WO2017158832A1 - Électrode pour électrolyse, unité électrode et dispositif de production d'eau électrolytique - Google Patents

Électrode pour électrolyse, unité électrode et dispositif de production d'eau électrolytique Download PDF

Info

Publication number
WO2017158832A1
WO2017158832A1 PCT/JP2016/058768 JP2016058768W WO2017158832A1 WO 2017158832 A1 WO2017158832 A1 WO 2017158832A1 JP 2016058768 W JP2016058768 W JP 2016058768W WO 2017158832 A1 WO2017158832 A1 WO 2017158832A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
recess
hole
holes
electrolysis
Prior art date
Application number
PCT/JP2016/058768
Other languages
English (en)
Japanese (ja)
Inventor
内藤　勝之
直美 信田
英男 太田
横田　昌広
Original Assignee
株式会社 東芝
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
Application filed by 株式会社 東芝 filed Critical 株式会社 東芝
Priority to JP2018505199A priority Critical patent/JP6639638B2/ja
Priority to CN201680002245.5A priority patent/CN107532313B/zh
Priority to PCT/JP2016/058768 priority patent/WO2017158832A1/fr
Publication of WO2017158832A1 publication Critical patent/WO2017158832A1/fr

Links

Images

Classifications

    • 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
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • Embodiments of the present invention relate to an electrode for electrolysis, an electrode unit, and an electrolyzed water generating apparatus.
  • electrolyzers that electrolyze water to produce electrolyzed water having various functions, such as alkaline ionized water, ozone water, or hypochlorous acid water, have been provided.
  • hypochlorous acid water has an excellent sterilizing power and is safe for the human body and approved as a food additive. Electrolyzers are also used for hydrogen production and the like.
  • an electrolyzed water generation apparatus having a three-chamber type electrolytic cell has been proposed.
  • the inside of the electrolytic cell is divided into three chambers, an intermediate chamber, and an anode chamber and a cathode chamber located on both sides of the intermediate chamber, by a cation exchange membrane and an anion exchange membrane.
  • the anode chamber and the cathode chamber are provided with an anode and a cathode, respectively.
  • a porous electrode is used in which a large number of holes are processed by expanding, etching, or punching on a metal plate base material.
  • salt water is passed through the intermediate chamber, and water is circulated through the anode chamber and the cathode chamber, respectively.
  • hypochlorous acid water and chlorine are generated at the anode
  • sodium hydroxide water and hydrogen are generated at the cathode chamber.
  • the generated hypochlorous acid water is used as sterilizing / disinfecting water
  • sodium hydroxide water is used as washing water.
  • Hydrogen is used as hydrogen water or fuel. In particular, when chlorine and hydrogen are mainly produced, electrolysis is performed with a larger current.
  • hypochlorous acid In these electrolysis, high production efficiency of hypochlorous acid is required in the course of producing hypochlorous acid. If the generation efficiency is low, a considerable part of the input electric power is consumed for oxygen gas generation or the like. Therefore, in order to obtain the required amount of hypochlorous acid, it is necessary to increase the current and voltage. This increases energy consumption and shortens the life of the electrolytic electrode and electrode unit.
  • An object of an embodiment of the present invention is to provide an electrolysis electrode, an electrode unit, and an electrolysis apparatus having a long lifetime.
  • An electrode for electrolysis includes a first surface, a second surface facing the first surface, and an electrode substrate having a plurality of through holes penetrating from the first surface to the second surface; A plurality of first recesses opening in the first surface; A plurality of second recesses opening in the second surface and having an opening area wider than the first recess; A catalyst layer provided on the first surface; At least a part of the through hole communicates the first recess and the second recess, The first recess has a larger number than the second recess, The plurality of through holes are: A first through hole; A second through hole adjacent to the first through hole at the shortest first distance; The first through hole includes at least a third through hole adjacent to the first through hole at a second distance longer than the first distance, and the third distance between the second through hole and the third through hole is greater than the second distance.
  • the catalyst layer has a first thickness in a first region between the first through hole and the second through hole, and a second thickness in a second region between
  • FIG. 1 is a diagram schematically illustrating an example of an electrolysis apparatus according to an embodiment.
  • FIG. 2 is a diagram illustrating an example of an electrode having a diamond-shaped through hole with rounded corners according to the embodiment.
  • FIG. 3 is a diagram illustrating an example of an electrode having a rectangular through hole with rounded ends according to the embodiment.
  • FIG. 4 is a diagram illustrating an example of an electrode having an elliptical through hole according to the embodiment.
  • FIG. 5 is a diagram schematically illustrating another example of the electrolysis apparatus according to the embodiment.
  • Drawing 6A is a figure showing an example of the manufacturing method of the electrode used for an embodiment.
  • Drawing 6B is a figure showing an example of the manufacturing method of the electrode used for an embodiment.
  • Drawing 6C is a figure showing an example of the manufacturing method of the electrode used for an embodiment.
  • FIG. 6D is a diagram illustrating an example of an electrode manufacturing method used in the embodiment.
  • Drawing 6E is a figure showing an example of the manufacturing method of the electrode used for an embodiment.
  • FIG. 7 is a schematic diagram illustrating an example of the configuration of electrodes and diaphragms used in the embodiment.
  • FIG. 8 is a diagram schematically illustrating another example of the electrode device according to the embodiment.
  • the electrode for electrolysis includes an electrode base material and a catalyst layer provided on the electrode base material.
  • the electrode substrate includes a first surface, a second surface facing the first surface, and a plurality of through holes penetrating from the first surface to the second surface.
  • the electrode substrate includes a plurality of first recesses that open to the first surface and a plurality of second recesses that open to the second surface and have a larger opening area than the first recess.
  • At least a part of the through hole communicates the first recess and the second recess, and the first recess has a larger number than the second recess.
  • the plurality of through holes are formed in the first through hole, the second through hole adjacent to the first through hole at the shortest first distance, and the first through hole. And a third through hole adjacent to each other at a second distance longer than the first distance. The third distance between the second through hole and the third through hole is longer than the second distance.
  • the plurality of first recesses include three recesses adjacent to each other, for example, the third recess, the fourth recess, and the fifth recess, and the plurality of second recesses are adjacent to each other.
  • Two recesses such as a sixth recess and a seventh recess adjacent to the sixth recess.
  • the plurality of through holes include a first through hole communicating with the third recess and the sixth recess, a second through hole communicating with the fourth recess and the sixth recess, the fifth recess, and the seventh recess. And a third through hole communicating with each other.
  • the plurality of first recesses include a third recess and a fourth recess adjacent to the third recess, and the plurality of second recesses are formed in the fifth recess and the fifth recess.
  • a plurality of through-holes including an adjacent sixth recess, the first through-hole communicating with the third recess and the fifth recess, the second through-hole communicating with the fourth recess and the fifth recess, and a third A recess and a third through hole communicating with the sixth recess.
  • the first thickness in the first region provided on the first surface of the electrode base material and between the first through hole and the second through hole is equal to It is larger than the second thickness in the second region between the first through hole and the third through hole.
  • An electrode unit is an electrode unit using the above-described electrode for electrolysis as a first electrode, and is disposed so as to face a first electrode having a first surface and a second surface, and the first surface of the first electrode.
  • the electrolysis apparatus is an example of an electrolysis apparatus to which the electrode for electrolysis and an electrode unit using the same are applied.
  • This electrolysis apparatus has an electrolytic cell, an electrode unit incorporated in the electrolytic cell, a first electrode chamber and a second electrode chamber partitioned by the electrode unit.
  • the electrode unit can be equipped with a mechanism for applying a voltage, for example, a power source for applying a voltage to the electrode, a control device, and the like.
  • the first electrode chamber is, for example, an anode chamber
  • the second electrode chamber is, for example, a cathode chamber
  • a line for introducing an electrolytic solution containing chloride ions into an electrolytic cell a line for taking out acidic electrolyzed water from the anode chamber, and a cathode chamber
  • a line for taking out alkaline electrolyzed water from can be further provided.
  • the thickness of the catalyst layer in the region between the short-distance through holes where current tends to concentrate is larger than the thickness of the catalyst layer in the region between the through-holes of longer distance. Since it is large, consumption of the catalyst layer is made uniform, and the catalyst life of the electrode for electrolysis can be extended.
