WO2022018962A1 - 酸素発生用電極 - Google Patents
酸素発生用電極 Download PDFInfo
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- WO2022018962A1 WO2022018962A1 PCT/JP2021/020007 JP2021020007W WO2022018962A1 WO 2022018962 A1 WO2022018962 A1 WO 2022018962A1 JP 2021020007 W JP2021020007 W JP 2021020007W WO 2022018962 A1 WO2022018962 A1 WO 2022018962A1
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- Prior art keywords
- catalyst layer
- oxygen
- ruthenium
- condition
- tin
- Prior art date
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- 239000003054 catalyst Substances 0.000 claims abstract description 112
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 52
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 43
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 35
- 230000004888 barrier function Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 238000005363 electrowinning Methods 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 141
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 32
- 229910052760 oxygen Inorganic materials 0.000 description 32
- 239000001301 oxygen Substances 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229910052741 iridium Inorganic materials 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections 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
- 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
- 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
-
- 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
- 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
-
- 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
-
- 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 oxygen generating electrode.
- titanium electrodes in which a coating layer containing a mixed metal oxide (MMO) is provided as a catalyst layer on the surface thereof have been conventionally used as an electrode for oxygen evolution because they have lower overvoltage characteristics with respect to an oxygen evolution reaction. It has been proposed as an anode for an electrowinning process that can reduce energy consumption as an alternative to lead alloy electrodes.
- MMO mixed metal oxide
- the mixed metal oxide for forming the catalyst layer is usually iridium (Ir) as an active element and tantalum (Ta), tin (Sn), titanium (Ti), zirconium (Zr), and niobium as binder elements. It is a composite oxide with a valve metal such as (Nb).
- Such composite oxide electrode using, IrO 2 -Ta 2 O 5 titanium electrodes for oxygen generation in which a catalyst layer containing has been proposed Non-Patent Document 1).
- iridium is one of the most expensive and rare elements, there is a problem that it lacks versatility in terms of economy as a material for forming a catalyst layer of an anode for an electrowinning process.
- Non-Patent Document 2 ruthenium (Ru) oxide (RuO 2 ), which is cheaper than iridium, exhibits high electrode catalytic activity for oxygen evolution reaction (OER), and is an alternative to iridium. Attention has been paid.
- RuO 2 ruthenium oxide
- TiO 2 titanium electrode having a catalyst layer containing RuO 2 -Ta 2 O 5 is a composite oxide using no iridium has been proposed (Non-Patent Document 2).
- the present invention has been made in view of the problems of the prior art, and the problems thereof are high conductivity and consumption of the catalyst component even when the acidic electrolytic solution is electrolyzed. It is an object of the present invention to provide an oxygen generating electrode provided with a catalyst layer which is difficult to be easily electrolyzed and can be electrolyzed for a long period of time and has excellent durability.
- the following oxygen-evolving electrodes are provided.
- a base material made of titanium or a titanium alloy and a catalyst layer made of a mixed metal oxide arranged on the base material are provided, and the catalyst layer is provided with the following conditions (1) and.
- Condition (2) Contains ruthenium and tin, and the content of ruthenium is 40 mol% or more based on the total content of ruthenium and tin.
- the catalyst layer satisfies the condition (1), and the content of the polyvalent metal element in the catalyst layer is 2 to 20 mol% with respect to all the metal elements in the catalyst layer.
- the catalyst layer satisfies the condition (1), and the content of ruthenium in the catalyst layer is 20 to 70 mol% based on all metal elements in the catalyst layer [1].
- oxygen evolution is provided with a highly durable catalyst layer that has high conductivity, is less likely to consume catalyst components even when electrolyzing an acidic electrolytic solution, and can be electrolyzed for a long period of time. Electrodes can be provided.
- the oxygen-evolving electrode of the present invention includes a base material made of titanium or a titanium alloy, and a catalyst layer made of a mixed metal oxide arranged on the base material. Then, this catalyst layer satisfies at least one of the following conditions (1) and (2).
- Condition (1) Contains ruthenium, tin, and a trivalent or higher (excluding tetravalent) polyvalent metal element.
