and the electrolytic device 10 are the same as those of the first embodiment described above. According to the second embodiment, in a manner similar to that of the first embodiment, it is possible to obtain a long-life electrode unit which can maintain the electrolytic performance for a long time, an electrolytic device comprising the electrode unit, and a method of manufacturing an electrode.
  • the dimension of the first holes 40 formed on the first surface 21 a on the porous membrane 24 side is made less than that of the second holes 42 .
  • the number density of the first holes 40 is made great. This structure allows the reduction in the concentration of stress applied from the first electrode 20 side to the porous membrane 24 .
  • the porous membrane 24 is brought into contact with the whole first surface 21 a of the first electrode 20 .
  • the holes of the first electrode 20 are covered by the porous membrane 24 .
  • the distance between the first electrode 20 and the diaphragm 26 can be easily maintained equally over the whole surface.
  • FIG. 11 shows the electrode unit according to a third modification example.
  • the electrode unit 12 may comprise the diaphragm 26 which transmits at least one of ions and liquid.
  • the diaphragm 26 is formed in a rectangular shape so as to have dimensions substantially equal to those of the first electrode 20 , and is interposed between the porous membrane 24 and the first surface 23 a of the second electrode 22 .
  • the diaphragm 26 adheres tightly to the porous membrane 24 , and further adheres tightly to the whole first surface 23 a of the second electrode 22 .
  • a diaphragm similar to that of the first modification example may be used.
  • FIG. 12 is a cross-sectional view showing an electrolytic device according to a third embodiment.
  • an electrolytic cell 11 of an electrolytic device 10 is structured as a one-chamber electrolytic cell comprising only one electrolytic chamber 17 .
  • An electrode unit 12 is provided in the electrolytic chamber 17 .
  • a pipe or a pump for supplying an electrolyte from outside or discharging an electrolyte may be connected to the electrolytic chamber 17 .
  • a second electrode (counterelectrode) 22 of the electrode unit 12 preferably has a porous configuration in a manner similar to that of the first electrode 20 .
  • the porous configuration enables the electrode area to be increased.
  • FIG. 13 is a cross-sectional view showing an electrolytic device according to a fourth embodiment.
  • an electrolytic device 10 comprises a three-chamber electrolytic cell 11 and an electrode unit 12 .
  • the electrolytic cell 11 is formed in the shape of a flat and rectangular box.
  • the electrolytic cell 11 is divided into three chambers, specifically, an anode chamber 16 , a cathode chamber 18 and an intermediate chamber 19 formed between the electrodes, by a dividing wall 14 and the electrode unit 12 .
  • the electrode unit 12 comprises a first electrode (anode) 20 located in the anode chamber 16 , a second electrode (a counterelectrode, a cathode) 22 located in the cathode chamber 18 , a porous membrane 24 formed on a first surface 21 a of the first electrode 20 , and a porous membrane 27 formed on a first surface 23 a of the second electrode 22 .
  • the first electrode 20 and the second electrode 22 face each other across an intervening space such that they are parallel to each other.
  • the intermediate chamber (electrolyte chamber) 19 which stores an electrolyte is formed between the porous membranes 24 and 27 of the first and second electrodes 20 and 22 .
  • a holder 25 which holds an electrolyte may be provided in the intermediate chamber 19 .
  • the first and second electrodes 20 and 22 may be connected to each other by a plurality of insulating bridges 60 .
  • the electrolytic device 10 comprises a power supply 30 which applies voltage to the first and second electrodes 20 and 22 of the electrode unit 12 , an ammeter 32 , a voltmeter 34 and a control device 36 which controls these elements.
  • a flow channel for liquid may be provided in the anode chamber 16 and the cathode chamber 18 .
  • a pipe or a pump for supplying liquid from outside or discharging liquid may be connected to the anode chamber 16 and the cathode chamber 18 .
  • a porous spacer may be provided between the electrode unit 12 and the anode chamber 16 or the cathode chamber 18 depending on the case.
  • the first and second electrodes 20 and 22 are formed to have a porous configuration similar to that of the second embodiment.
  • the continuous porous membrane 24 is formed in, for example, a rectangular shape so as to have dimensions substantially equal to those of the first electrode 20 , and faces the whole first surface 21 a.
