WO2020217817A1 - 電解用電極及び電解用電極の製造方法 - Google Patents

電解用電極及び電解用電極の製造方法 Download PDF

Info

Publication number
WO2020217817A1
WO2020217817A1 PCT/JP2020/013021 JP2020013021W WO2020217817A1 WO 2020217817 A1 WO2020217817 A1 WO 2020217817A1 JP 2020013021 W JP2020013021 W JP 2020013021W WO 2020217817 A1 WO2020217817 A1 WO 2020217817A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
tantalum
layers
conductive substrate
electrode
Prior art date
Application number
PCT/JP2020/013021
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
モハマド エルマン
奎敏 神農
足立　博史
佐名川　佳治
Original Assignee
パナソニックＩｐマネジメント株式会社
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 パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to US17/604,426 priority Critical patent/US20220178034A1/en
Priority to JP2021515887A priority patent/JP7194911B2/ja
Priority to CN202080031703.4A priority patent/CN113795612A/zh
Priority to EP20796016.2A priority patent/EP3960905A4/de
Publication of WO2020217817A1 publication Critical patent/WO2020217817A1/ja

Links

Images

Classifications

    • 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
    • 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
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • 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
    • C25B11/031—Porous 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
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
    • 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
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
    • 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
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Definitions

  • the present disclosure relates to a method for manufacturing an electrode for electrolysis and an electrode for electrolysis, and more specifically, to a method for manufacturing an electrode for electrolysis and an electrode for electrolysis used for generating chlorine by electrolyzing salt water.
  • Patent Document 1 a technique is known in which a dilute saline solution obtained by adding salt to tap water is electrolyzed to generate chlorine, and hypochlorous acid is produced by the reaction between the chlorine and water.
  • Patent Document 1 describes an electrode substrate made of titanium or a titanium alloy as an electrode for electrolysis, a titanium oxide layer provided on the electrode substrate, and iridium oxide provided on the titanium oxide layer in terms of metal.
  • An intermediate oxide layer composed of a composite of 3 to 30 mol% and 70 to 97 mol% of tantalum oxide, and 2 to 35 mol% of rhodium oxide and 30 of iridium oxide provided on the intermediate oxide layer in terms of metal.
  • An electrode for electrolysis comprising a composite of ⁇ 80 mol%, tantalum oxide 6-35 mol% and platinum 12-62 mol% is disclosed.
  • the electrode for electrolysis has a longer life by preventing peeling of the composite layer containing iridium that functions as a catalyst.
  • An object of the present disclosure is to provide an electrolytic electrode and a method for manufacturing an electrolytic electrode capable of suppressing peeling of a composite layer.
  • the electrode for electrolysis includes a conductive substrate, an intermediate layer, and a composite layer.
  • the conductive substrate contains at least titanium.
  • the intermediate layer is provided on one main surface of the conductive substrate.
  • the composite layer is provided on the intermediate layer.
  • the composite layer has a plurality of tantalum layers and a plurality of catalyst layers.
  • Each of the plurality of tantalum layers is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • Each of the plurality of catalyst layers contains platinum and iridium.
  • the plurality of tantalum layers and the plurality of catalyst layers are alternately arranged one by one in the thickness direction of the conductive substrate.
  • one tantalum layer among the plurality of tantalum layers is the lowest layer closest to the one main surface of the conductive substrate, and one catalyst layer among the plurality of catalyst layers is the conductive layer. The top layer farthest from the substrate.
  • the method for manufacturing an electrode for electrolysis includes an intermediate layer forming step and a composite layer forming step.
  • the intermediate layer forming step is a step of forming an intermediate layer on one main surface of a conductive substrate containing at least titanium.
  • the composite layer forming step is a step of forming a composite layer on the intermediate layer.
  • the composite layer has a laminated structure in which a plurality of tantalum layers and a plurality of catalyst layers are alternately arranged one by one.
  • Each of the plurality of tantalum layers is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • Each of the plurality of catalyst layers contains platinum and iridium.
  • the composite layer forming step includes a first step, a second step, and a third step.
  • a solution containing tantalum is applied onto the intermediate layer and then fired at a first specified temperature to form the lowest tantalum layer in the laminated structure among the plurality of tantalum layers.
  • a laminated body which is a base of a portion other than the tantalum layer of the lowermost layer in the laminated structure is formed.
  • a solution containing platinum and iridium is applied and then heated and dried at a second specified temperature to form a layer that is a source of one of the plurality of catalyst layers.
  • a solution containing tantalum is applied and then heated and dried at a third specified temperature to form a layer that is a source of one tantalum layer other than the lowermost tantalum layer among the plurality of tantalum layers.
  • the laminate is fired at a fourth specified temperature, which is higher than both the second specified temperature and the third specified temperature, so that the plurality of catalyst layers and the plurality of tantalum layers are formed.
  • a tantalum layer other than the lowermost tantalum layer is formed, and a plurality of cracks recessed from the main surface of the catalyst layer opposite to the intermediate layer side are formed.
  • the electrode for electrolysis includes a conductive substrate, an intermediate layer, and a composite layer.
  • the conductive substrate contains at least titanium.
  • the intermediate layer is provided on one main surface of the conductive substrate.
  • the composite layer is provided on the intermediate layer.
  • the composite layer has a plurality of tantalum layers and a plurality of catalyst layers.
  • Each of the plurality of tantalum layers is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • Each of the plurality of catalyst layers contains platinum and iridium.