- Condition (2) Contains ruthenium and tin, and the content of ruthenium is 40 mol% or more based on the total content of ruthenium and tin.
- FIG. 1 is a schematic view showing an embodiment of the oxygen evolving electrode of the present invention.
- the oxygen-evolving electrode 10 of the present embodiment includes a base material 2 and a catalyst layer 4 arranged on the base material 2.
- the base material 2 is made of titanium or a titanium alloy.
- the overall shape of the base material 2 is not particularly limited, and can be appropriately designed according to the intended use. Examples of the overall shape of the base material include a plate shape, a rod (pillar) shape, a mesh shape, and the like.
- the catalyst layer 4 arranged on the base material 2 is formed of a mixed metal oxide (FIG. 1).
- This mixed metal oxide is a composite oxide of a plurality of metal elements and functions as a catalyst for electrolysis.
- the catalyst layer is a layer that satisfies at least one of the following conditions (1) and (2), and is preferably a layer that satisfies both the following conditions (1) and (2).
- Condition (1) Contains ruthenium, tin, and a trivalent or higher (excluding tetravalent) polyvalent metal element.
- Condition (2) Contains ruthenium and tin, and the content of ruthenium is 40 mol% or more based on the total content of ruthenium and tin.
- the thickness of the catalyst layer is not particularly limited and can be set arbitrarily.
- the thickness of the catalyst layer may be, for example, 1 to 10 ⁇ m.
- the catalyst layer contains ruthenium (Ru), tin (Sn), and a trivalent or higher (excluding tetravalent) polyvalent metal element (hereinafter, also simply referred to as “polyvalent metal element”). That is, the catalyst layer is formed of ruthenium as an active element, tin as a binder element, and a mixed metal oxide which is a composite oxide of the above polyvalent metal elements.
- ruthenium and tin the coexistence of a polyvalent metal element having a different valence from these tetravalent metal elements in the catalyst layer makes it possible to increase the conductivity and make the electrode an electrode. It can be an electrode for generating oxygen having a lower potential.
- the catalyst component (particularly, ruthenium, which is an active element) is not easily consumed even when electrolyzing under acidic conditions such as sulfuric acid acidity, and the catalyst layer has excellent durability.
- the valence of the metal element in the present specification means the valence (oxidation number) of the metal element that can exist in the most stable state.
- multivalent metal element examples include bismuth (Bi), tantalum (Ta), lanthanum (La), niobium (Nb), molybdenum (Mo) and the like. Among them, bismuth, tantalum, lanthanum and niobium are preferable, and bismuth is more preferable. These multivalent metal elements can be used alone or in combination of two or more.
- the content of the polyvalent metal element in the catalyst layer is preferably 2 to 20 mol% based on the total metal elements in the catalyst layer, preferably 3.5. It is more preferably to 15 mol%, and particularly preferably 4 to 12 mol%.
- the conductivity can be further increased and the durability of the catalyst layer can be further improved. If the content of the polyvalent metal element in the catalyst layer is too small, the effect obtained by containing the polyvalent metal element may be slightly insufficient.
- the content of the polyvalent metal element in the catalyst layer is too large, the content of ruthenium as an active element and tin as a binder element is relatively reduced, so that the catalytic activity may be slightly insufficient. be.
- the type and content of the metal element in each layer including the catalyst layer can be measured and calculated by an analysis method such as a fluorescent X-ray (XRF) analysis method.
- XRF fluorescent X-ray
- the content of ruthenium in the catalyst layer is preferably 20 to 70 mol%, preferably 25 to 66 mol%, based on all the metal elements in the catalyst layer. It is more preferably present, and particularly preferably 30 to 55 mol%.
- the content of ruthenium in the catalyst layer is preferably 20 to 70 mol%, preferably 25 to 66 mol%, based on all the metal elements in the catalyst layer. It is more preferably present, and particularly preferably 30 to 55 mol%.