  • the continuous porous membrane 27 is formed in, for example, a rectangular shape so as to have dimensions substantially equal to those of the second electrode 22 , and faces the whole first surface 23 a.
  • porous membranes 24 and 27 porous membranes similar to those of the first embodiment may be used.
  • Various materials may be used for the porous membranes 24 and 27 .
  • the porous membranes 24 and 27 may also function as diaphragms as long as they are inorganic oxide films having irregular pores in a plane or in a three-dimensional manner.
  • the porous membranes 24 and 27 may be multilayer films of a plurality of porous membranes having different pore-dimensions.
  • FIG. 14 shows the electrode unit according to a fourth modification example.
  • the electrode unit 12 may comprise diaphragms 26 a and 26 b which transmit at least one of ions and liquid.
  • the diaphragm 26 a is formed in, for example, a rectangular shape so as to have dimensions substantially equal to those of the first electrode 20 , and faces the first surface 21 a of the first electrode 20 .
  • the porous membrane 24 is interposed between the first surface 21 a of the first electrode 20 and the diaphragm 26 a, and adheres tightly to the first electrode 20 and the diaphragm 26 a.
  • the diaphragm 26 b is formed in, for example, a rectangular shape so as to have dimensions substantially equal to those of the second electrode 22 , and faces the first surface 23 a of the second electrode 22 .
  • the porous membrane 27 is interposed between the first surface 23 a of the second electrode 22 and the diaphragm 26 b, and adheres tightly to the second electrode 22 and the diaphragm 26 b.
  • electrolyte membranes and porous membranes having nano-pores may be used.
  • a usable example of the electrolyte membranes is a polyelectrolyte membrane such as a cation-exchange solid polyelectrolyte membrane, more specifically, a cation-exchange membrane, or an anion-exchange membrane, or a hydrocarbon-series membrane.
  • Usable examples of the cation-exchange membrane are Nafion (registered trademark of E. I. du Pont de Nemours and Company) 112, 115 and 117, Flemion (registered trademark of Asahi Glass Co., Ltd.), Aciplex (registered trademark of Asahi Glass Co.,
  • a usable example of the anion-exchange membrane is A201 manufactured by Tokuyama Corporation.
  • Usable examples of the porous membranes having nano-pores are porous ceramic such as porous glass, porous alumina and porous titanium, and porous polymers such as porous polyethylene, porous propylene and porous teflon.
  • a flat titanium plate having a plate thickness (T 1 ) of 0.5 mm is employed for the electrode matrix 21 .
  • This titanium plate is etched as shown in FIG. 9 .
  • the electrode 20 shown in FIG. 6 and FIG. 7 is manufactured.
  • the thickness (T 2 ) of the area including the small first holes 40 (in other words, the depth of the first holes) is 0.15 mm.
  • the thickness (T 3 ) of the area including the large second holes 42 (in other words, the depth of the second holes) is 0.35 mm.
  • Each first hole 40 has a square shape.
  • the dimension (R 1 ) of each side is 0.57 mm.
  • Each second hole 42 has a square shape.
  • the dimension (R 2 ) of each side of the square which can be obtained by extrapolating the linear potion is 2 mm.
  • the width (W 1 ) of the linear portion formed between adjacent first holes 40 is 0.1 mm.
  • the width (W 2 ) of the broad linear portion formed between adjacent second holes 42 is 1.0 mm.
  • This etched electrode matrix 21 is processed in 10 wt % of an oxalic acid solution at 80° C. for an hour.
  • a solution adjusted by adding 1-butanol to iridium chloride (IrCl3.nH2O) so as to obtain 0.25M (Ir) is applied to the first surface 21 a of the electrode matrix 21 .
  • drying and burning are applied. In this case, drying is performed at 80° C. for 10 minutes, and burning is performed at 450° C. for 10 minutes.
  • the above application, drying and burning are repeated five times.
  • the electrode matrix made through this process is cut out such that the reactive electrode area can be 3 cm ⁇ 4 cm. In this manner, the first electrode (anode) 20 is manufactured.
  • Ethanol and diethanolamine are added to titanium (IV) tetraisopropoxide under ice bath. An aqueous solution of ethanol is added drop by drop while stirring it. Thus, sol is prepared.
  • the thin film is made porous by thermal processing. Polyethylene glycol (molecular weight: 5000) for increasing the viscosity of the sol is added to the sol cooled to a room temperature.