  • the plurality of tantalum layers and the plurality of catalyst layers are alternately arranged one by one in the thickness direction of the conductive substrate.
  • one tantalum layer among the plurality of tantalum layers is the lowest layer closest to the one main surface of the conductive substrate, and the other one tantalum layer among the plurality of tantalum layers is said. It is the top layer farthest from the conductive substrate.
  • the electrode for electrolysis has a plurality of recesses recessed from the main surface of the composite layer on the side opposite to the intermediate layer side. The depth of each of the plurality of recesses is a depth that penetrates at least one catalyst layer among the plurality of catalyst layers.
  • FIG. 1 is a cross-sectional view of the electrode for electrolysis according to the first embodiment.
  • FIG. 2 is a plan view of the same electrode for electrolysis.
  • 3A to 3D are process cross-sectional views for explaining the manufacturing method of the electrode for electrolysis of the same.
  • FIG. 4 is a graph showing the results of the durability test of the electrode for electrolysis as described above.
  • 5A to 5D are explanatory views of an estimation mechanism of durability improvement in the same electrolytic electrode.
  • FIG. 6 is a cross-sectional view of the electrode for electrolysis according to the second embodiment.
  • 7A to 7E are process cross-sectional views for explaining the manufacturing method of the electrode for electrolysis of the same.
  • FIG. 8 is a cross-sectional view of the electrode for electrolysis according to a modified example.
  • FIGS. 1, 2, 3A to 3D, 5A to 5D, 6, 7A to 7E and 8 described in the following embodiments 1, 2 and the like are schematic views, and the size and thickness of each component in the drawing are shown. Each ratio does not always reflect the actual dimensional ratio.
  • the electrode 1 for electrolysis is an electrode used to generate chlorine by electrolyzing salt water.
  • the salt water is, for example, a saline solution.
  • the electrode 1 for electrolysis is used for electrolyzing salt water, for example, a system using the electrode 1 for electrolysis as an anode among an anode and a cathode to which a DC voltage is applied from a power source electrolyzes salt water to generate chlorine. By reacting this chlorine with water, hypochlorous acid water can be produced.
  • the electrode 1 for electrolysis includes a conductive substrate 2, an intermediate layer 3, and a composite layer 4.
  • the conductive substrate 2 has one main surface 21 (hereinafter, also referred to as a first main surface 21) and a second main surface 22 on the opposite side of the first main surface 21.
  • the plan-view shape of the conductive substrate 2 (the outer peripheral shape of the conductive substrate 2 when viewed from the thickness direction D1 of the conductive substrate 2) is rectangular.
  • the thickness of the conductive substrate 2 is, for example, 100 ⁇ m or more and 2 mm or less, and as an example, 500 ⁇ m.
  • the size of the conductive substrate 2 in a plan view is, for example, 25 mm ⁇ 60 mm.
  • the conductive substrate 2 contains at least titanium.
  • the conductive substrate 2 is, for example, a titanium substrate.
  • the material of the conductive substrate 2 is titanium or an alloy containing titanium as a main component (hereinafter referred to as titanium alloy).
  • the titanium alloy is, for example, a titanium-palladium alloy, a titanium-nickel-ruthenium alloy, a titanium-tantal alloy, a titanium-aluminum alloy, a titanium-aluminum-vanadium alloy, or the like.
  • the first main surface 21 of the conductive substrate 2 is preferably a rough surface from the viewpoint of enhancing the adhesion of the intermediate layer 3.
  • the first main surface 21 of the conductive substrate 2 is roughened before the intermediate layer 3 is provided.
  • the surface roughness of the first main surface 21 of the conductive substrate 2 is, for example, 0.3 ⁇ m, and the maximum height Rz is 3 ⁇ m.
  • the arithmetic mean roughness Ra and the maximum height Rz are specified in, for example, JIS B 0601-2001 (ISO 4287-1997).
  • the arithmetic mean roughness Ra and the maximum height Rz are, for example, values measured from a cross-sectional SEM image (Cross-sectional Scanning Electron Microscope Image).
  • the intermediate layer 3 is provided on the first main surface 21 of the conductive substrate 2.
  • the electrode 1 for electrolysis has an interface between the conductive substrate 2 and the intermediate layer 3.
  • the intermediate layer 3 has corrosion resistance to salt water and chlorine.
  • the intermediate layer 3 is preferably formed of a material having higher corrosion resistance to salt water and chlorine than the conductive substrate 2.
  • the material of the intermediate layer 3 is preferably a material having conductivity and high electrical conductivity.
  • the material of the intermediate layer 3 is, for example, a transition metal or a mixture containing a transition metal, for example, platinum, a mixture of tantalum and platinum and iridium, iridium, iridium oxide, nickel and the like.
  • the material of the intermediate layer 3 is, for example, platinum.
  • the thickness of the intermediate layer 3 is, for example, 0.3 ⁇ m or more and 5 ⁇ m or less, and as an example, 0.6 ⁇ m.
  • the composite layer 4 is provided on the intermediate layer 3.
  • the electrode 1 for electrolysis has an interface between the composite layer 4 and the intermediate layer 3. That is, the composite layer 4 is provided on the conductive substrate 2 via the intermediate layer 3.
  • the composite layer 4 has a plurality of (four in the illustrated example) tantalum layers 41 and a plurality of (four in the illustrated example) catalyst layers 42.
  • Each of the plurality of catalyst layers 42 contains platinum and iridium.
  • Each of the plurality of catalyst layers 42 is a mixture of platinum and iridium.
  • Each of the plurality of tantalum layers 41 is a layer formed of tantalum oxide, but is not limited to this, and may be a layer formed of tantalum or a layer formed of a mixture of tantalum oxide and tantalum. It may be (a layer in which tantalum oxide and tantalum are mixed).
  • iridium is dispersed by platinum. Iridium functions as a catalyst for generating chlorine.
  • the molar ratio of platinum, iridium, and tantalum is, for example, 6 to 10: 1 to 10: 1 to 8.
  • the molar amount of iridium is preferably less than or equal to the molar amount of platinum.
  • the tantalum layer 41 has higher corrosion resistance than the catalyst layer 42 and is resistant to structural changes. As a result, the tantalum layer 41 located on the catalyst layer 42 can suppress the elution of iridium in the catalyst layer 42 immediately below the tantalum layer 41.