- the content of ruthenium in the catalyst layer within the above range, higher catalytic activity can be obtained. If the content of ruthenium in the catalyst layer is too small, the catalytic activity may be slightly insufficient. On the other hand, if the content of ruthenium in the catalyst layer is too large, the ruthenium component tends to aggregate. Further, the ratio of ruthenium that does not effectively contribute to the electrolytic reaction to the coating amount is high, and the ratio of the binder component is low, so that the durability may be
- the catalyst layer contains ruthenium (Ru) and tin (Sn), and the content of ruthenium is 40 mol% or more based on the total content of ruthenium and tin. That is, the catalyst layer is formed of a mixed metal oxide which is a composite oxide of ruthenium as an active element and tin as a binder element. The catalyst layer is preferably formed of a mixed metal oxide which is a composite oxide containing substantially only ruthenium and tin as metal elements.
- the conductivity can be increased by setting the ruthenium content to 40 mol% or more, preferably 43 mol% or more, and further preferably 45 mol% or more based on the total content of ruthenium and tin.
- the electrode for oxygen generation having a lower electrode potential can be used. Furthermore, by setting the ruthenium content within the above range, the catalyst component (particularly, ruthenium, which is an active element) is not easily consumed even when electrolyzing under acidic conditions such as sulfuric acid acidity, and the durability is excellent. It can be a catalyst layer.
- the catalyst layer can further contain a metal element (other metal element) other than ruthenium and tin. By further containing other metal elements in the catalyst layer, it can act as a semi-active ingredient in the electrolytic reaction.
- metal elements include manganese (Mn) and the like. That is, the catalyst layer preferably further contains manganese.
- the content of the other metal elements in the catalyst layer is usually 10 to 50 mol%, preferably 20 to 40, based on all the metal elements in the catalyst layer. It is mol%.
- FIG. 2 is a schematic view showing another embodiment of the oxygen evolving electrode of the present invention.
- the oxygen-evolving electrode 20 shown in FIG. 2 further includes an intermediate layer 6 arranged between the base material 2 and the catalyst layer 4.
- an intermediate layer between the base material and the catalyst layer it is possible to suppress the passivation of the base material made of titanium or a titanium alloy by electrolysis, and it is possible to protect the base material from corrosion. It is preferable because it becomes.
- the durability is further improved, and it is possible to obtain an oxygen-evolving electrode capable of electrolysis for a longer period of time.
- the intermediate layer can be formed of various metals.
- the metal for forming the intermediate layer include titanium (Ti), tantalum (Ta), tin (Sn), alloys thereof, and mixed oxides thereof. Above all, it is preferable to form an intermediate layer with an alloy of titanium and tantalum or a mixed oxide of titanium and tantalum.
- the thickness of the intermediate layer is not particularly limited and can be set arbitrarily. The thickness of the intermediate layer may be, for example, 0.2 to 5 ⁇ m.
- the oxygen-evolving electrode 30 shown in FIG. 3 includes a base material 2 and a catalyst layer 4 arranged on the base material 2, and further includes a barrier layer 8 arranged on the catalyst layer 4.
- the oxygen evolution electrode 40 shown in FIG. 4 includes a base material 2 and a catalyst layer 4 arranged on the base material 2, and an intermediate layer 6 arranged between the base material 2 and the catalyst layer 4.
- a barrier layer 8 arranged on the catalyst layer 4 are further provided. That is, the oxygen-evolving electrodes 30 and 40 shown in FIGS. 3 and 4 further include a barrier layer 8 arranged on the catalyst layer 4.
- a barrier layer top coat layer
- the consumption of components such as ruthenium in the catalyst layer can be reduced.
- the durability is further improved, and it is possible to obtain an oxygen-evolving electrode capable of electrolysis for a longer period of time.
- the barrier layer can be formed of, for example, the same as a composite oxide of a plurality of metal elements, which is a mixed metal oxide for forming a catalyst layer. That is, the barrier layer can be formed of ruthenium, tin, or a mixed metal oxide which is a composite oxide of the above-mentioned multivalent metal elements such as bismuth.
- the content of active metal elements such as ruthenium in the barrier layer is preferably 0.5 to 5% based on all the metal elements in the barrier layer.
- the content of the binder element such as tin in the barrier layer is preferably 95 to 99.5 mol% based on the total metal elements in the barrier layer.