  • the distance between the through holes refers to the shortest distance from one end of the through hole to one end of the through hole.
  • adjoining means that a part of another through hole does not exist on the line segment indicating the distance between the two through holes.
  • each drawing is a schematic diagram for promoting the embodiment and its understanding, and its shape, dimensions, ratio, etc. are different from the actual device, but these are considered in consideration of the following description and known techniques. The design can be changed as appropriate.
  • the electrode is drawn on a plane, but it may be bent according to the shape of the electrode unit or may be cylindrical.
  • FIG. 1 is a diagram schematically showing an example of an electrolysis apparatus according to the first embodiment.
  • the electrolyzer 10 includes a three-chamber electrolytic cell 11 and an electrode unit 12.
  • the electrolytic cell 11 is formed in a flat rectangular box shape, and the inside thereof is partitioned into three chambers by a partition wall 14 and an electrode unit 12, an anode chamber 16, a cathode chamber 18, and an intermediate chamber 19 formed between the electrodes. It has been.
  • the electrode unit 12 includes a first electrode 20 positioned in the anode chamber 16, a second electrode (counter electrode) 22 positioned in the cathode chamber 18 and having a plurality of predetermined through holes, and a first electrode 20.
  • a catalyst layer 28 is formed on one surface 21a, and a diaphragm 24 is provided thereon.
  • Another diaphragm 27 can be provided on the first surface 23 a of the second electrode 22.
  • the first electrode 20 and the second electrode 22 face each other in parallel with a gap therebetween, and an intermediate chamber (electrolyte chamber) 19 that holds the electrolyte is formed between the diaphragms 24 and 27.
  • a holding body 25 that holds the electrolytic solution may be provided in the intermediate chamber 19.
  • the first electrode 20 and the second electrode 22 may be connected to each other by a plurality of bridges 60 having insulating properties.
  • the electrolysis apparatus 10 includes a power supply 30 for applying a voltage to the first and second electrodes 20 and 22 of the electrode unit 12 and a control device 36 for controlling the power supply 30.
  • An ammeter 32 and a voltmeter 34 may be provided.
  • the first electrode 20 has a porous structure in which a large number of through holes are formed in a base material 21 made of, for example, a rectangular metal plate.
  • the substrate 21 has a first surface 21a and a second surface 21b that faces the first surface 21a substantially in parallel. The distance between the first surface 21a and the second surface 21b, that is, the plate thickness is formed at T1.
  • the first surface 21 a faces the diaphragm 24, and the second surface 21 b faces the anode chamber 16.
  • An anodic oxide film (not shown) may be formed on the surface 21a.
  • a plurality of first recesses 40 are formed on the first surface 21a of the base material 21 and open to the first surface 21a.
  • a plurality of second recesses 42 are formed on the second surface 21b and open to the second surface 21b.
  • the opening diameter R1 of the first recess 40 on the side of the diaphragm 24 is smaller than the opening diameter R2 of the second recess 42, and the number of recesses is such that the first hole 40 is larger than the second hole 42.
  • a through hole in which the first recess 40 and the second recess 42 are connected is formed, but there may be a recess that is not connected or a part of which is connected.
  • the substrate 21 is preferably the same substrate.
  • the opening diameter R1 of the first recess 40 on the side of the diaphragm 24 is smaller than the opening diameter R2 of the second recess 42, and the number of the recesses is such that the first hole 40 is larger than the second hole 42. Stress due to the edge of the recess from the diaphragm to the diaphragm is relieved and the life of the diaphragm is increased. In addition, since the number of second recesses can be reduced, the electrical resistance can be reduced, which is advantageous in place of wiring and mechanical holding.
  • At least one of the first electrode 20 and the second electrode 22 used in the electrolysis apparatus 10 according to the embodiment has a predetermined plurality of through holes.
  • FIG. 2 is a schematic diagram showing an example of an electrode that can be used as the first electrode 20 of FIG.
  • FIG. 2 is a view of the first electrode 20 as viewed from the second surface 21b.
  • the plurality of through holes are formed by connecting the first recess 40 and the second recess 42.
  • the plurality of through holes include a first through hole 51, a second through hole 52 adjacent to the first through hole 51 with a first distance D1, and a second through hole 51 longer than the first distance D1. And a third through hole 53 adjacent to each other at a distance D2.
  • the second through hole 52 and the third through hole 53 are arranged in different directions with respect to the first through hole 51.
  • the third distance D3 between the second through hole 52 and the third through hole 53 is longer than the second distance D2.
  • the catalyst layer 28 is provided on the first surface 21a facing the second surface 21b of the electrode substrate.
  • the first distance between the first through hole 51 and the second through hole 52 is When the maximum thickness of the catalyst layer in the first region C1 is the first thickness H1, and the maximum thickness of the catalyst layer in the second region C2 between the first through hole 51 and the third through hole 53 is the second thickness H2, The first thickness H1 is larger than the second thickness H2.
  • the distance between adjacent through holes can be set to 0.1 mm or more and 2.5 mm or less.
  • the thickness is less than 0.1 mm, chloride ions are not sufficiently retained and the efficiency tends to decrease. If the thickness exceeds 2.5 mm, the generated hypochlorous acid tends to be difficult to be discharged.
  • the current tends to concentrate in the region where the distance between adjacent through holes is the shortest. For this reason, the catalyst between the shortest penetrations is most easily consumed.
  • the maximum thickness of the catalyst layer in the first region between the through holes having the shortest adjacent distance is larger than the maximum thickness of the catalyst layer in the second region between the through holes having the long adjacent distance, consumption of the catalyst layer is made uniform. As a result, the catalyst life is extended, and the electrode life, the electrode unit life, and the electrolysis device life can be extended.
  • the ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the second region is preferably 1.2 times or more and 7 times or less. More preferably, it is 1.5 times or more and 5 times or less, more preferably 2 times or more and 4 times or less. If the ratio is too large, the amount of catalyst between the shortest through-holes becomes too large, and the cost becomes high, or stress is concentrated and peeling tends to occur.
  • the absolute thickness of the catalyst layer is preferably 0.5 ⁇ m or more and 20 ⁇ m or less. If it is less than 0.5 ⁇ m, the catalyst layer tends to be non-uniform and the life tends to be shortened.
  • the absolute thickness of the catalyst layer is preferably 1 ⁇ m or more and 10 ⁇ m or less, and more preferably 2 ⁇ m or more and 4 ⁇ m or less.
  • the thickness of the catalyst layer can be measured by cross-sectional SEM.
  • Distance 2 is preferably 1.5 times or more of distance 1. If the ratio is less than 1.5 times, chloride ions are difficult to stay and the efficiency is lowered, and it is difficult to increase the thickness of the catalyst layer in the first region. Also, the electric resistance tends to increase and the voltage tends to increase. Preferably it is 4 times or more. More preferably, it is 5 times or more. However, when it becomes larger than 10 times, hypochlorous acid tends to be difficult to discharge.
  • the predetermined plurality of through holes provided in the first electrode 20 are, for example, diamonds with rounded corners.
  • the aperture can be measured using an optical microscope.
  • the shape of the first recess 40 is also a rhombus with rounded corners like the through hole.
  • the concave section can be tapered or curved so that the inside is narrowed.
  • the contact angle between the opening of the through hole and the porous diaphragm 24 is obtuse by forming the through hole with a tapered surface or a curved surface in which the opening on the first surface side becomes wide.
  • stress concentration on the porous diaphragm 24 can be reduced.
  • the opening of the through hole is smaller than the opening of the first recess 40 on the first surface 21a.
  • the first recess may be formed on the entire first surface. In this case, the 1st recessed part which does not penetrate to the 2nd surface exists.
  • the first recess not penetrating is excellent in holding chloride ions, so that the condition where the chloride ion concentration is low, for example, the concentration of chloride held in the intermediate chamber 19 is low, or the pressure in the intermediate chamber 19 is the anode chamber 16. When the pressure is lower than the pressure, it is effective for improving the generation efficiency of hypochlorous acid and lowering the driving voltage.
  • a rhombus in which a plurality of first recesses 40 can be used can be used.
  • the plurality of first recesses 40 have substantially the same size, but the plurality of first recesses 40 provided in the electrode substrate have a minimum opening diameter passing through the center of the opening of the first recess 40 constituting the through hole.