  • the first surface 21 a of the electrode 20 is coated with a brush.
  • the coated film is burned at 500° C. for 7 minutes. Coating and burning are repeated at three times. Subsequently, burning is performed at 500° C. for an hour.
  • the porous membrane 24 formed of titanium oxide is obtained.
  • the electrode instead of preparing iridium oxide, platinum is sputtered to obtain the second electrode (the counterelectrode, the cathode) 22 .
  • the porous membrane 27 formed by a titanium oxide film is prepared on the second electrode 22 .
  • the electrode unit 12 shown in FIG. 13 is manufactured, using the above first and second electrodes 20 and 22 .
  • As the holder 25 which holds the electrolyte porous polystyrene having a thickness of 5 mm is used.
  • the first and second electrodes, the porous membranes, the dividing wall and the porous polystyrene are laid to overlap each other and are secured by a silicone sealant and screws. In this manner, the electrode unit 12 is obtained.
  • the electrolyte device 10 shown in FIG. 13 is manufactured, using this electrode unit 12 .
  • the anode and cathode chambers 16 and 18 of the electrolytic cell 11 are each formed from a vinyl-chloride container in which a straight flow channel is formed.
  • the control device 36 , the power supply 30 , the voltmeter 34 and the ammeter 32 are provided.
  • a pipe and a pump for supplying water to the anode and cathode chambers 16 and 18 are connected to the electrolytic cell 11 .
  • a saturated salt water tank, a pipe and a pump for circulating a saturated salt water to the holder (porous polystyrene) 25 of the electrode unit 12 are connected to the electrode unit.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 4 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • a stable electrolytic treatment can be carried out.
  • the electrolytic device 10 is manufactured in the same manner as in Example 1 except that A201 of Tokuyama Corporation, which is an anion-exchange membrane, is employed as the diaphragm 26 a, and Nafion 117 is provided as the diaphragm 26 b between the porous membrane 24 or 27 and the holder 25 which holds an electrolyte.
  • A201 of Tokuyama Corporation which is an anion-exchange membrane
  • Nafion 117 is provided as the diaphragm 26 b between the porous membrane 24 or 27 and the holder 25 which holds an electrolyte.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 5.2 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • the concentration of sodium chloride contained in the aqueous hypochlorous acid is decreased in comparison with Example 1. Even after continuous operation for 1000 hours, no substantial rise in voltage or change in product concentration is observed. Thus, the electrolytic treatment is stable.
  • the electrolytic device 10 is manufactured in the same manner as in Example 1 except that tetraethoxysilane is employed instead of titanium (IV) tetraisopropoxide.
  • This electrolytic device is operated for electrolysis at a voltage of 4.3 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • a stable electrolytic treatment can be carried out.
  • the electrolytic device 10 is manufactured in the same manner as in Example 1 except that aluminum triisopropoxide is employed instead of titanium (IV) tetraisopropoxide.
  • This electrolytic device is operated for electrolysis at a voltage of 4.0 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • a stable electrolytic treatment can be carried out.
  • the electrolytic device 10 is manufactured in the same manner as in Example 1 except that zirconium (IV) tetraisopropoxide is employed instead of titanium (IV) tetraisopropoxide.
  • This electrolytic device is operated for electrolysis at a voltage of 4.2 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • the first and second electrodes are manufactured in the same manner as in Example 1.
  • the porous membrane 24 formed of titanium oxide is prepared on the first electrode 20 . They are laid to overlap each other, using a silicone sealant and screws. Thus, the electrode unit 12 is obtained.
  • the electrolytic device 10 shown in FIG. 12 is manufactured, using this electrode unit 12 .
  • the control device 36 , the power supply 30 , the voltmeter 34 and the ammeter 32 are provided.
  • a pipe and a pump for supplying a salt water to the electrolytic chamber 17 are provided.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 3.7 V and a current of 1.5 A.
  • a sodium hypochlorite solution is produced.
  • Even after continuous operation for 1000 hours no substantial rise in voltage or change in product concentration is observed.
  • a stable electrolytic treatment can be carried out.
  • the first and second electrodes 20 and 22 are manufactured in the same manner as in Example 1.
  • Spin coating is applied to the second surface 21 b of the first electrode 20 with an ethyl acetate solution of PMMA to fill the second holes 42 and 46 of the electrode with PMMA.
