WO2013100165A2 - Anode for oxygen generation and manufacturing method for the same - Google Patents
Anode for oxygen generation and manufacturing method for the same Download PDFInfo
- Publication number
- WO2013100165A2 WO2013100165A2 PCT/JP2012/084263 JP2012084263W WO2013100165A2 WO 2013100165 A2 WO2013100165 A2 WO 2013100165A2 JP 2012084263 W JP2012084263 W JP 2012084263W WO 2013100165 A2 WO2013100165 A2 WO 2013100165A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst layer
- iridium oxide
- metal substrate
- electrode
- conductive metal
- Prior art date
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 51
- 239000001301 oxygen Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 103
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims description 132
- 238000000034 method Methods 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000007733 ion plating Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 26
- 238000000576 coating method Methods 0.000 abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011889 copper foil Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000011888 foil Substances 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 description 43
- 239000000047 product Substances 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 229910001362 Ta alloys Inorganic materials 0.000 description 5
- 229910052924 anglesite Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical group 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical class [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical group O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- -1 titanium Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C25B11/04—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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- 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
- the present invention relates to an anode for oxygen generation used for various industrial electrolyses and a manufacturing method for the same; more in detail, it relates to a high-load durable anode for oxygen generation and a manufacturing method for the same used for industrial electrolyses including manufacturing of electrolytic metal foils such as electrolytic copper foil, aluminum liquid contact, and continuously electrogalvanized steel plate, and metal extraction.
- electrolytic metal foils such as electrolytic copper foil, aluminum liquid contact, and continuously electrogalvanized steel plate, and metal extraction.
- Mixing of lead ions in the electrolytic cell is often seen in various types of industrial electrolysis.
- Mixing of lead compounds in the production of electrolytic copper foil as its typical example is derived from the following two points: that is, sticking to, as a lead alloy, a scrap copper which is one of the raw materials of copper sulfate in electrolyte, and before DSE (registered trademark of Permelec Electrode Ltd.) type of electrode being used, lead-antimony electrodes were used, this time of leaching lead ions become lead sulfate particles and residue in electrolytic cell.
- DSE registered trademark of Permelec Electrode Ltd.
- High purity electrolytic copper is best for raw materials, but in a practical manner, scrap copper which is recycled products is often used. Copper raw material is leached as copper ion by using concentrated sulfuric acid as an immersion liquid, or the copper raw material is compulsory eluted as anode for a short time. In an anodic dissolution, elution becomes easy from the complex morphology of clad metals and other metal parts. In a scrap copper, wax materials such as lead soldering material is adhered, and other metals included in the wax materials or the clad is eluted with elution of copper in the electrolyte of a sulfuric acid-copper sulfate, or is mixed as floating particles.
- lead ion is high corrosion resistance to sulfuric acid, but a small amount of it is dissolved in a concentrated sulfuric acid, and such lead ion crystallizes as a minute particle of lead sulfate in electrolyte and floats under a lower temperature than that in dissolving and a high pH conditions.
- lead sulfate, PbS0 4 is a water-insoluble salt in which a solubility product is 1.06 * 10 "8 mol/L (18°C), and is extremely small in which a solubility in 0% sulfuric acid and 25°C is approximately 7mg/L.
- oxidized Iead-P-Pb0 2 has a small electrode catalyst function, a total surface of an electrode is covered by it, although an electrode potential increases, an electrolysis continuously occurs and an electrode life as a coating to protect the electrode is prolonged, but if it is partially peeled off, an original electrode catalyst layer of which catalyst activity is high, is exposed, and therefore an electrolysis current of it increases and an unevenness of a foil thickness of copper foil growing on an opposite cathode drum is caused.
- an insoluble electrode comprising a conductive metal substrate, such as titanium, covered with a catalyst layer containing precious metal or precious metal oxide has been applied.
- PTL 1 discloses an insoluble electrode prepared in such a manner that a catalyst layer containing iridium oxide and valve metal oxide is coated on a substrate of conductive metals, such as titanium, heated in oxidizing atmosphere and baked at a temperature of 650°C - 850°C, to crystallize valve metal oxide partially.
- This electrode has the following drawbacks.