  • the aperture ratio of the through hole located at the center of the electrode substrate can be different from the aperture ratio of the through hole located at the peripheral edge of the electrode substrate.
  • the electrical resistance at the center becomes small, and current supply to the center becomes easy.
  • the opening ratio of the through hole located in the central portion is larger than that in the peripheral portion, gas can be easily released. Which is preferred depends on the size of the electrode, the operating conditions, and the relationship with other members, but can be selected.
  • FIG. 3 schematically shows an exploded perspective view showing an example of an electrode unit using the electrode according to the present embodiment.
  • the two electrodes 220 and 222 have the same structure.
  • the maximum thickness of the catalyst layer in the region C4 between the first and second through holes where the adjacent distance 1 is the shortest, the adjacent distance 2 is greater than the distance 1. It is larger than the maximum thickness of the catalyst layer in the region C5 between the large through holes. Further, the distance 3 of the region C6 between the second and third through holes is larger than the distance 2.
  • each of the six first recesses 63 has a rectangular shape that reaches from the right end to the left end of the electrode 223 excluding the seal portion 224, and the first recess 63 does not communicate with the second surfaces 221b and 223b. It has a recessed part and the opening part (through-hole) 61 connected to 2nd surface 221b, 223b. The depth of the 1st recessed part in which the through-hole 61 is arrange
  • FIG. Reference numeral 64 denotes a voltage application port, and the thick beam 65 faces the voltage application direction.
  • Each of the three second recesses 62 has a rectangular shape that reaches from the upper end to the lower end of the electrode 221 excluding the seal portion.
  • Six through holes respectively arranged in the six first recesses communicate with one second recess 62.
  • the number density of the first recesses 61 on the first surface 221a is sufficiently larger than the number density of the second recesses 62 on the second surface 221b. In FIG. 3, the number of openings is reduced for easy understanding, but the number of openings is larger.
  • any shape can be used as the shape of the through-hole, but a rectangular shape with a round end, or an ellipse with rounded corners is preferable.
  • FIG. 3 shows a part of the electrode. In such a shape, since the end is round, stress concentration on the porous diaphragm hardly occurs. Further, if the opening interval can be made dense, the opening ratio can be increased.
  • hypochlorous acid generated due to the first recess 63 is easy to move, and therefore easily flows out from the through hole. If hypochlorous acid does not flow out, chlorine gas is generated or diffuses to the diaphragm side, resulting in a low efficiency. This is likely to occur when the chloride ion concentration is high, and is likely to occur when the chloride concentration in the intermediate chamber 19 is high or the pressure in the intermediate chamber 19 is higher than that in the anode chamber 16. Therefore, the electrode structure as shown in FIG. 3 is particularly effective when the chloride concentration in the intermediate chamber 19 is high or the pressure in the intermediate chamber 19 is higher than that in the anode chamber 16.
  • the opening area of the through hole can be from 0.01 mm 2 to 4 mm 2 .
  • the thickness is preferably 0.1 mm 2 to 1.5 mm 2 . More preferably, it is 0.2 mm 2 to 1 mm 2 .
  • the opening area of the second recess can be 1 to 1600 mm 2 .
  • the thickness is preferably 4 mm 2 to 900 mm 2 , more preferably 9 mm 2 to 400 mm 2 .
  • the opening of the second concave portion 42 can be various shapes such as a square, a rectangle, a rhombus, a circle, an ellipse and the like.
  • a larger opening diameter of the second recess 42 can improve hypochlorous acid and outgassing, but it cannot be increased because the electrical resistance increases.
  • the opening of the second recess 62 may be a recess that is elongated in one direction, such as a rectangle or an ellipse, and is connected to the end of the electrode excluding the seal portion.
  • the opening of the first recess 63 can have various shapes such as a square, a rectangle, a rhombus, a circle, and an ellipse. As shown in the figure, an opening that extends in one direction, such as a rectangle or an ellipse, and is connected to the end of the electrode excluding the seal portion is also possible.
  • Two recesses that connect from end to end of the first recess and the second recess may be orthogonal or parallel. If it goes straight, gas diffusion is easy. If parallel, chloride ions are easy to collect. Orthogonal means intersecting at an angle of 87 to 93 degrees, and parallel means that the intersecting angle is within 3 degrees.
  • openings 61 are arranged in the direction of the voltage application port 64.
  • the beams 65 having a large electrode thickness and a small electrical resistance are arranged in the voltage application direction, power supply is facilitated, and the drive voltage can be reduced.
  • FIG. 4 schematically shows an exploded perspective view showing another example of the electrode unit using the electrode according to the embodiment.
  • the two electrodes 220 'and 222' have the same structure.
  • openings 61 ′ are arranged in the direction of the voltage application port 64 ′.
  • the beams 65 ' having a large electrode thickness and a small electrical resistance are arranged in the voltage application direction, so that power supply is facilitated and the driving voltage can be reduced.
  • the maximum thickness of the catalyst layer in the region C7 between the first and second through holes where the adjacent distance 1 is the shortest is the first where the adjacent distance 2 is long. And larger than the maximum thickness of the catalyst layer in the region C8 between the third through holes. Further, the distance 3 of the region C9 between the second and third through holes is larger than the distance 2.
  • the first recess 61 'constituting the through hole has an elliptical shape.
  • two recesses, that is, the first recess 62 ′ and the second recess 63 that are connected from end to end of the electrode excluding the seal portion are parallel to each other.
  • the first recess 62 ′ has a larger area than the second recess 63, and the arrangement of the through holes 61 ′ in the first recess 62 ′ is two rows of the arrangement of the through holes 61 ′ in the second recess 63.
  • FIG. 4 schematically shows the electrode structure, but the number of first recesses, second recesses and through holes is actually much larger.
  • the contact angle between the opening of the through hole and the porous diaphragm 24 becomes an obtuse angle by forming the through hole with a tapered surface or a curved surface where the opening on the first surface side becomes wide. Stress concentration on the porous diaphragm 24 can also be reduced.
  • first recess 62 ′ only needs to communicate with the second recess 63, and may include a first recess that is not the through hole 61 ′.
  • the first recess that is not in communication has the effect of increasing the electrode area and the effect of promoting the retention and diffusion of the substance.
  • the radius of curvature of the edge excluding the catalyst layer on the first surface of the through hole is 0.01 mm or more.
  • the current concentration at the edge portion can be relaxed and the catalyst layer can be formed uniformly.
  • it is 0.05 mm to 1 mm, More preferably, it is 0.1 mm to 0.5 mm.
  • FIG. 5 is a diagram schematically showing another example of the electrolysis apparatus according to the embodiment.
  • a liquid flow path may be provided in 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.
  • a line L1 for introducing an electrolyte containing chloride ions into the electrolytic cell 11, a salt water reservoir 107, lines L2 and L3 for supplying water to the electrolytic cell, a line L4 for extracting acidic electrolytic water from the electrolytic cell, and alkaline electrolysis from the electrolytic cell A line L5 for taking out water may be further provided.
  • a line L7 for circulating an electrolyte containing chloride ions may be provided, or a line for discharging may be provided.
  • the water softener 109 and a line L6 for supplying the water softener 109 with acidic electrolyzed water for adsorbent regeneration from the acidic electrolyzed water reservoir 106 may be further provided.
  • the water softener may be used only for water supplied to the cathode side.
  • a tank for storing alkaline electrolyzed water may be provided. Moreover, you may provide the tank for mixing an acidic liquid and an alkaline liquid and approaching neutrality.
  • FIGS. 6A to 6F are views showing an example of a method for manufacturing an electrode unit according to the embodiment.
  • the first electrode 20 can be produced, for example, by an etching method using a mask.
  • a single flat substrate 21 is prepared.
  • Resist films 50a and 50b are applied to the first surface 21a and the second surface 21b of the substrate 21.
  • the resist films 50a and 50b are exposed using an optical mask (not shown) to produce etching masks 52a and 52b, respectively.
  • the aperture area and aperture ratio are defined by the optical mask.
  • the first surface 21a and the second surface 21b of the base material 21 are wet-etched with a solution through the masks 52a and 52b, whereby a plurality of first recesses 40 and a plurality of second recesses are obtained. 42 is formed. Thereafter, the first electrode 20 is obtained by removing the masks 52a and 52b.
  • the planar shapes of the first recess 40 and the second recess 42 can be controlled by an optical mask and etching conditions. By designing the mask, the aperture ratio, aperture area, aperture shape, etc. in the electrode can be freely controlled.
  • the taper of the first and second recesses 40 and 42 and the shape of the curved surface can be controlled by the material of the substrate 21 and the etching conditions.