  • the composite layer 4 has a laminated structure in which a plurality of tantalum layers 41 and a plurality of catalyst layers 42 are alternately arranged one by one in the thickness direction D1 of the conductive substrate 2.
  • the thickness of each of the plurality of tantalum layers 41 is, for example, 15 nm to 300 nm, and 100 nm as an example.
  • the thickness of each of the plurality of catalyst layers 42 is, for example, 15 nm to 100 nm, and 50 nm as an example.
  • the four tantalum layers 41 are arranged in the order of proximity to the first main surface 21 of the conductive substrate 2, the first tantalum layer 411, the second tantalum layer 412, the third tantalum layer 413, and the fourth tantalum layer. It may also be called 414. Further, the four catalyst layers 42 may be referred to as a first catalyst layer 421, a second catalyst layer 422, a third catalyst layer 423, and a fourth catalyst layer 424 in the order of proximity to the first main surface 21 of the conductive substrate 2. is there.
  • the first tantalum layer 411, the first catalyst layer 421, the second tantalum layer 412, the second catalyst layer 422, the third tantalum layer 413, the third catalyst layer 423, and the fourth are arranged in this order.
  • one of the plurality of tantalum layers 41 is the lowest layer closest to the main surface 21 of one of the conductive substrates 2, and one of the plurality of catalyst layers 42 is conductive. This is the top layer farthest from the sex substrate 2.
  • one of the plurality of tantalum layers 41, the tantalum layer 41 is the lowest layer closest to the first main surface 21 of the conductive substrate 2.
  • one of the plurality of catalyst layers 42, the catalyst layer 42 is the uppermost layer farthest from the conductive substrate 2.
  • the electrode 1 for electrolysis has a plurality of recesses 5 recessed from the main surface 40 on the side opposite to the intermediate layer 3 side in the composite layer 4.
  • the depth of each of the plurality of recesses 5 is greater than the distance L1 between the main surface 40 of the composite layer 4 and the catalyst layer 42 (third catalyst layer 423), which is the second farthest from the conductive substrate 2 among the plurality of catalyst layers 42. Is also large, and the distance between the main surface 40 of the composite layer 4 and the intermediate layer 3 is L2 or less.
  • the width H1 (see FIG. 2) of each of the plurality of recesses 5 is 0.1 ⁇ m or more and 10 ⁇ m or less, and 0.3 ⁇ m or more and 3 ⁇ m or less. , More preferred.
  • the width H1 of the recess 5 in a plan view from the thickness direction D1 of the conductive substrate 2 is the opening width in the lateral direction (direction orthogonal to the length direction) of the main surface 40 of the composite layer 4.
  • the area of the main surface 40 of the composite layer 4 is S1
  • the total area of the opening areas of the plurality of recesses 5 in the main surface 40 of the composite layer 4 is the total area.
  • the ratio of S2 to S1 + S2 is, for example, 5% to 50%.
  • the ratio of S2 to S1 + S2 is preferably 5% or more from the viewpoint of improving the chlorine generation efficiency.
  • the ratio of S2 to S1 + S2 is preferably 50% or less, more preferably 20% or less from the viewpoint of suppressing peeling of the composite layer 4. That is, the ratio of S2 to S1 + S2 is more preferably 5% or more and 20% or less.
  • the total length of the opening edges of the portions of the plurality of recesses 5 existing in the square region of 0.01 mm 2 is 1 mm or more in a plan view from the thickness direction D1 of the conductive substrate 2. is there.
  • the conductive substrate 2 is prepared, and then the roughening step, the intermediate layer forming step, and the composite layer forming step are sequentially performed.
  • the first main surface 21 of the conductive substrate 2 is roughened by immersing the conductive substrate 2 in an oxalic acid aqueous solution.
  • the roughening step is not an essential step.
  • the arithmetic average roughness Ra is, for example, 0.3 ⁇ m
  • the maximum height Rz is 3 ⁇ m.
  • the arithmetic mean roughness Ra and the maximum height Rz are, for example, values measured by a surface roughness meter Zygo.
  • the intermediate layer 3 is formed on the first main surface 21 of the conductive substrate 2 (see FIG. 3B).
  • the intermediate layer 3 is, for example, a platinum layer.
  • the solution that is the source of the intermediate layer 3 is applied onto the first main surface 21 of the conductive substrate 2, then naturally dried, then heat-treated, and then fired. , The intermediate layer 3 is formed.
  • the solution is a solution in which a platinum compound is dissolved in a solvent.
  • the solvent is, for example, a liquid obtained by mixing ethylene glycol monoethyl ether, hydrochloric acid, and ethanol.
  • the platinum compound is, for example, chloroplatinic acid, but is not limited to this, and may be, for example, platinum chloride or the like.
  • the method for forming the intermediate layer 3 is not limited to the above-mentioned example, and may be, for example, a vapor deposition method, a sputtering method, a CVD method, a plating method, or the like.
  • the composite layer 4 (see FIG. 3D) is formed on the intermediate layer 3.
  • the composite layer forming step includes a laminate forming step and a firing step.
  • the first step of the first specified number of times (for example, four times) and the second step of the second specified number of times (for example, four times) are alternately repeated once, thereby forming a conductive substrate.
  • a laminated body 400 (see FIG. 3C), which is a base of the composite layer 4, is formed on the intermediate layer 3 on the 2.
  • a solution containing the tantalum compound which is the source of the tantalum layer 41 (hereinafter referred to as the first solution) is applied, and then heat-dried under the first condition without natural drying (drying treatment).
  • the first solution is a solution in which a tantalum compound is dissolved in a solvent (hereinafter referred to as a first solvent).
  • the first solvent is, for example, a liquid in which ethylene glycol monoethyl ether, hydrochloric acid, and ethanol are mixed.
  • the tantalum compound is, for example, tantalum chloride, but is not limited to this, and may be, for example, tantalum ethoxide or the like.
  • the metal concentration (tantalum concentration) of the first solution is, for example, 26 mg / L.
  • the coating amount of the first solution is, for example, 1 ⁇ L / cm 2 .
  • the first condition includes a heat treatment temperature and a heat treatment time.
  • the heat treatment temperature under the first condition is, for example, 100 ° C. to 400 ° C., and 220 ° C. as an example.