  • An aqueous dispersion containing titanium oxide nanoparticles having a grain size of 50 nm is applied to the first surface 21 a of the first electrode 20 by screen printing.
  • the PMMA is removed by ethyl acetate.
  • burning is performed at 450° C.
  • the electrode is put into water. Titanium tetrachloride is added drop by drop. After the electrode is left at room temperature for five hours, it is rinsed in water and burned at 450° C.
  • the porous membrane 24 formed of titanium oxide is obtained.
  • the electrode unit 12 shown in FIG. 13 is manufactured, using the above first and second electrodes 20 and 22 .
  • As the holder 25 which holds the electrolyte porous polystyrene having a thickness of 5 mm is used.
  • the first and second electrodes, the porous membranes, the diving wall and the porous polystyrene are laid to overlap each other and are secured by a silicone sealant and screws. In this manner, the electrode unit 12 is obtained.
  • the electrolytic device 10 shown in FIG. 13 is manufactured, using this electrode unit 12 .
  • the anode and cathode chambers 16 and 18 of the electrolytic cell 11 are each formed from a vinyl-chloride container in which a straight flow channel is formed.
  • the control device 36 , the power supply 30 , the voltmeter 34 and the ammeter 32 are provided.
  • a pipe and a pump for supplying tap water to the anode and cathode chambers 16 and 18 are connected to the electrolytic cell 11 .
  • a saturated salt water tank, a pipe and a pump for circulating a saturated salt water to the holder (porous polystyrene) 25 of the electrode unit 12 are connected to the electrode unit.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 4 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • a stable electrolytic treatment can be carried out.
  • the first and second electrodes are manufactured in the same manner as in Example 1.
  • An aqueous dispersion containing titanium oxide nanoparticles having a grain size of 50 nm is applied to fabric formed of polyvinylidene chloride fibers with a thickness of 200 ⁇ m by dip coating and arranged on the first surface of the first electrode. After burning is performed at 150° C., the electrode is put into water. Titanium tetrachloride is added drop by drop. After the electrode is left at room temperature for five hours, it is rinsed in water and burned at 150° C. Thus, the porous membrane 24 containing titanium oxide is obtained.
  • the electrode instead of preparing iridium oxide, platinum is sputtered to obtain the second electrode (cathode) 22 .
  • the porous membrane 27 containing a titanium oxide film is prepared on the second electrode 22 .
  • the electrode unit 12 shown in FIG. 14 is manufactured, using the above first and second electrodes.
  • A201 of Tokuyama Corporation which is an anion-exchange membrane, is employed as the diaphragm 26 a.
  • Nafion 117 is employed as the diaphragm 26 b.
  • As the holder 25 which holds the electrolyte porous polystyrene having a thickness of 5 mm is used. They are laid to overlap each other and are bonded together by a silicone sealant and screws. Thus, the electrode unit 12 is obtained.
  • the electrolytic device is manufactured, using this electrode unit 12 .
  • the anode and cathode chambers 16 and 18 of the electrolytic cell 11 are each formed from a vinyl-chloride container in which a straight flow channel is formed.
  • the control device 36 , the power supply 30 , the voltmeter 34 and the ammeter 32 are provided.
  • a pipe and a pump for supplying tap water to the anode and cathode chambers 16 and 18 are connected to the electrolytic cell 11 .
  • a saturated salt water tank, a pipe and a pump for circulating a saturated salt water to the holder (porous polystyrene) 25 of the electrode unit 12 are connected to the electrode unit.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 5.5 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • a stable electrolytic treatment can be carried out.
  • the first and second electrodes are manufactured in the same manner as in Example 1.
  • a hydrophilic Teflon-coated filter is put into water.
  • titanium tetrachloride is added drop by drop.
  • the electrode is left at 50° C. for two hours, it is rinsed in water and burned at 250° C.
  • the porous membrane 24 containing titanium oxide is obtained.
  • the electrode unit 12 shown in FIG. 14 is manufactured, using the above first and second electrodes.
  • A201 of Tokuyama Corporation which is an anion-exchange membrane, is employed as the diaphragm 26 a.
  • Nafion 117 is employed as the diaphragm 26 b.