- the metal substrate such as of titanium causes interfacial corrosion, and becomes poor conductor, causing oxygen overvoltage to increase to an unserviceable degree as electrode.
- the crystallite diameter of iridium oxide in the catalyst layer enlarges, resulting in decreased an electrode effective surface area of the catalyst layer, leading to a poor catalytic activity.
- PTL 2 discloses use of an anode for copper plating and copper foil manufacturing prepared in such a manner that a catalyst layer comprising amorphous iridium oxide and amorphous tantalum oxide in a mixed state is provided on a substrate of conductive metal, such as titanium.
- This electrode features amorphous iridium oxide, and is insufficient in electrode durability.
- the reason why durability decreases when amorphous iridium oxide is applied is that amorphous iridium oxide shows unstable bonding between iridium and oxygen, compared with crystalline iridium oxide.
- PTL 3 discloses an electrode coated with a catalyst layer comprising a double layer structure by a lower layer of crystalline iridium oxide and an upper layer of amorphous iridium oxide, in order to suppress consumption of the catalyst layer and to enhance durability of the electrode.
- the electrode disclosed by PTL 3 is insufficient in electrode durability because the upper layer of the catalyst layer is amorphous iridium oxide.
- crystalline iridium oxide exists only in the lower layer, not uniformly distributed over the entire catalyst layer, resulting in insufficient electrode durability.
- PTL 4 discloses an anode for zinc electrowinning in which a catalyst layer containing amorphous iridium oxide as a prerequisite and crystalline iridium oxide, as a mixed state is provided on a substrate of conductive metal like titanium.
- PTL 5 discloses an anode for cobalt electrowinning in which a catalyst layer containing amorphous iridium oxide as a prerequisite and crystalline iridium oxide, as a mixed state is provided on a substrate of conductive metal like titanium.
- electrode durability of these two electrodes is not enough because they contain a large amount of amorphous iridium oxide, as a prerequisite.
- the present invention aims to provide an anode for oxygen generation and a manufacturing method for the same, which can reduce the oxygen overvoltage of the anode for oxygen evolution to use for production of an electrode for industrial electrolysis to coat the electrolysis active substance layer particularly the electrolysis copper foil and metal winning by the electrolytic method and control adhesion, coating of the lead dioxide to the anode and raise the durability.
- the present invention provides an anode for oxygen generation comprising a conductive metal substrate and a catalyst layer containing iridium oxide formed on the conductive metal substrate, wherein the coating is baked in a low temperature region of 370°C - 400°C in an oxidation atmosphere to form the catalyst layer containing amorphous iridium oxide and the catalyst layer containing amorphous iridium oxide is post-baked in a further high temperature region of 520°C - 600°C in an oxidation atmosphere to crystallize almost all amount of iridium oxide in the catalyst layer.
- the present invention provides an anode for oxygen generation comprising a conductive metal substrate and a catalyst layer containing iridium oxide formed on the conductive metal substrate, wherein the degree of crystallinity of iridium oxide in the catalyst layer after the post-baking is made to be 60% or more.
- the present invention provides an anode for oxygen generation comprising a conductive metal substrate and a catalyst layer containing iridium oxide formed on the conductive metal substrate wherein the crystallite diameter of iridium oxide in the catalyst layer is 8.0nm or less.
- the present invention provides an anode for oxygen generation comprising a conductive metal substrate and a catalyst layer containing iridium oxide formed on the conductive metal substrate, wherein an arc ion plating (hereafter called AlP) base layer containing tantalum and titanium ingredients is formed by AlP process on the conductive metal substrate before the formation of the catalyst layer.
- AlP arc ion plating
- the present invention provides a manufacturing method for an anode for oxygen generation, wherein the catalyst layer containing amorphous iridium oxide is formed on the surface of the conductive metal substrate by baking in a low temperature region of 370°C - 400°C in an oxidation atmosphere and the catalyst layer containing amorphous iridium oxide is post-baked in a high temperature region of 520°C - 600°C in an oxidation atmosphere to crystallize almost all amount of iridium oxide in the catalyst layer.