  • the first and second recesses are formed so that T2 ⁇ T3.
  • both surfaces of the base material 21 may be etched simultaneously, or one surface may be etched.
  • the type of etching is not limited to wet etching, and dry etching or the like may be used.
  • the first electrode 20 can be manufactured not only by etching but also by an expanding method, a punching method, or processing by laser or precision cutting, but the etching method is most preferable.
  • a valve metal such as titanium, chromium, aluminum or an alloy thereof, or a conductive metal can be used. Of these, titanium is preferred.
  • Electrolytic catalyst (catalyst layer) 28 is formed on at least the first surface 21 a of the first electrode 20.
  • a noble metal catalyst such as platinum or an oxide catalyst such as iridium oxide is preferably used, and an oxide catalyst containing iridium oxide is most preferable.
  • minute oxide film irregularities by anodizing the electrode from the viewpoint of improving the adhesion between the catalyst and the substrate.
  • the catalyst layer formed on the first surface 21a has a distance in which the maximum thickness of the catalyst layer is adjacent in the region C1 between the through holes having the shortest adjacent distance among the distances between the adjacent through holes of the plurality of through holes. Is larger than the maximum thickness of the catalyst layer in the region C2 between the long through holes.
  • the structure of the catalyst thickness can be prepared by repeating the steps of applying the liquid to the first surface 21a, drying and sintering the electrode substrate easily with the liquid containing the catalyst precursor. Since the opening area of the through hole of the present embodiment is small or the width of the through hole is small, the entire first surface including the through hole is initially covered with the liquid containing the catalyst precursor by coating.
  • the liquid covering the through-holes collects in the electrode part in contact with the through-holes, but the liquid is more concentrated between the shortest through-holes, so the maximum thickness of the catalyst layer is greater than the maximum thickness of the catalyst layer between the long through-holes. Can be bigger.
  • the thickness ratio can be controlled by the concentration of the liquid containing the catalyst precursor used, the type of liquid, and the drying conditions. The higher the concentration and the greater the surface tension, the greater the ratio of thickness. Moreover, the ratio tends to increase when drying is performed slowly.
  • the catalyst precursor is preferably an alcohol containing an iridium alkoxide, and more preferably a propanol solution containing iridium propoxide or a butanol solution containing iridium butoxide.
  • the catalyst layer preferably contains tantalum oxide from the viewpoint of catalyst life. It is also preferable to produce minute oxide film irregularities by anodic oxidation of the electrode and to form a tantalum oxide layer on the surface because the base material is easily wetted with the alcohol solution containing the catalyst precursor.
  • the average amount of the electrocatalyst per unit area may be different on both surfaces of the first electrode. Thereby, a side reaction etc. can be suppressed.
  • the surface (first surface) of the positive electrode on the porous membrane side is substantially flat except for the concave portion.
  • the surface roughness of the flat portion is preferably 0.01 ⁇ m to 3 ⁇ m. If it is smaller than 0.01 ⁇ m, the actual surface area of the electrode tends to decrease, and if it is larger than 3 ⁇ m, stress on the diaphragm tends to concentrate on the convex portion of the electrode. More preferably, it is 0.02 ⁇ m to 2 ⁇ m, and further preferably 0.03 ⁇ m to 1 ⁇ m.
  • the diaphragm 24 is formed in, for example, a rectangular shape having substantially the same dimensions as the first electrode 20, and faces the entire surface of the first surface 21a.
  • the diaphragm 27 is formed in a rectangular shape having substantially the same dimensions as the second electrode 22 and faces the entire surface of the first surface 23a.
  • films having many pores of 1 ⁇ m or less can be used.
  • a laminate of a first porous layer having a first pore diameter and a second porous layer having a second pore diameter different from the first pore diameter can be used.
  • an ion-selective membrane such as a hydrocarbon polymer ion permeable membrane or a fluorine polymer ion permeable membrane can be used.
  • the diaphragm preferably contains an inorganic oxide.
  • the positive electrode side diaphragm is preferably an inorganic oxide having a positive zeta potential in a pH range of 2 to 6.
  • the transport performance of the diaphragm to anions can be increased in a chemically stable and weakly acidic region.
  • inorganic oxides examples include zirconium oxide, titanium oxide, aluminum oxide, tin oxide, zircon, copper oxide, iron oxide, and mixed oxides thereof.
  • zirconium oxide, titanium oxide, aluminum oxide, or zircon can be used as the inorganic oxide having good chemical stability.
  • zirconium oxide and aluminum oxide that tends to have a positive zeta potential even when neutral are more preferable.
  • Inorganic oxides can include hydroxides, alkoxides, oxyhalides, and hydrates. When an inorganic oxide is produced through hydrolysis of a metal halide or metal alkoxide, a mixture of these may be formed depending on the post-treatment temperature.
  • the abundance ratio of the inorganic oxide in the diaphragm can vary depending on the location.
  • the abundance ratio of the inorganic oxide can be increased around the pores and on the surface.
  • the inorganic oxide a composite oxide such as zircon or a mixture of different inorganic oxides can be used.
  • the diaphragm may further include two or more different oxides, and the abundance ratio of each oxide may vary depending on the position of the diaphragm. For example, a region containing zirconium oxide having a high bending strength can be present on the surface, and a region containing titanium oxide having a large positive potential can be present inside.
  • the zeta potential of the diaphragm surface can be greater than ⁇ 30 mV at pH 4. If it is smaller than ⁇ 30 mV, there is a tendency that chlorine ions do not easily enter even when a voltage is applied to the diaphragm. Furthermore, the zeta potential on the surface of the diaphragm can be greater than -15 mV.
  • the diaphragm can be arranged on the positive electrode side on the negative electrode.
  • the porous diaphragm provided on the negative electrode can contain an inorganic oxide having a negative zeta potential within a pH range of 8 to 10. Thereby, the cation transport performance can be increased in the vicinity of the cathode in the weak alkali region.
  • an inorganic oxide an oxide whose zeta potential tends to be negative in an alkaline region can be used.
  • examples of such an inorganic oxide include zirconium oxide, titanium oxide, aluminum oxide, tungsten oxide, and zircon. , Silicon oxide, and zeolite can be used.
  • the inorganic oxide a mixture of the above oxides can be used.
  • the abundance ratio of the inorganic oxide in the diaphragm can vary depending on the location. For example, there may be a region containing zirconium oxide having a high bending strength on the surface, and a region containing silicon oxide having a wide negative potential pH range inside.
  • the inorganic oxide diaphragm 24 can have pores irregularly in-plane and three-dimensionally by forming a film by applying nanoparticles or by producing it with a sol-gel.
  • the diaphragm 24 is resistant to bending and the like.
  • the diaphragm 24 may contain a polymer in addition to the inorganic oxide.
  • the polymer gives the membrane flexibility.
  • a chemically stable main chain substituted with a halogen atom can be used, and examples thereof include polyvinylidene chloride, polyvinylidene fluoride, and Teflon (registered trademark). Among these, Teflon is preferable from the viewpoint of chemical and thermal stability.
  • polymers examples include hydrocarbon polymers such as polyethylene and polypropylene.
  • polyethylene is preferable from the viewpoint of chemical stability and low cost, and high-density polyethylene is more preferable.
  • engineering plastics such as polyimide, polysulfone, polyphenylene sulfide and the like can be used.
  • the aperture diameter of the diaphragm 24 can be different from the aperture diameter on the first electrode 20 side and the aperture diameter on the second electrode 22 side.
  • By increasing the opening diameter of the hole on the second electrode 22 side it is possible to make the movement of ions easier and reduce the stress concentration due to the through hole 40 of the first electrode 20. This is because the larger the opening on the electrode 22 side, the easier the ion movement by diffusion. Anions are attracted to the electrode relatively easily even if the hole diameter on the electrode 20 side is small. Conversely, if the pore diameter on the electrode 20 side is large, the generated chlorine or the like tends to diffuse to the porous diaphragm side.
  • the pore diameter on the surface of the diaphragm can be measured by using a high-resolution scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the internal holes can be measured by cross-sectional SEM observation.
  • FIG. 7 is a schematic diagram showing an example of the configuration of electrodes and diaphragms used in the embodiment.
  • the diaphragm 24 includes a first region 24 a that covers the first surface 21 a portion of the first electrode 20, and a second region 24 b that covers the openings of the plurality of first recesses 40 that communicate with the second hole 42. ,have.
  • the generated gas such as chlorine is difficult to be discharged. Therefore, the electrode unit 12 tends to deteriorate. Therefore, in the diaphragm 24, the surface holes in the first region are eliminated, that is, formed without holes, or the diameter of the surface holes in the first region 24a is made smaller than the diameter of the holes in the second region, The electrolytic reaction in the region in contact with the first region 24a can be suppressed, and deterioration of the electrode unit 12 can be prevented.