  • the heat treatment time under the first condition is, for example, 5 minutes to 15 minutes, and 10 minutes as an example.
  • a solution containing a platinum compound and an iridium compound, which is the source of the catalyst layer 42 is applied (hereinafter referred to as a second solution), and then heat-dried under the second condition without natural drying.
  • a second solution is a solution in which a platinum compound and an iridium compound are dissolved in a solvent (hereinafter referred to as a second solvent).
  • the second solvent is, for example, a liquid obtained by mixing ethylene glycol monoethyl ether, hydrochloric acid, and ethanol.
  • the platinum compound is, for example, chloroplatinic acid, but is not limited to this, and may be, for example, platinum chloride or the like.
  • the iridium compound is, for example, iridium chloride, but is not limited to this, and may be, for example, iridium chloride, iridium nitrate, or the like.
  • the metal concentration of the second solution (total concentration of platinum and iridium) is, for example, 26 mg / L.
  • the coating amount of the second solution is, for example, 2 ⁇ L / cm 2 .
  • the second condition includes a heat treatment temperature and a heat treatment time.
  • the heat treatment temperature under the second condition is, for example, 100 ° C. to 400 ° C., and 220 ° C. as an example.
  • the heat treatment time under the second condition is, for example, 5 minutes to 15 minutes, and 10 minutes as an example.
  • the composite layer 4 and a plurality of cracks (recesses 5) are formed by performing a heat treatment in which the laminated body 400 is fired under predetermined firing conditions (see FIG. 3D).
  • the firing conditions include a firing temperature and a firing time.
  • the firing temperature is, for example, 500 ° C. to 700 ° C., for example, 560 ° C.
  • the firing time is, for example, 10 to 20 minutes, for example, 15 minutes.
  • the shapes of the plurality of cracks (recesses 5) are different from each other. Further, the crack may be formed along the thickness direction of the composite layer 4, or may be bent in the middle of the composite layer 4.
  • Example FIG. 4 shows the molar ratio of platinum (Pt), iridium (Ir), and tantalum (Ta) in the composite layer 4 with respect to the electrode 1 for electrolysis, and the number of layers of the laminated structure of the composite layer 4 (tantalum layer). It is a graph which shows the result of having performed the durability test about the following 9 kinds of Examples 1 to 9 which changed the total number of layers of 41 layers and the catalyst layer 42, etc.
  • the durability test is an accelerated test.
  • two electrolytic electrodes 1 prepared under the same conditions are used as a pair of electrodes, and the pair of electrodes are immersed in salt water in an electrolytic cell of a durability test facility, and initial aging is performed by energizing the pair of electrodes. After that, every time the pair of electrodes are continuously energized for a predetermined time, the pair of electrodes are immersed in salt water in an electrolytic cell for measuring chlorine concentration and energized for a predetermined time (3 minutes). The chlorine concentration (average value) of was measured.
  • the electrolytic cell of the durability test facility has a salt water supply port and a drainage port.
  • salt water is added so that the conductivity of the salt water in the electrolytic cell of the durability test facility becomes 1650 ⁇ 200 ⁇ S / m. Further, in the durability test, tap water is drained while constantly being supplied to the electrolytic cell of the durability test facility at a flow rate of 2 L / min.
  • the salt water supplied to the electrolytic cell of the durability test facility is a salt solution produced by dissolving salt (sodium chloride) in tap water.
  • the current value of the energizing current in the durability test is 400 mA.
  • salt water in the electrolytic cell for measuring the chlorine concentration salt water produced by dissolving 4.5 g of salt (sodium chloride) in 800 mL of pure water was used.
  • the current value of the energizing current in the chlorine concentration measurement is 400 mA.
  • the polarity reversal means that the combination of the anode and the cathode in the pair of electrodes is reversed.
  • polarity reversal means changing the electrode used as the anode and the electrode used as the cathode on the high potential side of the pair of electrodes so that they are the cathode and the anode, respectively. means.
  • the horizontal axis in FIG. 4 is the durability test time (elapsed time) after the initial aging.
  • the vertical axis of FIG. 4 is the chlorine concentration. Chlorine generated near the anode contributes to the production of hypochlorous acid, so the chlorine concentration is roughly determined by the amount of chlorine generated per unit time.
  • FIGS. 5A, 5B, 5C and 5D The estimation mechanism for improving the durability of the electrolytic electrode 1 according to the first embodiment will be described with reference to FIGS. 5A, 5B, 5C and 5D.
  • the order of FIGS. 5A, 5B, 5C and 5D is in chronological order.
  • the surface forming a part of the inner peripheral surface of the recess 5 in each of the main surface 40 of the composite layer 4 and the plurality (4) catalyst layers 42 is salt water.
  • Each of the plurality (4) catalyst layers 42 can contribute to the generation of chlorine by being in contact with the catalyst layer 42.
  • FIG. 5B shows a state in which the uppermost catalyst layer 42 (fourth catalyst layer 424) has disappeared in the electrode 1 for electrolysis of FIG. 5A.
  • the surfaces forming a part of the inner peripheral surface of the recess 5 in each of the plurality (three) catalyst layers 42 come into contact with salt water, so that each of the plurality (three) catalyst layers 42 becomes , Can contribute to the generation of chlorine.
  • FIG. 5C shows a state in which a part of each of the plurality (three) catalyst layers 42 disappears in the in-plane direction from the state of FIG. 5B.
  • the in-plane direction is a direction orthogonal to the thickness direction D1 of the conductive substrate 2. That is, the in-plane direction is the direction along the first main surface 21 of the conductive substrate 2.
  • each of the plurality (three) catalyst layers 42 can contribute to the generation of chlorine by contacting the surface on the recess 5 side with the salt water. ..
  • FIG. 5D shows the tantalum layer 41 (fourth tantalum layer 414) on the catalyst layer 42 (third catalyst layer 423) farthest from the conductive substrate 2 among the plurality (three) catalyst layers 42 from the state of FIG. 5C. Is a state in which a part of is disappeared in the in-plane direction.