  • As the holder 25 which holds the electrolyte porous polystyrene having a thickness of 5 mm is used. They are laid to overlap each other and are bonded together by a silicone sealant and screws. Thus, the electrode unit 12 is obtained.
  • the electrolytic device is manufactured, using this electrode unit 12 .
  • the anode and cathode chambers 16 and 18 of the electrolytic cell 11 are each formed from a vinyl-chloride container in which a straight flow channel is formed.
  • the control device 36 , the power supply 30 , the voltmeter 34 and the ammeter 32 are provided.
  • a pipe and a pump for supplying tap water to the anode and cathode chambers 16 and 18 are connected to the electrolytic cell 11 .
  • a saturated salt water tank, a pipe and a pump for circulating a saturated salt water to the holder (porous polystyrene) 25 of the electrode unit 12 are connected to the electrode unit.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 5.7 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the first electrode (anode) 20 side
  • aqueous sodium hydroxide is produced on the second electrode (cathode) 22 side.
  • a stable electrolytic treatment can be carried out.
  • a flat titanium plate having a plate thickness (T 1 ) of 0.5 mm is employed for the electrode matrix 21 .
  • This titanium plate is etched as shown in FIG. 9 .
  • an electrode is manufactured.
  • the thickness (T 2 ) of the area including the small first holes 40 (in other words, the depth of the first holes) is 0.15 mm.
  • the thickness (T 3 ) of the area including the large second holes 42 (in other words, the depth of the second holes) is 0.35 mm.
  • the first holes 40 have a rhomboid shape.
  • the dimension of the longer diagonal line is 0.69 mm.
  • the dimension of the shorter diagonal line is 0.4 mm.
  • the second holes 42 have a rhomboid shape.
  • the dimension of the longer diagonal line is 6.1 mm.
  • the dimension of the shorter diagonal line is 3.5 mm.
  • the width (W 1 ) of the linear portion formed between adjacent first holes 40 is 0.15 mm.
  • the width (W 2 ) of the broad linear portion formed between adjacent second holes 42 is 1 mm.
  • the other structures are the same as those of Example 1. On these conditions, the electrode unit 12 and the electrolytic device 10 are manufactured.
  • the electrolytic device 10 is operated for electrolysis at a voltage of 5.3 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the anode 20 side
  • aqueous sodium hydroxide is produced on the cathode 22 side. Even after continuous operation for 1000 hours, no substantial rise in voltage or change in product concentration is observed. Thus, a stable electrolytic treatment can be carried out.
  • An electrolytic device is manufactured in the same manner as in Example 1 except that a porous polystyrene membrane is employed instead of the continuous inorganic porous membrane.
  • This electrolytic device is operated for electrolysis at a voltage of 4 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the anode side, and aqueous sodium hydroxide is produced on the cathode side.
  • a significant rise in voltage and a decrease in product concentration are observed. Thus, it is found that this device lacks a long-term stability.
  • An electrode unit and an electrolytic device are manufactured in the same manner as in Example 7 without coating with PMMA.
  • the through-holes are not covered by an inorganic porous membrane.
  • This electrolytic device is operated for electrolysis at a voltage of 3.5 V and a current of 1.5 A.
  • Aqueous hypochlorous acid is produced on the anode side, and aqueous sodium hydroxide is produced on the cathode side.
  • a great amount of salt is contained in the aqueous hypochlorous acid.
  • the present invention is not limited to the embodiments described above but the constituent elements of the invention can be modified in various manners without departing from the spirit and scope of the invention.
  • Various aspects of the invention can also be extracted from any appropriate combination of a plurality of constituent elements disclosed in the embodiments. Some constituent elements may be deleted from all of the constituent elements disclosed in the embodiments. The constituent elements described in different embodiments may be combined arbitrarily.
  • first electrode and the second electrode are not limited to rectangular shapes, but various other forms may be selected.
  • the first and second holes of the first electrode are not limited to rectangular shapes, and may have various other shapes such as a circular or elliptical shape.
  • the material of each structural member is not limited to that employed in the embodiments or examples discussed, but various other materials may be selected as needed.
  • the electrolytic cell of the electrolytic device is not limited to one- to three-chamber electrolytic cells, and may be applied to any types of electrolytic cells using electrodes in general.