- the thickness of the barrier layer is not particularly limited and can be set arbitrarily.
- the thickness of the barrier layer may be, for example, 0.5 to 5 ⁇ m.
- the electrode for oxygen generation of the present invention has high conductivity, and ruthenium in the catalyst layer is not easily consumed even when electrolyzing an acidic electrolytic solution such as sulfuric acid acid, so that the electrode has durability suitable for long-term electrolysis.
- the oxygen generating electrode of the present invention is useful as, for example, an anode for an electrowinning process of a non-iron metal (anode for electrowinning (anode)) used in combination with a cathode for electrowinning of a non-iron metal. be. Further, it is useful as an oxygen generating electrode used in an electrolytic process in which an applied current density is 10 A / m 2 or less.
- the electrode for oxygen generation of the present invention can be manufactured by forming a catalyst layer made of a mixed metal oxide on a substrate.
- a coating liquid containing various metals or salts of various metals in a desired ratio is prepared, and surface treatments such as blasting and etching are performed as necessary.
- the prepared coating liquid is applied to the surface of the base material to which the above-mentioned material has been applied to form a coating layer.
- a catalyst layer made of a mixed metal oxide is formed on the substrate, and a target electrode for oxygen generation can be obtained.
- the firing temperature is usually 450 to 550 ° C, preferably 480 to 520 ° C.
- an intermediate layer on the substrate before forming the catalyst layer.
- a coating liquid containing various metals, salts of various metals, etc. in a desired ratio is applied to the surface of the base material. Apply to form a coating layer.
- an intermediate layer can be formed on the substrate.
- the firing temperature is usually 450 to 550 ° C, preferably 480 to 520 ° C.
- a catalyst layer can be formed on the formed intermediate layer according to the above-mentioned procedure.
- a desired intermediate layer can be formed on the base material by an ion plating method, a sputtering method, a plasma spraying method, or the like.
- a coating liquid containing various metals and salts of various metals is applied to the surface of the catalyst layer and coated in the same manner as in the case of forming the catalyst layer described above. Form a layer. Then, by firing under appropriate temperature conditions, a barrier layer can be formed on the catalyst layer. By repeating the application and firing of the coating liquid, the thickness of the formed barrier layer and the content of the metal element can be controlled.
- the firing temperature is usually 450 to 550 ° C, preferably 480 to 520 ° C.
- Pretreatment of base material> A 100 mm ⁇ 100 mm ⁇ 1 mm titanium mesh substrate was prepared. This mesh substrate was annealed at 590 ° C. for 60 minutes in an air atmosphere and then blasted with alumina (# 60). After being immersed in boiling 20% hydrochloric acid and etched for 12 minutes, it was washed and dried with ion-exchanged water to obtain a pretreated substrate.
- Method (A) The pretreated substrate was set in an arc ion plating apparatus using a Ta—Ti alloy target as an evaporation source. Then, an intermediate layer made of Ta—Ti alloy was formed on the surface of the base material according to the coating conditions shown in Table 1.
- the prepared coating liquid was applied to the surface of the pretreated substrate by brushing, and then dried at 60 ° C. for 10 minutes. In an electric muffle furnace, the mixture was fired at 520 ° C. for 10 minutes in an air atmosphere, and then air-cooled to room temperature. The cycle from application of the coating liquid to air cooling was repeated until the coating amount became 1.3 g / m 2 (metal mass conversion) to form an intermediate layer made of a mixed oxide of Ta-Ti on the surface of the base material. ..
- the coating liquid prepared by the above-mentioned method (A) was applied by brushing to the intermediate layer of the base material having the intermediate layer formed on the surface thereof, and then dried at 60 ° C. for 10 minutes. In an electric muffle furnace, the mixture was fired at 520 ° C. for 10 minutes in an air atmosphere, and then air-cooled to room temperature. The cycle from application of the coating liquid to air cooling was repeated until the coating amount became 10 g / m 2 (mass equivalent of Ru and Mn), and a catalyst layer was formed on the intermediate layer.