  • the main surface of the third catalyst layer 423 on the fourth tantalum layer 414 side and the surface of the plurality (three) catalyst layers 42 on the recess 5 side are in contact with salt water, so that the plurality (three) Each of the catalyst layers 42 of the above can contribute to the generation of chlorine.
  • At least one catalyst layer 42 can contribute to the generation of chlorine even if the state changes as described above. As a result, the durability of the electrode 1 for electrolysis according to the first embodiment is improved.
  • the electrolytic electrode 1 according to the first embodiment is provided with a composite layer 4 in which a plurality of tantalum layers 41 and a plurality of catalyst layers 42 are alternately arranged one by one, thereby suppressing peeling of the composite layer 4. It becomes possible to do. Further, the electrolytic electrode 1 according to the first embodiment is provided with the above-mentioned composite layer 4, so that the consumption of the composite layer 4 at the time of use can be suppressed. Further, the electrolysis electrode 1 according to the first embodiment can suppress the aggregation of iridium by providing the above-mentioned composite layer 4.
  • the electrode 1 for electrolysis according to the first embodiment with a plurality of recesses 5, the area of the surface of the composite layer 4 that contributes to the generation of chlorine is increased, and the efficiency of chlorine generation can be improved. Become.
  • the electrolysis electrode 1a according to the second embodiment is substantially the same as the electrolysis electrode 1 according to the first embodiment.
  • the depths of the plurality of recesses 5 are different from the depths of the plurality of recesses 5 in the electrolysis electrode 1 according to the first embodiment.
  • the same components as the electrolytic electrode 1 according to the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.
  • the depth of each of the plurality of recesses 5 in the electrolytic electrode 1a according to the second embodiment is a distance L3 or less between the main surface 40 of the composite layer 4 and the lowest layer (first tantalum layer 411) of the composite layer 4.
  • the conductive substrate 2 is prepared, and then the roughening step, the intermediate layer forming step, and the composite layer forming step are sequentially performed.
  • the first main surface 21 of the conductive substrate 2 is roughened by immersing the conductive substrate 2 in an oxalic acid aqueous solution.
  • the roughening step is not an essential step.
  • the intermediate layer 3 is formed on the first main surface 21 of the conductive substrate 2 (see FIG. 7B).
  • the composite layer 4 (see FIG. 7E) is formed on the intermediate layer 3.
  • the composite layer forming step includes a first step, a second step, and a third step.
  • a solution containing tantalum which is the source of the tantalum layer 41, is applied onto the intermediate layer 3 and then fired to obtain the lowest tantalum in the laminated structure of the composite layer 4 among the plurality of tantalum layers 41.
  • Layer 41 is formed (see FIG. 7C).
  • the solution is, for example, a solution in which a tantalum compound is dissolved in a solvent. That is, the solution contains tantalum.
  • the solvent is, for example, a liquid obtained by mixing ethylene glycol monoethyl ether, hydrochloric acid, and ethanol.
  • the tantalum compound is, for example, tantalum chloride, but is not limited to this, and may be, for example, tantalum ethoxide or the like.
  • the tantalum layer 41 is not a layer formed by tantalum oxide but a layer formed by tantalum, for example, a solution in which a tantalum element is dissolved in a solvent may be used as a solution.
  • the metal concentration (tantalum concentration) of the solution is, for example, 26 mg / L.
  • the coating amount of the solution is, for example, 1 ⁇ L / cm 2 .
  • the firing conditions include a firing temperature (first specified temperature) and a firing time.
  • the firing temperature is, for example, 500 ° C. to 700 ° C., for example, 560 ° C.
  • the firing time is, for example, 10 to 20 minutes, for example, 15 minutes.
  • the second step by repeating the first step of the first specified number of times (for example, four times) and the second step of the second specified number of times (for example, three times), the lowest layer in the laminated structure of the composite layer 4 is formed.
  • a laminated body 401 that is the basis of a portion other than the tantalum layer 41 is formed (see FIG. 7D).
  • a second solution containing a platinum compound and an iridium compound, which is the source of the catalyst layer 42 is applied, and then heat-dried under the second condition without natural drying (drying).
  • the second material layer 420 which is the source of one of the plurality of catalyst layers 42 is formed.
  • the second solution is a solution containing platinum and iridium.
  • the second solution is applied on the exposed layer on the first main surface 21 side of the conductive substrate 2 (for example, the lowermost tantalum layer 41, the first material layer 410 described later).
  • the second condition includes a heat treatment temperature and a heat treatment time.
  • the heat treatment temperature (second specified temperature) under the second condition is, for example, 100 ° C. to 400 ° C., and 220 ° C. as an example.
  • the heat treatment time under the second condition is, for example, 5 minutes to 15 minutes, and 10 minutes as an example.
  • a first solution containing the tantalum compound that is the source of the tantalum layer 41 is applied, and then heat treatment (drying treatment) is performed in which the tantalum compound is heat-dried under the first condition without being naturally dried.
  • the first solution is a solution containing tantalum.
  • the first solution is applied on the exposed layer (second material layer 420) on the first main surface 21 side of the conductive substrate 2.
  • the first condition includes a heat treatment temperature and a heat treatment time.
  • the heat treatment temperature (third specified temperature) under the first condition is, for example, 100 ° C. to 400 ° C., and 220 ° C. as an example.
  • the heat treatment time under the first condition is, for example, 5 minutes to 15 minutes, and 10 minutes as an example.
  • the laminate 401 is fired at a specified temperature (fourth specified temperature) to form a tantalum layer 41 other than the lowermost tantalum layer 41 among the plurality of catalyst layers 42 and the plurality of tantalum layers 41.
  • a plurality of cracks (recesses 5) recessed from the main surface 40 on the side opposite to the intermediate layer 3 side in the catalyst layer 42 are formed (see FIG. 7E).