- the present invention provides a manufacturing method for an anode for oxygen generation, wherein the catalyst layer containing amorphous iridium oxide is formed on the surface of the conductive metal substrate by baking in a low temperature region of 370°C - 400°C in an oxidation atmosphere and the catalyst layer containing amorphous iridium oxide is post-baked in a high temperature region of 520°C - 600°C in an oxidation atmosphere to make the degree of crystallinity of iridium oxide in the catalyst layer to be 60% or more.
- the present invention provides a manufacturing method for an anode for oxygen generation, wherein the catalyst layer containing amorphous iridium oxide is formed by baking in a low temperature region of 370°C - 400°C in an oxidation atmosphere and the catalyst layer containing amorphous iridium oxide is post-baked in a high temperature region of 520°C - 600°C in an oxidation atmosphere to make the crystallite diameter of iridium oxide in the catalyst layer to be 8.0nm or less.
- the present invention provides a manufacturing method for an anode for oxygen generation comprising a conductive metal substrate and a catalyst layer containing iridium oxide formed on the conductive metal substrate, wherein the AIP base layer containing tantalum and titanium ingredients is formed by the AIP process on the conductive metal substrate before the formation of the catalyst layer.
- baking is conducted, instead of the conventional repeated baking operations at 500°C or more, which are the perfect crystal deposition temperature, by two steps: baking in a low temperature region of 370°C - 400°C in an oxidation atmosphere to form a catalyst layer containing amorphous iridium oxide and post-baking in a high temperature region of 520°C - 600°C in an oxidation atmosphere to suppress the crystallite diameter of iridium oxide in the electrode catalyst layer preferably to 8.0nm or less and to crystallize most of the iridium oxide preferably to 60% or more in crystallinity.
- the growth of crystallite diameter of iridium oxide and coexistence of amorphous and crystalline iridium oxides was able to be suppressed and the electrode effective surface area of the catalyst layer was able to be increased.
- the growth of crystallite diameter of iridium oxide can be suppressed.
- the baking is conducted by two stages: first, coating and baking is repeated in a low temperature region of 370°C - 400°C in an oxidation atmosphere and then post-baking in a high temperature of 520°C - 600°C in an oxidation atmosphere. Compared with the baking at a high temperature from the beginning by the conventional method, crystallite diameter under the present invention will not enlarge beyond a certain degree.
- the current distribution is dispersed at the same time and the current concentration is suppressed and also wear rate of the catalyst layer by electrolysis can be suppressed, and then the durability of the electrode is improved.
- Fig. 1 is a graph indicating the change of degree of crystallinity of iridium oxide (Ir0 2 ) of the catalyst layer by baking temperature and post-bake temperature.
- Fig. 2 is a graph indicating the change of crystallite diameter of iridium oxide (Ir0 2 ) of the catalyst layer by baking temperature and post-bake temperature.
- Fig. 3 is a graph indicating the change of the electrostatic capacity of the electrode by baking temperature and post-bake temperature.
- Fig. 4 is a graph indicating the dependence of oxygen overvoltage on baking conditions.
- the present invention it is found that if the electrode effective surface area of the electrode catalyst layer is increased to suppress adhesive reaction of lead oxide to the electrode surface, oxygen generation overvoltage can be reduced and then, oxygen generation is promoted and at the same time the adhesive reaction of lead oxide can be suppressed.
- the present invention has been completed from the idea that it is necessary that iridium oxide of the catalyst layer is mainly crystalline in order to improve the electrode durability at the same time, and experiments were repeated.
- a two-step baking is performed, first, in a low temperature region of 370°C - 400°C in an oxidation atmosphere to form a catalyst layer containing amorphous Ir0 2 in the baking, then, in a high temperature region of 520°C - 600°C in an oxidation atmosphere to post-bake, through which the iridium oxide of the catalyst layer is almost crystallized.
- the catalyst layer containing amorphous iridium oxide which can greatly increase the electrode effective surface area, consumes amorphous iridium oxide quite rapidly by electrolysis and durability is reduced relatively. In other words, it is considered that the electrode durability cannot be improved unless iridium oxide of the catalyst layer is crystallized.