- the prepared coating liquid was applied to the catalyst layer by brushing, and then dried at 60 ° C. for 10 minutes. In an electric muffle furnace, the mixture was fired at 520 ° C. for 10 minutes in an air atmosphere, and then air-cooled to room temperature. The cycle from application of the coating liquid to air cooling was repeated until the coating amount became 3 g / m 2 (in terms of mass of Sn) to form a barrier layer on the catalyst layer layer, and an oxygen generating electrode was obtained.
- Oxygen-evolving electrodes were manufactured in the same manner as in Example 1 above, except that each material was used so as to have the layer structure shown in Table 2 and firing was performed under the conditions shown in Table 2. After forming the catalyst layer, post-baking was carried out by holding the catalyst layer at 520 ° C. for 1 hour in an electric muffle furnace under an air atmosphere. Further, as the tantalum (Ta) source, the lanthanum (La) source, the niobium (Nb) source, and the iridium (Ir) source used in the coating liquid for forming the catalyst layer, those shown below were used.
- Ta tantalum
- La lanthanum
- Nb niobium
- Ir iridium
- Tantalum (Ta) Source 125g / L TaCl 5 solution-lanthanum (La) source: La (NO 3) 3 ⁇ 6H 2 O -Niobium (Nb) source: Ammonium oxalate hydrate with niobium (V) -Iridium (Ir) source: 20.5% iridium chloride solution
- Electrolyte solution 150 g / L sulfuric acid aqueous solution
- Electrolyte solution temperature 50 ° C
- Working pole area 10 mm x 10 mm
- Counter electrode Zr plate (20 mm x 70 mm)
- Reference electrode Mercury sulfate (Hg / Hg 2 SO 4 )
- Electrolyte 150 g / L sulfuric acid aqueous solution
- Electrolyte temperature 40 ° C
- Anode area 20 mm x 50 mm -Cathode: Zr plate (30 mm x 70 mm) -Current density applied to the anode: 300 A / m 2
- the remaining amount of the coating after a certain period of time was measured by the XRF analysis method, and the consumption amount (g / m 2 ) of the active metal element (Ru, Mn, Ir) was calculated. Further, the consumption rate (mg / m 2 / h) of the active metal element (Ru, Mn, Ir) was calculated from the calculated consumption amount and the electrolysis time. The results are shown in Table 4.