  • Embodiments 1 and 2 are only one of the various embodiments of the present disclosure.
  • the embodiment can be changed in various ways depending on the design and the like as long as the object of the present disclosure can be achieved.
  • plan view shape of the conductive substrate 2 is not limited to a rectangular shape, and may be, for example, a square shape.
  • the number of each of the tantalum layer 41 and the catalyst layer 42 in the composite layer 4 is not limited to four, and may be, for example, two or three, or five or more. Further, in the composite layer 4, the number of the tantalum layers 41 and the number of the catalyst layers 42 are not limited to the same, but may be different.
  • the thicknesses of the plurality of tantalum layers 41 are not limited to the same, and may be different from each other, for example, and some of the plurality of tantalum layers 41 have the same thickness and remain. The thickness of the tantalum layer 41 may be different.
  • the thicknesses of the plurality of catalyst layers 42 are not limited to the same, and may be different from each other, for example, and some of the catalyst layers 42 of the plurality of catalyst layers 42 have the same thickness and remain. The thickness of the catalyst layer 42 may be different.
  • the plurality of tantalum layers 41 are not limited to having the same composition as each other, and may have different compositions from each other, for example.
  • the plurality of catalyst layers 42 are not limited to having the same composition as each other, and may have different compositions, for example.
  • each of the plurality of catalyst layers 42 is a porous layer, and for example, at least among the remaining catalyst layers 42 other than the uppermost catalyst layer 42 among the plurality of catalyst layers 42.
  • One catalyst layer 42 may be a porous layer.
  • each of the plurality of catalyst layers 42 may be a non-porous layer.
  • the shapes of the plurality of recesses 5 may be the same as each other.
  • a plurality of recesses 5 may be formed by using an etching technique, a laser processing technique, or the like.
  • the composite layer 4 has a plurality of recesses 5 recessed from the main surface 40 on the side opposite to the intermediate layer 3 side, the composite layer 4 has a plurality of recesses 5 as in the electrolytic electrode 1b according to one modification shown in FIG.
  • the uppermost layer may be the tantalum layer 41.
  • the same components as those of the electrolytic electrode 1 are designated by the same reference numerals, and the description thereof will be omitted.
  • the depth of each of the plurality of recesses 5 is such that the depth penetrates at least one of the plurality of catalyst layers 42. is there. From the viewpoint of increasing the chlorine generation efficiency, it is more preferable that the depth of each of the plurality of recesses 5 is a depth that penetrates the plurality of catalyst layers 42.
  • one of the plurality of tantalum layers 41 is the lowest layer in which one tantalum layer 41 is in contact with one main surface 21 of the conductive substrate 2 without interposing the intermediate layer 3, and the plurality of catalyst layers 42.
  • One of the catalyst layers 42 may be the uppermost layer farthest from the conductive substrate 2.
  • the electrode for electrolysis (1; 1a) includes a conductive substrate (2), an intermediate layer (3), and a composite layer (4).
  • the conductive substrate (2) contains at least titanium.
  • the intermediate layer (3) is provided on one main surface (21) of the conductive substrate (2).
  • the composite layer (4) is provided on the intermediate layer (3).
  • the composite layer (4) has a plurality of tantalum layers (41) and a plurality of catalyst layers (42).
  • Each of the plurality of tantalum layers (41) is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • Each of the plurality of catalyst layers (42) contains platinum and iridium.
  • a plurality of tantalum layers (41) and a plurality of catalyst layers (42) are alternately arranged one by one in the thickness direction (D1) of the conductive substrate (2).
  • one tantalum layer (41) out of the plurality of tantalum layers (41) is the lowest layer closest to one main surface (21) of the conductive substrate (2), and the plurality of catalyst layers.
  • One of the catalyst layers (42) of (42) is the uppermost layer farthest from the conductive substrate (2).
  • the electrolysis electrode (1; 1a) has a plurality of recesses recessed from the main surface (40) opposite to the intermediate layer (3) side in the composite layer (4). It has (5).
  • the depth of each of the plurality of recesses (5) is the catalyst layer 42 (third) which is the second farthest from the conductive substrate (2) among the main surface (40) of the composite layer (4) and the plurality of catalyst layers (42). It is larger than the distance (L1) from the three catalyst layers 423) and less than or equal to the distance (L2) between the main surface (40) of the composite layer (4) and the intermediate layer (3).
  • the catalyst layer (third catalyst layer 423) which is the second farthest from the conductive substrate (2) among the plurality of catalyst layers (42), also generates chlorine. Since it can contribute, the plurality of catalyst layers (42) can be gradually consumed from each side surface of the plurality of recesses (5), and thus the ratio of iridium in each of the plurality of catalyst layers (42). By changing at least one of the number of the catalyst layer (42) and the number of the catalyst layer (42), it is possible to efficiently consume the catalyst layer (42) and improve the chlorine generation efficiency while improving the durability.
  • the depths of the plurality of recesses (5) are the main surface (40) and the bottom layer (first) of the composite layer (4). It is less than or equal to the distance (L3) from the tantalum layer 411).
  • each of the plurality of recesses (5) is a linear crack in a plan view from the thickness direction (D1). is there.
  • the catalyst layer (42) farther from the conductive substrate (2) is more likely to contribute to chlorine generation, and the plurality of catalysts Of the layers (42), the catalyst layer (42) closer to the conductive substrate (2) is less likely to be consumed, so that durability can be improved.
  • the width (H1) of each of the plurality of recesses (5) is 0.3 ⁇ m or more and 3 ⁇ m or less.
  • the main surface (40) of the composite layer (4) is viewed in a plan view from the thickness direction (D1) of the conductive substrate. ) Is S1, and the total area of the opening areas of the plurality of recesses (5) on the main surface (40) of the composite layer (4) is S2, the ratio of S2 to S1 + S2 is 5% to 50. %.