- the present invention applies two-step baking: low temperature baking plus high temperature post-baking in order to control the crystallite diameter of iridium oxide of the catalyst layer, through which iridium oxide crystal, smaller in size than the conventional product precipitates, resulting in increased the electrode effective surface area of the electrode catalyst layer and reduced overvoltage.
- a catalyst layer containing amorphous Iridium oxide is formed on the surface of the conductive metal substrate by baking in a low temperature region of 370°C - 400°C in an oxidation atmosphere; thereafter, the catalyst layer of amorphous iridium oxide is post-baked in a further high temperature region of 520°C - 600°C in an oxidation atmosphere to crystallize the almost iridium oxide in the catalyst layer.
- the coating amount of iridium oxide by the present invention is preferable to control to 2.0g/m 2 or less per time as a metal. This amount is determined by electrolytic conditions and an ordinal electrolysis is performed at a current density of 50A/dm 2 - 130A/dm 2 and in this case, a coating amount of iridium oxide of 1.0 - 2.0g/m 2 per time as a metal is used, and a coating times is ordinarily 10 - 15 times and a total amount is 10 - 30g/m 2 .
- the baking temperature in a low temperature region of 370°C - 400°C in an oxidation atmosphere and the post-baking temperature in a high temperature region of 520°C - 600°C in an oxidation atmosphere are determined by the crystal particle size and the degree of crystallinity of iridium oxide to be formed in the catalyst layer, and the catalyst layer with a low oxygen overvoltage and a high corrosion resistance is formed in the above-mentioned temperature region.
- the degree of crystallinity of the iridium oxide of the catalyst layer is preferably to 60% or more and if it being less than this value, the amorphous iridium oxide of the catalyst layer becomes more and the iridium oxide of the catalyst layer become unstable and a sufficient durability is not obtained.
- the crystallite diameter of iridium oxide in the catalyst layer is preferably equal to or less thanto 8.0nm and if it being more than this value, the electrode effective surface area iridium oxide of the catalyst layer becomes smaller and the oxygen generation overvoltage of the electrode increases and a reaction of generation of PbO 2 from lead ions is not suppressed.
- the AIP base layer comprising a valve metal base alloy containing crystalline tantalum and titanium components by AIP process on the conductive metal substrate. If the AIP base layer is provided on the conductive metal substrate, it is possible to prevent further interfacial corrosion of the metal substrate.
- the base layer consisting of TiTaO x oxide layer may be applied instead of the AIP base layer.
- the catalyst layer was formed in such a manner that hydrochloric acid aqueous solution of lrCl3/Ta 2 CI 5 as a coating liquid was coated on the AIP coated titanium substrate at 1.1 g - lr/m 2 per time and baked in a low temperature region of 370°C - 400°C.
- the electrode sample was prepared.
- the prepared sample was measured for Ir0 2 crystalline of the catalyst layer by X-ray diffraction, oxygen generation overvoltage, electrostatic capacity of electrode, etc. and evaluated for sulfuric acid electrolysis and gelatin-added sulfuric acid electrolysis and lead adherence test.
- the cleaned metal substrate of the electrode was set to the AIP unit applying Ti-Ta alloy target as a vapor source and a coating of tantalum and titanium alloy was applied as the base layer on the surface of the metal substrate of the electrode. Coating condition is shown in Table 1.
- the degree of crystallinity was estimated from the X-ray diffraction peak intensity.
- Electrolyte 150g/L H 2 S0 4 aq.
- Electrolysis area 10 x 10 mm 2
- Counter electrode Zr plate (20 mm * 70 mm)
- Electrolyte 150g/L H 2 SO 4 aq.
- Electrolysis area 10 x 10 mm 2
- Counter electrode Zr plate (20 mm ⁇ 70 mm)
- Electrolyte 100g/L H 2 S0 4 aq.
- Electrolysis area 20 ⁇ 20 mm 2
- Cathode Zr plate (20 20 mm)
- adhesion amount An anode regularly was taken out and adhesion amount was calculated by the anodic weight change.
- Fig. 1 is a graph showing the degree of crystallinity based on the data in Table 2
- Fig. 2 is a graph showing crystallite diameter based on the data in Table 2.