- the oxygen-evolving electrode of the present invention is useful as an anode for an electrowinning process of non-ferrous metal, or as an oxygen-evolving electrode used in an electrolytic process in which an applied current density is 10 A / m 2 or less.
- Electrode for oxygen generation 2 Base material 4: Catalyst layer 6: Intermediate layer 8: Barrier layer
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Abstract
Description
[1]チタン又はチタン合金で形成された基材と、前記基材上に配置される、混合金属酸化物で形成された触媒層と、を備え、前記触媒層が、下記条件(1)及び条件(2)の少なくともいずれかを満たす酸素発生用電極。
条件(1):ルテニウム、スズ、及び3価以上(但し、4価を除く)の多価金属元素を含有する。
条件(2):ルテニウム及びスズを含有するとともに、ルテニウムの含有量が、ルテニウムとスズの合計含有量を基準として、40モル%以上である。
[2]前記触媒層が、前記条件(1)を満たし、前記触媒層中の前記多価金属元素の含有量が、前記触媒層中の全金属元素を基準として、2~20モル%である前記[1]に記載の酸素発生用電極。
[3]前記多価金属元素が、ビスマス、タンタル、ランタン、ニオブ、及びモリブデンからなる群より選択される少なくとも一種である前記[1]又は[2]に記載の酸素発生用電極。
[4]前記触媒層が、前記条件(1)を満たし、前記触媒層中のルテニウムの含有量が、前記触媒層中の全金属元素を基準として、20~70モル%である前記[1]~[3]のいずれかに記載の酸素発生用電極。
[5]前記触媒層が、マンガンをさらに含有する前記[1]~[4]のいずれかに記載の酸素発生用電極。
[6]前記基材と前記触媒層の間に配置される中間層をさらに備える前記[1]~[5]のいずれかに記載の酸素発生用電極。
[7]前記触媒層上に配置されるバリア層をさらに備える前記[1]~[6]のいずれかに記載の酸素発生用電極。
[8]非鉄金属の電解採取プロセス用陽極として用いられる前記[1]~[7]のいずれかに記載の酸素発生用電極。
条件(1):ルテニウム、スズ、及び3価以上(但し、4価を除く)の多価金属元素を含有する。
条件(2):ルテニウム及びスズを含有するとともに、ルテニウムの含有量が、ルテニウムとスズの合計含有量を基準として、40モル%以上である。
図1は、本発明の酸素発生用電極の一実施形態を示す模式図である。図1に示すように、本実施形態の酸素発生用電極10は、基材2と、基材2上に配置される触媒層4とを備える。基材2は、チタン又はチタン合金で形成されている。基材2の全体形状は特に限定されず、用途に応じて適宜設計することができる。基材の全体形状としては、例えば、板状、棒(柱)状、メッシュ状等を挙げることができる。
基材2上に配置される触媒層4は、混合金属酸化物で形成されている(図1)。この混合金属酸化物は複数の金属元素の複合酸化物であり、電解用の触媒として機能する。そして、触媒層は、下記条件(1)及び条件(2)の少なくともいずれかを満たす層であり、好ましくは下記条件(1)及び条件(2)のいずれも満たす層である。
条件(1):ルテニウム、スズ、及び3価以上(但し、4価を除く)の多価金属元素を含有する。
条件(2):ルテニウム及びスズを含有するとともに、ルテニウムの含有量が、ルテニウムとスズの合計含有量を基準として、40モル%以上である。
触媒層は、ルテニウム(Ru)、スズ(Sn)、及び3価以上(但し、4価を除く)の多価金属元素(以下、単に「多価金属元素」とも記す)を含有する。すなわち、触媒層は、活性元素としてのルテニウム、バインダー元素としてのスズ、及び上記の多価金属元素の複合酸化物である混合金属酸化物で形成されている。4価の金属元素であるルテニウムとスズに加えて、これらの4価の金属元素とは価数の異なる多価金属元素を触媒層に共存させることで、導電率を高めることが可能となり、電極電位がより低い酸素発生用電極とすることができる。また、多価金属元素を含有させることで、硫酸酸性等の酸性条件下で電解する場合であっても触媒成分(特に、活性元素であるルテニウム)が消耗しにくく、耐久性に優れた触媒層とすることができる。なお、本明細書における金属元素の価数は、最も安定した状態で存在しうる金属元素の価数(酸化数)を意味する。