  • a thin non-porous film or a small-diameter diaphragm can be formed on the first surface 21a of the first electrode by screen printing or the like.
  • the reaction area of the electrode is reduced, it is possible to cause a sufficient reaction in the electrode region where gas tends to escape.
  • FIG. 7 also shows the first recess 40 that is not a through hole.
  • a multilayer film in which a plurality of porous films having different pore diameters are stacked can be used as the diaphragm 24 .
  • the hole diameter of the diaphragm located on the second electrode 22 side larger than the hole diameter of the diaphragm located on the first electrode 20 side, it is easier to move ions and stress concentration due to the through holes of the electrode. Can be reduced.
  • the first electrode 20 and the diaphragm 24, and the second electrode 22 are in contact with each other.
  • the electrode unit 12 is obtained.
  • the electrode unit 12 is disposed in the electrolytic cell 11 and attached to the partition wall 14.
  • the electrolytic cell 11 is partitioned into an anode chamber 16 and a cathode chamber 18 by the partition wall 14 and the electrode unit 12.
  • the electrode unit 12 is arrange
  • the first electrode 20 of the electrode unit 12 is disposed facing the anode chamber 16, and the second electrode 22 is disposed facing the cathode chamber 18.
  • both electrodes of the power supply 30 are electrically connected to the first electrode 20 and the second electrode 22.
  • the power supply 30 applies a voltage to the first and second electrodes 20 and 22 under the control of the control device 36.
  • the voltmeter 34 is electrically connected to the first electrode 20 and the second electrode 22 and detects a voltage applied to the electrode unit 12.
  • the detection information 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 through the electrode unit 12.
  • the detection information is supplied to the control device 36.
  • the control device 36 controls the application of voltage or the load to the electrode unit 12 by the power supply 30 according to the detection information according to the program stored in the memory.
  • the electrolyzer 10 applies an electric voltage or loads between the first electrode 20 and the second electrode 22 in a state in which the reaction target substance is supplied to the anode chamber 16 and the cathode chamber 18, and performs electrochemistry for electrolysis. Allow the reaction to proceed.
  • the diaphragm 24 As an example of forming the diaphragm 24 on the first surface 21a in which the catalyst 28 is formed on the surface of the first electrode 20, first, as shown in FIG. 6E, inorganic oxide particles and / or inorganic oxide precursors are used.
  • the pre-treatment film 24c is prepared by applying the solution containing the first surface 21a.
  • the pretreatment film 24c is sintered to produce a porous diaphragm 24 having porosity.
  • a metal alkoxide is dissolved in alcohol, and a high-boiling solvent such as glycerin is added or sintered to produce a porous structure.
  • a solution can be prepared by mixing organic substances such as fatty acids that easily oxidize into carbon dioxide.
  • a solution can raise a viscosity by adding a small amount of water and hydrolyzing a metal alkoxide partially.
  • a solution containing inorganic oxide particles and / or an inorganic oxide precursor can be applied to another porous film.
  • a porous film having large pores can be formed in advance on the first surface 21a of the first electrode 20, and the surface and pores can be covered with inorganic oxide particles and / or inorganic oxide precursors.
  • the diaphragm which has an inorganic oxide can be formed on the holding body 25 which hold
  • the sintering temperature can be about 100 to 600 ° C.
  • Example 1 A flat titanium plate having a plate thickness T1 of 0.5 mm is prepared as the substrate 21 of the first electrode.
  • the first electrode 20 of the first embodiment is manufactured by etching this titanium plate in the same manner as the steps shown in FIGS. 6A to 6D.
  • the electrode is 15 cm long in the water flow direction and 10 cm wide.
  • the thickness of the region including the first recess 63 having a small area is 0.1 mm, and the second having a large area.
  • the thickness of the region including the recess 62 (depth of the second recess) is 0.4 mm.
  • the first recess 63 is a rectangle that is connected from end to end excluding the electrode seal portion, and the second recess 62 is also a rectangle that is connected from end to end excluding the electrode seal portion, and is orthogonal to the first recess 63. ing.
  • the through holes 61 are rectangular with round ends as shown in FIG. 3, the average width of the apertures is 0.22 mm, the average length of the apertures is 2.5 mm, and the shorter pitch of the apertures is 0.5 mm on the average. The average pitch is 5 mm.
  • the etched electrode substrate 221 is treated at 80 ° C. for 1 hour in a 10 wt% oxalic acid aqueous solution. Furthermore, it is anodized at 10 V for 2 hours in a mixed aqueous solution of 1M ammonium sulfate and 0.5M ammonium fluoride.
  • a solution prepared by adding 1-butanol to iridium chloride and tantalum chloride to have a metal amount of 0.25 M is applied to the first surface 221 a of the electrode base 221, and then dried and fired.
  • a catalyst layer (not shown) is created. In this case, drying is performed at 80 ° C. for 10 minutes, and baking is performed at 450 ° C. for 10 minutes.
  • Two electrode base materials are produced by repeating such coating, drying, and firing five times, and a first electrode (anode) 220 is obtained.
  • the distance between the through holes in the first region C4 shown in FIG. 3 of this electrode is an average of 0.28 mm, and the distance between the through holes in the second region C5 is an average of 2.5 mm.
  • the ratio of the first distance to the second distance is 1: 8.9 on average.
  • the distance between the through holes in the third region C6 is an average of 2.6 mm.
  • an aqueous dispersion mixture of titanium oxide fine particles having a particle diameter of 100 nm and polyvinylidene fluoride particles is applied to a glass cloth having a thickness of 100 ⁇ m and dried. Furthermore, it is immersed in a 5% isopropanol solution of triisopropoxyaluminum and pulled up to the atmosphere. Dry in the atmosphere at 120 ° C. for 1 hour to prepare a diaphragm having a porous structure. The zeta potential of this diaphragm surface at pH 4 is 15 mV.
  • the second electrode (counter electrode, cathode) 22 is formed in the same manner as the first electrode 21 except that platinum is sputtered as the catalyst layer.
  • the membrane 27 is immersed in a 5% isopropanol solution of tetraisopropoxyzirconium in a polyethylene porous membrane having a thickness of 30 ⁇ m as the diaphragm 27 and pulled up to the atmosphere. Subsequently, the membrane is dried in the atmosphere at 90 ° C. for 1 hour to prepare a diaphragm having a porous structure.
  • the zeta potential of this diaphragm surface at pH 8 is -30 mV.
  • porous polystyrene having a thickness of 5 mm is used as the holding body 25 that holds the electrolytic solution.
  • the first electrode 20, the diaphragm 24, the porous polystyrene 25, the diaphragm 27, and the second electrode 22 are overlaid and fixed using silicone packing and screws, and the electrode unit 12 is created.
  • the electrode unit 12 is placed in the electrolytic cell 11, and the partition wall 14 and the electrode unit 12 are used to form an anode chamber 16, a cathode chamber 18, and an intermediate chamber 19 provided with a porous polystyrene 25 disposed between the electrodes. Divided into three rooms.
  • the anode chamber 16 and the cathode chamber 18 of the electrolytic cell 11 are each formed of a vinyl chloride container in which straight channels are formed.
  • a control device 36, a power source 30, a voltmeter 34, and an ammeter 32 are installed.
  • a pipe and a pump for supplying water from the water supply source 106 to the anode chamber 16 and the cathode chamber 18 are connected to the electrolytic cell 11 to secure the water supply lines 104 and 105.
  • a line L4 for extracting hypochlorous acid water from the anode chamber 16 and a line L5 for extracting alkaline water from the cathode chamber 18 can be provided.
  • a line L1 and a line 108 for collecting excess electrolyte are secured. Thereby, an electrolyzer having the same configuration as that of FIG. 5 is obtained.
  • Electrolysis is performed using the electrolyzer 10 at a flow rate of 2 L / min, a voltage of 5.7 V, and a current of 10 A.
  • Hypochlorous acid water is supplied on the first electrode (anode) 20 side, and hydrogen is supplied on the second electrode (cathode) 22 side.
  • the production efficiency of hypochlorous acid is 73 ⁇ 2%.
  • the production efficiency of hypochlorous acid is obtained from the amount of charge charged by measuring the effective chlorine concentration of the treated water.
  • the electrodes are removed, and the following measurements are performed on 10 through-holes using a cross-sectional SEM.
  • the maximum thickness of the catalyst layer in the first region between the through holes with the shortest adjacent distance is 4 to 5 ⁇ m
  • the catalyst layer in the second region between the through holes with the longest adjacent distance is The maximum thickness is 2.2 to 3.5 ⁇ m
  • the ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the second region is 1.3 to 2.2 times.
  • An electrolysis apparatus is produced using the 1st electrode produced by the same method.
  • the production efficiency of hypochlorous acid is the same.
  • the increase in voltage is 10%.
  • Example 2 Initial characteristics are the same as in Example 1. The electrode is removed and a cross-sectional SEM is taken to measure 10 through holes.
  • the maximum thickness of the catalyst layer in the first region between the through holes with the shortest adjacent distance is 2.0 to 2.5 ⁇ m