- the degree of crystallinity of samples of iridium oxide samples 2 - 4 and 6 - 8 by examples of the present invention after being post baked was more than 60%.
- a clear peak of lrO 2 belonging to an electrode catalyst layer by baking of 370°C and 390°C without post baking (samples 1 and 5) is not found and it is confirmed that the electrode catalysts of these examples are formed composed of amorphous lrO 2 .
- sample 9 which is conventional product is completely crystalized a degree of the crystallinity of the iridium oxide is 100% and the crystallite diameter became large and was 0.7nm.
- the change in crystallite diameter of lrO 2 by baking conditions was as shown in Table 2. It was found that the crystallite diameter of the sample after post baking was not changed due to the increase of post-baking temperature and it became smaller, compared with conventional products. That is, amorphous lrO 2 of the catalyst layer formed at a low temperature baking was crystallized by post-baking, but the growth of the crystallite diameter could be suppressed as compared with conventional products.
- Fig. 2 shows the graph that was created based on data for the crystallite diameter shown in Table 2. The amorphous lrO 2 was formed by baking at 370°C and 390°C without post-baking and the crystallite diameter was set to "0". It was also found that in case of a baking at more than 410°C without post baking, with increasing baking temperature, the crystallite diameter of lrO 2 was increased.
- amorphous lrO 2 formed by the baking of 370°C and 390°C was found to be crystallized, but the crystallite diameter was found to be smaller, with conventional products.
- the change of the crystallite diameter of lrO 2 due to an increase of post baking temperature was not nearly recognized.
- the crystallite size of the iridium oxide after post-baking of samples 2 - 4 and 6 - 8 according to the examples of the present invention was 8.0nm or less.
- Electrostatic capacity of the electrode calculated by the cyclic voltammetry method is shown in Table 2 and Fig. 3. Consequently, it is found that electrostatic capacity of the electrode (samples 2 - 4 and 6 - 8) formed by low temperature baking plus high post baking temperature electrostatic are increased, compared with the conventional product (sample 9), that is, the electrode effective surface area is also increased.
- Table 2 and Fig. 3 show that the degree of crystallinity and the crystallite diameter of the iridium oxide were not changed with the increase of the post baking temperature, but the electrode effective surface area of the electrode was decreased with the increase of the post baking temperature. The reason is considered that if a catalytic layer is post-baked at a high temperature, the catalytic layer became fine.
- the electrode effective surface area of the electrode baked at 370°C and 390°C and post baked was increased, compared with the conventional products and it was found that it is desirable for the goal of lowering the oxygen overvoltage.
- the surface of titanium plate (JIS-I) was subjected to the dry blast with iron grit (G120 size), followed by pickling in an aqueous solution of concentrated hydrochloric acid for 10 minutes at the boiling point for cleaning treatment of the metal substrate of the electrode.
- the cleaned metal substrate of the electrode is set to the AIP unit applying Ti-Ta alloy target as a vapor source and a coating of tantalum and titanium alloy was applied as the AIP base layer on the surface of the metal substrate of the electrode. Coating condition is shown in Table 1.
- the coated metal substrate was treated at 530°C in an electric furnace of air circulation type for 180 minutes.
- the coating solution prepared by dissolving iridium tetrachloride and tantalum pentachlonde in concentrated hydrochloric acid is applied on the coated metal substrate.
- the thermolysis coating was conducted for 15 minutes in the electric furnace of air circulation type at 370°C to form an electrode catalyst layer comprising mixture oxides of iridium oxide and tantalum oxide.
- the amount of coating solution was determined so that the thickness of coating per time of the coating solution corresponds to approx. 1.1g/m 2 , as iridium metal.
- This coating-baking operation was repeated twelve times to obtain the electrode catalyst layer of approx. 13.2g/m 2 , as iridium metal.
- the X-ray diffraction was carried out for this sample. A clear peak of iridium oxide attributable to the electrode catalyst layer was not observed, and the catalytic layer of this sample was composed of amorphous Ir0 2 .
- an electrode for electrolysis was manufactured in such a manner that the sample coated with the catalyst layer is post-baked in an electric furnace of air circulation type at 520°C for one hour.