  • the electrolytes and products are not limited to salt or hypochlorous acid, and may be developed into various electrolytes and products.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
US15/065,170 2014-09-19 2016-03-09 Electrode unit, electrolytic cell comprising electrode unit, electrolytic device and method of manufacturing electrode of electrode unit Abandoned US20160186335A1 (en)

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PCT/JP2015/056388 WO2016042801A1 (ja) 2014-09-19 2015-03-04 電極ユニット、電極ユニットを備える電解槽、電解装置、電極ユニットの電極の製造方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3569740A4 (en) * 2017-01-13 2020-04-08 Asahi Kasei Kabushiki Kaisha ELECTRODE FOR ELECTROLYSIS, ELECTROLYTIC CELL, ELECTRODE LAMINATE AND METHOD FOR RENEWING THE ELECTRODE
US20210288331A1 (en) * 2018-07-09 2021-09-16 Schaeffler Technologies AG & Co. KG Catalyst system, electrode, and fuel cell or electrolyzer

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017158832A1 (ja) * 2016-03-18 2017-09-21 株式会社 東芝 電解用電極、電極ユニット、及び電解水生成装置
CN111018061B (zh) * 2019-12-30 2021-08-24 江苏大学 一种在含锂的水溶液中提取锂的电解池用离子筛阴极及其制造方法
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CN113044933A (zh) * 2021-04-07 2021-06-29 湖南满缘红水科技有限公司 低盐eow电解槽、低盐eow电解装置及低盐eow制备方法
JP2023065251A (ja) * 2021-10-27 2023-05-12 株式会社イープラン 水素発生装置
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Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2927566C2 (de) * 1979-07-07 1986-08-21 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma für alkalische Elektrolyse, Verfahren zur Herstellung desselben und dessen Verwendung
GB8600401D0 (en) * 1986-01-08 1986-02-12 Hydrogen Systems Nv Ion-permeable diaphragms
JP3551288B2 (ja) * 1997-09-26 2004-08-04 ファースト・オーシャン株式会社 水電気分解装置及び水電気分解方法
JP2002110182A (ja) * 2000-09-29 2002-04-12 Sony Corp ガス拡散電極及びその製造方法、並びに、電気化学デバイス及びその製造方法
AU2003281180A1 (en) * 2002-07-11 2004-02-02 Sumitomo Electric Industries, Ltd. Porous semiconductor and process for producing the same
JP2005144240A (ja) * 2003-11-11 2005-06-09 Honda Motor Co Ltd 電解槽及び電解水生成装置
CN100562606C (zh) * 2004-08-31 2009-11-25 三洋电机株式会社 电解用电极及电解用电极的制造方法
JP2006176835A (ja) * 2004-12-22 2006-07-06 Nissan Motor Co Ltd 水電解装置の製造方法
US7951274B2 (en) * 2005-11-24 2011-05-31 Sumitomo Electric Hardmetal Corp. Diamond electrode, method for producing same, and electrolytic cell
CN103258979A (zh) * 2007-03-15 2013-08-21 日立麦克赛尔株式会社 电化学元件用隔膜、电化学元件用电极和电化学元件
US20120080310A1 (en) * 2009-06-02 2012-04-05 Panasonic Corporation Photoelectrochemical cell
JP5113892B2 (ja) * 2010-04-30 2013-01-09 アクアエコス株式会社 膜−電極接合体、これを用いる電解セル、オゾン水製造装置、オゾン水製造方法、殺菌方法及び廃水・廃液処理方法
JP2011246747A (ja) * 2010-05-25 2011-12-08 Yokogawa Electric Corp 電気分解電極及び電気分解装置
JP2012172199A (ja) * 2011-02-22 2012-09-10 Japan Carlit Co Ltd:The 電解用電極及びその製造方法
CN102653870B (zh) * 2011-03-01 2017-05-17 常州大学 一种电氧化臭氧发生器

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3569740A4 (en) * 2017-01-13 2020-04-08 Asahi Kasei Kabushiki Kaisha ELECTRODE FOR ELECTROLYSIS, ELECTROLYTIC CELL, ELECTRODE LAMINATE AND METHOD FOR RENEWING THE ELECTRODE
US20210288331A1 (en) * 2018-07-09 2021-09-16 Schaeffler Technologies AG & Co. KG Catalyst system, electrode, and fuel cell or electrolyzer

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CN106661743B (zh) 2019-12-10
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CN106661743A (zh) 2017-05-10

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