  • the maximum thickness of the catalyst layer in the second region between the through holes with the longest adjacent distance is The ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the second region is 0.9 to 1.1 times.
  • hypochlorous acid The production efficiency of hypochlorous acid is the same as in Example 1. When this device is operated for 2000 hours, the increase in voltage is 25%, which is larger than that in Example 1.
  • Examples 2 to 14 Comparative Examples 2 to 4 Comparative Examples 2 to 4.
  • the ratio of the first distance in the first region C4 and the second distance in the second region C5 is changed as shown in the following Table 1 in the electrode shape of FIG.
  • the electrodes are produced by changing the number of coatings and various times.
  • the third distance in the third region C6 is longer than the second distance.
  • Table 1 below shows the results of the above measurement and the magnification of the maximum thickness of the catalyst layer in the first region with respect to the maximum thickness of the catalyst layer in the second region.
  • the thickness of the catalyst layer is changed using electrodes having substantially the same opening structure.
  • the initial electrolysis efficiency is 70 to 75%.
  • Example 9 to 14 the thickness of the catalyst is similarly changed in the opening structure.
  • the initial electrolysis efficiency is 72 to 74%, but Example 11 is 68%, Example 12 is 66%, Example 13 is 67%, and Example 14 is 64%. descend. Therefore, the initial drive voltage is slightly high and the voltage increase rate is also slightly high.
  • Comparative Example 2 the number of times the solution is applied, dried, and fired is repeated more than in Comparative Example 1.
  • Example 15 A flat titanium plate having a plate thickness T1 of 0.5 mm is prepared as the substrate 21 of the first electrode.
  • the first electrode 20 of the embodiment is manufactured by etching this titanium plate in the same manner as in the steps shown in FIGS. 6A to 6D.
  • the electrode is 15 cm long in the water flow direction and 10 cm wide.
  • the thickness of the region including the first recess 40 having a small area is 0.1 mm
  • the thickness of the region including the second recess 42 having a large area is 0.4 mm.
  • the first recessed hole portion 40 has a diamond shape with rounded corners (the angles of the apexes of the extrapolated diamond shape are 60 ° and 120 °) similarly to the electrode shown in FIG. Through-holes are also rounded corners diamond, the opening area is 0.08mm 2 ⁇ 0.10mm 2.
  • the 2nd recessed part 42 is also a rhombus, and one side of a rhombus is about 3.6 mm.
  • the electrode unit and the electrolysis apparatus are prepared in the same manner as in Example 1 except that the first electrode and the second electrode are used.
  • the average ratio of the first distance and the second distance shown in FIG. 2 is 1: 5.0.
  • electrolysis is performed at a flow rate of 2 L / min, a voltage of 6.2 V, and a current of 10 A.
  • Hypochlorous acid water is supplied on the first electrode (anode) 20 side, and hydrogen is supplied on the second electrode (cathode) 22 side. And produces aqueous sodium hydroxide.
  • the production efficiency of hypochlorous acid is 75 ⁇ 2%.
  • the first electrode is removed from the apparatus, and 10 through holes are measured with a cross-sectional SEM.
  • the maximum thickness of the catalyst layer in the first region between the through holes with the shortest adjacent distance is 5 to 7 ⁇ m
  • the maximum thickness of the catalyst layer in the second region between the through holes with the longest adjacent distance is 2 to 3 ⁇ m.
  • the ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the second region is 2 to 3 times.
  • the electrolysis apparatus is produced in the same manner using the first electrode produced by the same method.
  • the production efficiency of hypochlorous acid is almost the same. If the device is operated for 2000 hours, the voltage increases by 9%.
  • Example 15 Initial characteristics are the same as in Example 15.
  • the cross section SEM is measured by removing the electrode, and 10 through holes are measured.
  • the maximum thickness of the catalyst layer in the first region between the through holes with the shortest adjacent distance is 2.0 to 2.6 ⁇ m
  • the maximum thickness of the catalyst layer in the second region between the through holes with the longest adjacent distance is The ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the second region is 0.9 to 1.1 times.
  • an electrolysis apparatus is produced using the second electrode produced by the same method as the first electrode.
  • the production efficiency of hypochlorous acid is the same as in Example 15. When this device is operated for 2000 hours, the increase in voltage is 30%, and the increase rate is large.
  • Example 16 A flat titanium plate having a plate thickness T1 of 0.5 mm is prepared as the substrate 221 ′ of the first electrode.
  • This titanium plate is etched except that the first recess, the second recess, and the through hole having the pattern shown in FIG. 4 are formed by etching and punching from both sides in the same manner as in Example 1.
  • the first electrode 220 ′ of the third embodiment is produced.
  • the electrode is 15 cm long in the water flow direction and 10 cm wide.
  • the first recess 63 is a rectangle connected from end to end excluding the electrode seal portion
  • the second recess 62 ′ is a rectangle connected from end to end excluding the electrode seal portion, and the end of the electrode excluding the seal portion
  • Two recesses that are connected to the end from each other, that is, the first recess 62 ′ and the second recess 63 are parallel.
  • the through hole of the first electrode is an ellipse as shown in FIG.
  • the rectangular groove is formed by etching, and the elliptical through hole 61 ′ is formed by punching.
  • Area of the through-hole is 0.53mm 2 ⁇ 0.55mm 2.
  • the first recess 62 ′ has a larger area than the second recess 63, and the arrangement of the through holes 61 ′ in the first recess 62 ′ is two rows of the arrangement of the through holes 61 ′ in the second recess 63.
  • the second electrode 222 ' can be formed in the same manner as the first electrode 220'.
  • the electrode unit and the electrolysis apparatus are produced in the same manner as in Example 1 except that the first electrode 220 'and the second electrode 222' are used instead of the first electrode 20 and the second electrode 22.
  • hypochlorous acid water was used on the first electrode (anode) side, and hydrogen and water were used on the second electrode (cathode) side. Produces sodium oxide water. The production efficiency of hypochlorous acid is 63 ⁇ 3%.
  • the first electrode is removed from the apparatus, and the cross-sectional SEM is measured.
  • the maximum thickness of the catalyst layer in the first region C7 between the through holes with the shortest adjacent distance is 3 to 4 ⁇ m
  • the maximum thickness of the catalyst layer in the second region C8 between the through holes with the long adjacent distance is 2 to 3 ⁇ m
  • the ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the second region is 1.3 to 1.5 times.
  • the average ratio of the first distance and the second distance shown in FIG. 4 is 1: 4.3.
  • the third distance in the third region C9 is greater than the second distance.
  • the electrolysis apparatus is produced in the same manner using the first electrode produced by the same method.
  • the production efficiency of hypochlorous acid is almost the same. If the device is run for 2000 hours, the voltage increases by 12%.
  • FIG. 8 is a diagram schematically illustrating another example of the electrolysis apparatus according to the embodiment.
  • this electrolysis apparatus 310 has a cathode chamber 318 and an anode chamber 316 disposed so as to surround the cathode chamber 318 instead of the electrolytic cell 11, and is free from natural convection without a channel and piping.
  • the configuration is the same as that shown in FIG. 1 except that a batch-type electrolytic cell 311 in which a water flow is formed is used.
  • the capacities of the anode chamber 316 and the cathode chamber 318 are 2 L and 0.1 L, respectively, and electrodes manufactured in the same manner as in Example 15 are used. However, the size of the electrode is 4 ⁇ 3 cm.
  • Electrolysis is performed at a voltage of 7 V and a current of 2 A for 5 minutes to produce hypochlorous acid water on the first electrode (anode) side and hydrogen and sodium hydroxide water on the second electrode (cathode) side.
  • the production efficiency of hypochlorous acid is 80 ⁇ 2%.
  • the first electrode is removed from the apparatus, and 10 through holes are measured with a cross-sectional SEM.
  • the maximum thickness of the catalyst layer in the first region between the through holes having the shortest adjacent distance is 5 to 7 ⁇ m
  • the maximum thickness of the catalyst layer in the second region between the through holes having the long adjacent distance is 2 to 3 ⁇ m.
  • the ratio of the maximum thickness of the catalyst layer in the first region to the maximum thickness of the catalyst layer in the region is 2 to 3 times.
  • the electrolysis apparatus is produced in the same manner using the first electrode produced by the same method.
  • the production efficiency of hypochlorous acid is almost the same. If this device is operated intermittently for 2000 hours, the voltage rises by 12%.
  • Electrolytic apparatus 11 ... Electrolytic cell, 12 ... Electrode unit, 14 ... Partition, 16 ... Anode chamber, 18 ... Cathode chamber, 19 ... Intermediate chamber, 20, ... 1st electrode, 21, 23, ... Base material, 22 , ... 2nd electrode, 21a, 23a, ... 1st surface, 21b, 23b, ... 2nd surface, 24, 27 ... diaphragm, 25 ... holder, 26, 26a, 26b ... diaphragm, 28 ... catalyst layer, 30 ... Power source, 32 ... ammeter, 34 ... voltmeter, 40, 44, 61, 63 ... through hole (first recess), 42, 46, 62 ... second recess, 50 ... resist film, 60 ... bridge, 64 ... voltage Application port, 65 ... Beam