- the X-ray diffraction was carried out for the sample after post-baking. A clear peak of iridium oxide attributable to the electrode catalyst layer was observed. From this, it has been found that an amorphous Ir0 2 was crystallized by a high temperature post baking. However, the intensity of the peak was smaller than that of Comparative Example 1 , and it was considered that an amorphous Ir0 2 was remained. Also the crystallite diameter calculated from X-ray diffraction peak was found to be smaller than that of Comparative Example 1.
- the electrode for evaluation was manufactured in the same manner as with Example 1 except that post-bake was conducted in an electric furnace of air circulation type for one hour at 560°C and the same electrolysis evaluation was performed.
- the X-ray diffraction performed after post-bake showed the degree of crystallinity and crystallite diameter of Ir0 2 in the catalyst layer equivalent to Example 1.
- an amount of a lead adhesion to the electrode of Example 2 is one-fourth to that of the Comparative Example 1 and a suppression effect of the lead adhesion was confirmed.
- the accelerated electrolysis life was increased to 80 % and their durability has also have been improved.
- the electrode for evaluation was manufactured in the same manner as with Example 1 except that post-bake was conducted in an electric furnace of air circulation type for one hour at 600°C and the same electrolysis evaluation was performed.
- the X-ray diffraction performed after post-bake showed the degree of crystallinity and crystallite diameter of Ir0 2 in the catalyst layer equivalent to Example 1 .
- the coating solution similar to Example 1 is coated on the tantalum and titanium alloy base coating layer and the heat-treated metal substrate similar to Example 1 , and after drying, the thermal decomposition is performed at the baking temperature in the electric furnace of circulation air type to 520°C and the baking time to fifteen minutes and then an electrode catalyst layer comprising a mixture oxide of iridium oxide and tantalum oxide is formed. The repeating time and an amount of coating were performed similar to Example 1 .
- the electrode thus manufactured without post-bake was subjected to electrolysis evaluation and the X-ray diffraction as with Example 1 .
- Example 1 In the same manner as with Example 1 except that post-bake was not carried out, the electrode for evaluation was manufactured and electrolysis evaluation was carried out in the same manner with Example 1.
- the crystallite diameter of Ir0 2 in the catalyst layer is small, the electrode surface area increased and an oxygen generation overvoltage decreased, compared with the conventional product, by means of a baking in a relatively low temperature region of 370°C - 400°C and a post baking in a further high temperature region of 520°C - 600°C. Accordingly, by promoting the oxygen generation reaction, a suppression effect of a lead adhesion were performed simultaneously. Furthermore, since iridium oxides of the catalyst layer mainly exist as a crystalline, a durability of the electrode was performed.
- the present invention relates to an anode for oxygen generation used for various industrial electrolyses and a manufacturing method for the same; more in detail, it is applicable to an anode for oxygen generation used for industrial electrolyses including manufacturing of electrolytic metal foils such as electrolytic copper foil, aluminum liquid contact, continuously electrogalvanized steel plate and metal extraction.