  • the electrode for electrolysis (1; 1a) in the seventh aspect, in the sixth aspect, 0 out of the plurality of recesses (5) in a plan view from the thickness direction (D1) of the conductive substrate (2).
  • the total length of the opening edges of the portions existing in the .01 mm 2 square region is 1 mm or more.
  • each of the plurality of catalyst layers (42) is a porous layer.
  • the electrode for electrolysis (1; 1a) according to the eighth aspect it is possible to improve the durability.
  • one main surface (21) of the conductive substrate (2) is a rough surface.
  • the electrode for electrolysis (1; 1a) it is possible to improve the adhesion between the conductive substrate (2) and the intermediate layer (3), and the composite layer (4) is the conductive substrate (4). 2) It is possible to suppress peeling from the side.
  • the method for manufacturing the electrode (1a) for electrolysis according to the tenth aspect includes an intermediate layer forming step and a composite layer forming step.
  • the intermediate layer forming step is a step of forming the intermediate layer (3) on one main surface (21) of the conductive substrate (2) containing at least titanium.
  • the composite layer forming step is a step of forming a composite layer (4) on the intermediate layer (3).
  • the composite layer (4) has a laminated structure in which a plurality of tantalum layers (41) and a plurality of catalyst layers (42) are alternately arranged one by one. Each of the plurality of tantalum layers (41) is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • the composite layer forming step includes a first step, a second step, and a third step.
  • a solution containing tantalum is applied onto the intermediate layer (3) and then fired at a first specified temperature to obtain the lowest tantalum layer (41) in the laminated structure among the plurality of tantalum layers (41). ) Is formed.
  • the second step by repeating the first step and the second step, a laminated body (401) which is a base of a portion other than the lowermost tantalum layer (41) in the laminated structure is formed.
  • first step a solution containing platinum and iridium is applied and then heated and dried at a second specified temperature to form a layer (first layer) which is the source of one of the plurality of catalyst layers (42). 2 Material layer 420) is formed.
  • second step one tantalum layer (41) other than the lowermost tantalum layer (41) among the plurality of tantalum layers (41) is applied by applying a solution containing tantalum and then heating and drying at a third specified temperature. (First material layer 410) is formed.
  • the laminate (401) is fired at a fourth specified temperature, which is higher than both the second specified temperature and the third specified temperature, so that a plurality of catalyst layers (42) and a plurality of tantalum layers ( Of the 41), the tantalum layer (41) other than the lowest tantalum layer (41) is formed, and the catalyst layer (42) is recessed from the main surface (40) opposite to the intermediate layer (3) side.
  • a plurality of cracks (recesses 5) are formed.
  • the electrode for electrolysis (1b) includes a conductive substrate (2), an intermediate layer (3), and a composite layer (4).
  • the conductive substrate (2) contains at least titanium.
  • the intermediate layer (3) is provided on one main surface (21) of the conductive substrate (2).
  • the composite layer (4) is provided on the intermediate layer (3).
  • the composite layer (4) has a plurality of tantalum layers (41) and a plurality of catalyst layers (42). Each of the plurality of catalyst layers (42) contains platinum and iridium.
  • Each of the plurality of tantalum layers (41) is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • a plurality of tantalum layers (41) and a plurality of catalyst layers (42) are alternately arranged one by one in the thickness direction (D1) of the conductive substrate (2).
  • one tantalum layer (41) out of the plurality of tantalum layers (41) is the lowest layer closest to one main surface (21) of the conductive substrate (2), and the plurality of tantalum layers
  • the other tantalum layer (41) of (41) is the uppermost layer farthest from the conductive substrate (2).
  • the electrode for electrolysis (1; 1a) has a plurality of recesses (5) recessed from the main surface (40) on the side opposite to the intermediate layer (3) side in the composite layer (4).
  • the depth of each of the plurality of recesses (5) is a depth that penetrates at least one catalyst layer (42) among the plurality of catalyst layers (42).
  • the electrode for electrolysis (1b) according to the eleventh aspect can suppress peeling of the composite layer (4).
  • the electrode for electrolysis (1; 1a) includes a conductive substrate (2), an intermediate layer (3), and a composite layer (4).
  • the conductive substrate (2) contains at least titanium.
  • the intermediate layer (3) is provided on one main surface (21) of the conductive substrate (2).
  • the composite layer (4) is provided on the intermediate layer (3).
  • the composite layer (4) has a plurality of tantalum layers (41) and a plurality of catalyst layers (42).
  • Each of the plurality of tantalum layers (41) is formed of tantalum oxide, tantalum, or a mixture of tantalum oxide and tantalum.
  • Each of the plurality of catalyst layers (42) contains platinum and iridium.
  • a plurality of tantalum layers (41) and a plurality of catalyst layers (42) are alternately arranged one by one in the thickness direction (D1) of the conductive substrate (2).
  • the tantalum layer (41) is the lowest layer closest to one main surface (21) of the conductive substrate (2), and the catalyst layer (42) is the farthest from the conductive substrate (2). It is the top layer.
  • Electrodes for electrolysis 2 Conductive substrate 21 One main surface 3 Intermediate layer 4
  • Composite layer 40 Main surface 41 Tantalum layer 42
  • Catalyst layer 5 Recessed 401 Laminated body L1 Distance L2 Distance L3 Distance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
PCT/JP2020/013021 2019-04-26 2020-03-24 電解用電極及び電解用電極の製造方法 WO2020217817A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/604,426 US20220178034A1 (en) 2019-04-26 2020-03-24 Electrode for electrolysis, and method for producing electrode for electrolysis
JP2021515887A JP7194911B2 (ja) 2019-04-26 2020-03-24 電解用電極及び電解用電極の製造方法
CN202080031703.4A CN113795612A (zh) 2019-04-26 2020-03-24 电解用电极和制造电解用电极的方法
EP20796016.2A EP3960905A4 (de) 2019-04-26 2020-03-24 Elektrode für elektrolyse und verfahren zur herstellung einer elektrode für elektrolyse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-086733 2019-04-26
JP2019086733 2019-04-26