Landscapes

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

Abstract

La présente invention concerne une électrode pour électrolyse qui comprend : un substrat d'électrode ayant une première surface, une seconde surface opposée à la première surface et de multiples trous traversants passant de la première surface à la seconde surface ; de multiples premiers évidements débouchant dans la première surface ; de multiples seconds évidements débouchant sur la seconde surface et ayant une aire d'ouverture plus large que les premiers évidements ; et une couche de catalyseur disposée sur la première surface. Au moins certains des trous traversants permettent une communication entre les premiers évidements et les seconds évidements, les premiers évidements sont plus nombreux que les seconds évidements et les multiples trous traversants comprennent au moins des premiers trous traversants, des deuxièmes trous traversants adjacents à un premier trou traversant au niveau d'une première distance minimale, et des troisièmes trous traversants adjacents à un premier trou traversant au niveau d'une deuxième distance supérieure à la première distance. Une troisième distance entre le deuxième trou traversant et le troisième trou traversant est supérieure à la deuxième distance. Dans la couche de catalyseur, une première épaisseur dans une première région entre un premier trou traversant et un deuxième trou traversant est supérieure à une seconde épaisseur dans une seconde région entre un premier trou traversant et un troisième trou traversant.
PCT/JP2016/058768 2016-03-18 2016-03-18 Électrode pour électrolyse, unité électrode et dispositif de production d'eau électrolytique WO2017158832A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018505199A JP6639638B2 (ja) 2016-03-18 2016-03-18 電解用電極、電極ユニット、及び電解水生成装置
CN201680002245.5A CN107532313B (zh) 2016-03-18 2016-03-18 电解用电极、电极单元及电解水生成装置
PCT/JP2016/058768 WO2017158832A1 (fr) 2016-03-18 2016-03-18 Électrode pour électrolyse, unité électrode et dispositif de production d'eau électrolytique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2016/058768 WO2017158832A1 (fr) 2016-03-18 2016-03-18 Électrode pour électrolyse, unité électrode et dispositif de production d'eau électrolytique

Publications (1)

Publication Number Publication Date
WO2017158832A1 true WO2017158832A1 (fr) 2017-09-21

Family

ID=59851034

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/058768 WO2017158832A1 (fr) 2016-03-18 2016-03-18 Électrode pour électrolyse, unité électrode et dispositif de production d'eau électrolytique

Country Status (3)