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Electroplating Methods And Accessories (AREA)
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Abstract
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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KR1020147019022A KR20140101423A (en) | 2011-12-26 | 2012-12-25 | Anode for oxygen generation and manufacturing method for the same |
US14/368,687 US20140353148A1 (en) | 2011-12-26 | 2012-12-25 | Anode for oxygen generation and manufacturing method for the same |
CN201280063009.6A CN104011263A (en) | 2011-12-26 | 2012-12-25 | Anode For Oxygen Generation And Manufacturing Method For The Same |
CA2859941A CA2859941A1 (en) | 2011-12-26 | 2012-12-25 | Anode for oxygen generation and manufacturing method for the same |
JP2014512994A JP5686457B2 (en) | 2011-12-26 | 2012-12-25 | Method for producing oxygen generating anode |
MX2014007762A MX2014007762A (en) | 2011-12-26 | 2012-12-25 | Anode for oxygen generation and manufacturing method for the same. |
AU2012361469A AU2012361469A1 (en) | 2011-12-26 | 2012-12-25 | Anode for oxygen generation and manufacturing method for the same |
PH12014501347A PH12014501347A1 (en) | 2011-12-26 | 2014-06-13 | Anode for oxygen generation and manufacturing method for the same |
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JP2011283848 | 2011-12-26 | ||
JP2011-283848 | 2011-12-26 |
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WO2013100165A2 true WO2013100165A2 (en) | 2013-07-04 |
WO2013100165A3 WO2013100165A3 (en) | 2013-10-10 |
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PCT/JP2012/084263 WO2013100165A2 (en) | 2011-12-26 | 2012-12-25 | Anode for oxygen generation and manufacturing method for the same |
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US (1) | US20140353148A1 (en) |
JP (1) | JP5686457B2 (en) |
KR (1) | KR20140101423A (en) |
CN (1) | CN104011263A (en) |
AU (1) | AU2012361469A1 (en) |
CA (1) | CA2859941A1 (en) |
CL (1) | CL2014001718A1 (en) |
MX (1) | MX2014007762A (en) |
PE (1) | PE20150086A1 (en) |
PH (1) | PH12014501347A1 (en) |
TW (1) | TW201337041A (en) |
WO (1) | WO2013100165A2 (en) |
Cited By (1)
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KR20170083593A (en) | 2014-11-10 | 2017-07-18 | 고쿠리츠다이가쿠호진 요코하마 고쿠리츠다이가쿠 | Oxygen-generating anode |
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JP2017115232A (en) | 2015-12-25 | 2017-06-29 | 株式会社東芝 | Electrode, membrane electrode composite, electrochemical cell and stack |
KR102126183B1 (en) * | 2017-11-29 | 2020-06-24 | 한국과학기술연구원 | Diffusion layer and oxygen electrode composite layers of polymer electrolyte membrane water electrolysis apparatus and method for preparing the same and polymer electrolyte membrane water electrolysis apparatus using the same |
CN109989075B (en) * | 2019-05-10 | 2019-11-22 | 建滔(连州)铜箔有限公司 | A kind of back coating technique producing electrolytic copper foil titanium anode plate |
CN112981450B (en) * | 2021-02-07 | 2022-02-11 | 天津大学 | Titanium-based iridium oxide electrode, electrochemical preparation method and application thereof |
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2012
- 2012-12-25 PE PE2014001029A patent/PE20150086A1/en not_active Application Discontinuation
- 2012-12-25 KR KR1020147019022A patent/KR20140101423A/en active IP Right Grant
- 2012-12-25 CN CN201280063009.6A patent/CN104011263A/en active Pending
- 2012-12-25 AU AU2012361469A patent/AU2012361469A1/en not_active Abandoned
- 2012-12-25 US US14/368,687 patent/US20140353148A1/en not_active Abandoned
- 2012-12-25 MX MX2014007762A patent/MX2014007762A/en not_active Application Discontinuation
- 2012-12-25 JP JP2014512994A patent/JP5686457B2/en not_active Expired - Fee Related
- 2012-12-25 WO PCT/JP2012/084263 patent/WO2013100165A2/en active Application Filing
- 2012-12-25 CA CA2859941A patent/CA2859941A1/en not_active Abandoned
- 2012-12-26 TW TW101150077A patent/TW201337041A/en unknown
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2014
- 2014-06-13 PH PH12014501347A patent/PH12014501347A1/en unknown
- 2014-06-24 CL CL2014001718A patent/CL2014001718A1/en unknown
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Also Published As
Publication number | Publication date |
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PH12014501347A1 (en) | 2014-09-15 |
MX2014007762A (en) | 2014-09-15 |
CL2014001718A1 (en) | 2014-09-05 |
CN104011263A (en) | 2014-08-27 |
KR20140101423A (en) | 2014-08-19 |
JP2014526609A (en) | 2014-10-06 |
AU2012361469A1 (en) | 2014-06-26 |
WO2013100165A3 (en) | 2013-10-10 |
US20140353148A1 (en) | 2014-12-04 |
CA2859941A1 (en) | 2013-07-04 |
JP5686457B2 (en) | 2015-03-18 |
TW201337041A (en) | 2013-09-16 |
PE20150086A1 (en) | 2015-02-28 |
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