Publications (1)

Publication Number Publication Date
WO2020217817A1 true WO2020217817A1 (ja) 2020-10-29

Family

ID=72942599

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/013021 WO2020217817A1 (ja) 2019-04-26 2020-03-24 電解用電極及び電解用電極の製造方法

Country Status (5)

Country Link
US (1) US20220178034A1 (de)
EP (1) EP3960905A4 (de)
JP (1) JP7194911B2 (de)
CN (1) CN113795612A (de)
WO (1) WO2020217817A1 (de)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006322026A (ja) * 2005-05-18 2006-11-30 Furuya Kinzoku:Kk 電解的水処理電極及び装置
JP2009052069A (ja) 2007-08-24 2009-03-12 Ishifuku Metal Ind Co Ltd 電解用電極
CN101435084A (zh) * 2008-12-04 2009-05-20 福州大学 具有交替叠层结构涂层钛阳极及其制备方法
JP2009195884A (ja) * 2008-02-25 2009-09-03 Purotekku:Kk 電解水生成装置
CN107051431A (zh) * 2017-04-10 2017-08-18 广东卓信环境科技股份有限公司 一种用于析氯电极的活性涂液及其制备方法
JP2018104790A (ja) * 2016-12-28 2018-07-05 Toto株式会社 電解用電極および水回り機器

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3378918D1 (en) * 1982-10-29 1989-02-16 Ici Plc Electrodes, methods of manufacturing such electrodes and use of such electrodes in electrolytic cells
JP2931812B1 (ja) * 1998-04-24 1999-08-09 ティーディーケイ株式会社 電解用電極およびその製造方法
CN106367777B (zh) * 2016-12-14 2018-09-04 青岛双瑞海洋环境工程股份有限公司 适用于低盐度海水环境的氧化物阳极材料及制备工艺

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006322026A (ja) * 2005-05-18 2006-11-30 Furuya Kinzoku:Kk 電解的水処理電極及び装置
JP2009052069A (ja) 2007-08-24 2009-03-12 Ishifuku Metal Ind Co Ltd 電解用電極
JP2009195884A (ja) * 2008-02-25 2009-09-03 Purotekku:Kk 電解水生成装置
CN101435084A (zh) * 2008-12-04 2009-05-20 福州大学 具有交替叠层结构涂层钛阳极及其制备方法
JP2018104790A (ja) * 2016-12-28 2018-07-05 Toto株式会社 電解用電極および水回り機器
CN107051431A (zh) * 2017-04-10 2017-08-18 广东卓信环境科技股份有限公司 一种用于析氯电极的活性涂液及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3960905A4

Also Published As

Publication number Publication date
JPWO2020217817A1 (de) 2020-10-29
EP3960905A4 (de) 2022-08-03
CN113795612A (zh) 2021-12-14
EP3960905A1 (de) 2022-03-02
US20220178034A1 (en) 2022-06-09
JP7194911B2 (ja) 2022-12-23

Similar Documents

Publication Publication Date Title
WO2021117311A1 (ja) 電解用電極
US8580091B2 (en) Multi-layer mixed metal oxide electrode and method for making same
JP4972991B2 (ja) 酸素発生用電極
JP2009197284A (ja) 電極及びその製造方法
KR20040098575A (ko) 전해용 전극 및 이의 제조방법
EP0955395B1 (de) Elektrode für Elektrolyse und deren Herstellungsverfahren
WO2020217817A1 (ja) 電解用電極及び電解用電極の製造方法
JP2020180315A (ja) 電解用電極
RU2007132164A (ru) Высокоэффективное анодное покрытие для получения гипохлорита
KR101199669B1 (ko) 전기분해장치용 양극 제조방법
JP2007302925A (ja) 酸素発生用電極
JP5317012B2 (ja) 低水素過電圧陰極の製法
JP2004360067A (ja) 電解用電極及びその製造方法
JP2008156684A (ja) 塩酸電解用の陽極電極
WO2023188704A1 (ja) 電解用電極
JP2024502947A (ja) 電気塩素化方法のための電解槽および自己洗浄型電気塩素化システム
US20230257893A1 (en) Current Reversal Tolerant Multilayer Material, Method of Making the Same, Use as an Electrode, and Use in Electrochemical Processes
JP2007287362A (ja) 燃料電池構成部品及びその製造方法
WO2023188991A1 (ja) 電解用電極及び次亜塩素酸発生機器
JP5359133B2 (ja) 酸素発生用電極
JP7391661B2 (ja) 交流エッチング方法
WO2023188992A1 (ja) 電解用電極及び次亜塩素酸発生機器
JP2020139225A (ja) 電解用電極、及び電解用電極の製造方法
FI63784B (fi) Oloeslig elektrod omfattande ett skikt av aedelmetall och foerfarande foer dess framstaellning
JP3780410B2 (ja) 金属メッキ用電極

Legal Events

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

Ref document number: 20796016

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021515887

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020796016

Country of ref document: EP

Effective date: 20211126