Country Link
JP (1) JP6639638B2 (fr)
CN (1) CN107532313B (fr)
WO (1) WO2017158832A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6371489B1 (ja) * 2018-04-03 2018-08-08 株式会社ドクターズ・マン 水素水の製造装置
WO2019155731A1 (fr) * 2018-02-09 2019-08-15 田中貴金属工業株式会社 Corps d'alimentation électrique
CN113165914A (zh) * 2018-11-21 2021-07-23 李娟周 杀菌电极及其制造方法以及使用该电极的杀菌装置
JP2022179943A (ja) * 2021-05-24 2022-12-06 本田技研工業株式会社 電気化学セル、セル運転システム及びセル運転方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10291808A (ja) * 1997-04-16 1998-11-04 Permelec Electrode Ltd 過酸化水素水の製造方法及び装置
JP2004204328A (ja) * 2002-12-26 2004-07-22 Takatoshi Nakajima 次亜塩素酸水の製造方法及び利用方法
JP2005259650A (ja) * 2004-03-15 2005-09-22 Honda Motor Co Ltd 固体高分子型燃料電池
JP2007119881A (ja) * 2005-10-31 2007-05-17 Permelec Electrode Ltd 酸素還元ガス拡散陰極及び食塩電解方法
JP2007173225A (ja) * 2005-11-25 2007-07-05 Matsushita Electric Ind Co Ltd 膜触媒層接合体、膜電極接合体、燃料電池および燃料電池スタック
JP2010257642A (ja) * 2009-04-22 2010-11-11 Fuji Electric Systems Co Ltd ガス拡散電極の製造方法
JP2014101549A (ja) * 2012-11-20 2014-06-05 Toshiba Corp 電気化学セル、及びこのセルを用いた減酸素装置、並びにこの減酸素装置を用いた冷蔵庫
WO2016043072A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Dispositif électrolytique, unité d'électrode, et procédé de production d'eau électrolytique
WO2016043109A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Dispositif d'électrolyse et électrodes
WO2016042802A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Unité d'électrode, bain électrolytique pourvu d'une d'unité d'électrode, et dispositif d'électrolyse
WO2016042801A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Unité d'électrode, bain électrolytique muni de l'unité d'électrode, dispositif d'électrolyse, et procédé de fabrication d'électrode de l'unité d'électrode

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1953853B1 (fr) * 2005-11-25 2011-10-19 Panasonic Corporation Membrane avec revêtement catalytique, assemblage membrane-électrodes, pile à combustible et empilement de piles à combustibles
JP5400414B2 (ja) * 2009-02-18 2014-01-29 本田技研工業株式会社 電解装置
JP5480542B2 (ja) * 2009-06-23 2014-04-23 クロリンエンジニアズ株式会社 導電性ダイヤモンド電極並びに導電性ダイヤモンド電極を用いたオゾン生成装置
GB201315992D0 (en) * 2013-09-09 2013-10-23 Afc Energy Plc Fuel cells and method of manufacture
JP6353294B2 (ja) * 2014-06-30 2018-07-04 ダイハツ工業株式会社 燃料電池用ガス拡散シートおよび燃料電池
CN106574382B (zh) * 2014-09-19 2018-12-04 株式会社东芝 电极单元、电解装置和用于电解装置的电极

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10291808A (ja) * 1997-04-16 1998-11-04 Permelec Electrode Ltd 過酸化水素水の製造方法及び装置
JP2004204328A (ja) * 2002-12-26 2004-07-22 Takatoshi Nakajima 次亜塩素酸水の製造方法及び利用方法
JP2005259650A (ja) * 2004-03-15 2005-09-22 Honda Motor Co Ltd 固体高分子型燃料電池
JP2007119881A (ja) * 2005-10-31 2007-05-17 Permelec Electrode Ltd 酸素還元ガス拡散陰極及び食塩電解方法
JP2007173225A (ja) * 2005-11-25 2007-07-05 Matsushita Electric Ind Co Ltd 膜触媒層接合体、膜電極接合体、燃料電池および燃料電池スタック
JP2010257642A (ja) * 2009-04-22 2010-11-11 Fuji Electric Systems Co Ltd ガス拡散電極の製造方法
JP2014101549A (ja) * 2012-11-20 2014-06-05 Toshiba Corp 電気化学セル、及びこのセルを用いた減酸素装置、並びにこの減酸素装置を用いた冷蔵庫
WO2016043072A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Dispositif électrolytique, unité d'électrode, et procédé de production d'eau électrolytique
WO2016043109A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Dispositif d'électrolyse et électrodes
WO2016042802A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Unité d'électrode, bain électrolytique pourvu d'une d'unité d'électrode, et dispositif d'électrolyse
WO2016042801A1 (fr) * 2014-09-19 2016-03-24 株式会社 東芝 Unité d'électrode, bain électrolytique muni de l'unité d'électrode, dispositif d'électrolyse, et procédé de fabrication d'électrode de l'unité d'électrode

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019155731A1 (fr) * 2018-02-09 2019-08-15 田中貴金属工業株式会社 Corps d'alimentation électrique
KR20200015832A (ko) * 2018-02-09 2020-02-12 다나카 기킨조쿠 고교 가부시키가이샤 급전체
KR102088243B1 (ko) 2018-02-09 2020-05-15 다나카 기킨조쿠 고교 가부시키가이샤 급전체
JP6371489B1 (ja) * 2018-04-03 2018-08-08 株式会社ドクターズ・マン 水素水の製造装置
WO2019193776A1 (fr) * 2018-04-03 2019-10-10 株式会社ドクターズ・マン Appareil de production d'eau hydrogénée
JP2019181316A (ja) * 2018-04-03 2019-10-24 株式会社ドクターズ・マン 水素水の製造装置
CN113165914A (zh) * 2018-11-21 2021-07-23 李娟周 杀菌电极及其制造方法以及使用该电极的杀菌装置
JP2022179943A (ja) * 2021-05-24 2022-12-06 本田技研工業株式会社 電気化学セル、セル運転システム及びセル運転方法
JP7220742B2 (ja) 2021-05-24 2023-02-10 本田技研工業株式会社 電気化学セル、セル運転システム及びセル運転方法

Also Published As

Publication number Publication date
CN107532313B (zh) 2019-08-30
JP6639638B2 (ja) 2020-02-05
CN107532313A (zh) 2018-01-02
JPWO2017158832A1 (ja) 2018-06-07

Similar Documents

Publication Publication Date Title
JP6441308B2 (ja) 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
JP6542265B2 (ja) 多孔質隔膜、その製造方法、次亜塩素酸水製造用電極ユニット、及びそれを用いた次亜塩素酸水製造装置
US20160186336A1 (en) Electrode unit, electrolytic cell comprising electrode unit and electrolytic device
JP6258515B2 (ja) 電極ユニット、電解装置、および電解装置に用いる電極
JP6639638B2 (ja) 電解用電極、電極ユニット、及び電解水生成装置
JP6585176B2 (ja) 電極、電極ユニット、及び電解装置
JP6216806B2 (ja) イオン交換膜電解槽
JP6408033B2 (ja) 電極ユニットおよびそれを用いた電解装置
JP6208380B2 (ja) 電解用電極、電極ユニット、及び電解装置
JP2018076554A (ja) 陰イオン交換膜、電解セル、及び電解水生成装置
JP2018154908A (ja) 電解用電極，これを用いた電解ユニット及び電解水生成装置
CN109072462B (zh) 电极单元的制造方法、及电解水生成装置的制造方法
JP2018044229A (ja) 電解セルおよびそれを用いた電解水生成装置および電解セルの製造方法
JPWO2017047121A1 (ja) 電極および電解装置
JP6862232B2 (ja) 隔膜の製造方法、及びそれを用いた電極ユニットの製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018505199

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16894450

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 16894450

Country of ref document: EP

Kind code of ref document: A1