触媒層は、ルテニウム(Ru)及びスズ(Sn)を含有するとともに、ルテニウムの含有量が、ルテニウムとスズの合計含有量を基準として、40モル%以上である。すなわち、触媒層は、活性元素としてのルテニウム、及びバインダー元素としてのスズの複合酸化物である混合金属酸化物で形成されている。なお、触媒層は、実質的にルテニウム及びスズのみを金属元素として含有する複合酸化物である混合金属酸化物で形成されていることが好ましい。そして、ルテニウムの含有量を、ルテニウムとスズの合計含有量を基準として40モル%以上、好ましくは43モル%以上、さらに好ましくは45モル%以上とすることで、導電率を高めることが可能となり、電極電位がより低い酸素発生用電極とすることができる。さらに、ルテニウムの含有量を上記の範囲とすることで、硫酸酸性等の酸性条件下で電解する場合であっても触媒成分(特に、活性元素であるルテニウム)が消耗しにくく、耐久性に優れた触媒層とすることができる。
触媒層には、ルテニウムやスズ以外金属元素(その他の金属元素)をさらに含有させることができる。その他の金属元素を触媒層にさらに含有させることで、電解反応に対して、準活性成分として作用させることができる。その他の金属元素としては、マンガン(Mn)等を挙げることができる。すなわち、触媒層は、マンガンをさらに含有することが好ましい。
図2は、本発明の酸素発生用電極の他の実施形態を示す模式図である。図2に示す酸素発生用電極20は、基材2と触媒層4の間に配置される中間層6をさらに備える。このような中間層を基材と触媒層の間に設けることで、電解によるチタン又はチタン合金製の基材の不動態化を抑制することができるとともに、基材を腐食から保護することが可能となるために好ましい。これにより、耐久性がさらに向上し、より長期間の電解が可能な酸素発生用電極とすることができる。
図3及び4は、本発明の酸素発生用電極のさらに他の実施形態を示す模式図である。図3に示す酸素発生用電極30は、基材2と、基材2上に配置される触媒層4とを備えるとともに、触媒層4上に配置されるバリア層8をさらに備える。また、図4に示す酸素発生用電極40は、基材2と、基材2上に配置される触媒層4とを備えるとともに、基材2と触媒層4の間に配置される中間層6と、触媒層4上に配置されるバリア層8とをさらに備える。すなわち、図3及び4に示す酸素発生用電極30,40は、いずれも、触媒層4上に配置されるバリア層8をさらに備える。このようなバリア層(トップコート層)を触媒層上に設けることで、触媒層中のルテニウム等の成分の消耗を軽減することができるために好ましい。また、電解液中に存在するとともに、電解によって析出しうるヒ素(As)、アンチモン(Sb)、マンガン(Mn)等の成分が触媒層の表面に拡散するのを抑制することができる。これにより、耐久性がさらに向上し、より長期間の電解が可能な酸素発生用電極とすることができる。
本発明の酸素発生用電極は、導電率が高いとともに、硫酸酸性等の酸性電解液を電解する場合であっても触媒層中のルテニウムが消耗しにくく、長期間の電解に適した耐久性を有する。このため、本発明の酸素発生用電極は、例えば、非鉄金属の電解採取用陰極(カソード)と組み合わせて用いられる、非鉄金属の電解採取プロセス用陽極(電解採取用陽極(アノード))として有用である。さらには、印加される電流密度が10A/m2以下の電解プロセスに用いられる酸素発生用電極として有用である。
本発明の酸素発生用電極は、混合金属酸化物からなる触媒層を基材上に形成することで製造することができる。基材上に触媒層を形成するには、例えば、各種金属や各種金属の塩等を所望とする比率で含有するコーティング液を調製するとともに、必要に応じてブラスト処理やエッチング処理等の表面処理を施した基材の表面に調製したコーティング液を塗布して塗工層を形成する。次いで、適当な温度条件下で焼成することで、混合金属酸化物からなる触媒層が基材上に形成され、目的とする酸素発生用電極を得ることができる。なお、コーティング液の塗布と焼成を繰り返すことで、形成される触媒層の厚さや金属元素の含有量を制御することができる。焼成温度は、通常、450~550℃、好ましくは480~520℃とすればよい。
100mm×100mm×1mmのチタン製のメッシュ基材を用意した。このメッシュ基材を、空気雰囲気下、590℃で60分間焼鈍した後、アルミナ(#60)を用いてブラスト処理した。沸騰した20%塩酸に浸漬して12分間エッチング処理した後、イオン交換水で洗浄及び乾燥させて、前処理済みの基材を得た。
(方法(A))
Ta-Ti合金ターゲットを蒸発源とするアークイオンプレーティング装置に前処理済みの基材をセットした。そして、表1に示す被覆条件にしたがって、Ta-Ti合金からなる中間層を基材の表面に形成した。
270g/LのTiCl4溶液、125g/LのTaCl5溶液、及び10%塩酸水溶液を混合して、Ti:Ta=50:50(モル比)のコーティング液を調製した。前処理済みの基材の表面に調製したコーティング液を刷毛塗りして塗布した後、60℃で10分間乾燥した。電気マッフル炉内で、空気雰囲気下、520℃で10分間焼成した後、室温まで空冷した。コーティング液の塗布から空冷までのサイクルを、コーティング量が1.3g/m2(金属質量換算)となるまで繰り返して、Ta-Tiの混合酸化物からなる中間層を基材の表面に形成した。
(実施例1)
[触媒層の形成]
国際公開第2005/014885号に記載の手順にしたがって、1.65mol/Lのスズ(Sn)ヒドロキシアセトクロリド錯体(SnHAC)溶液を調製した。国際公開第2010/055065号に記載の手順にしたがって、0.9mol/Lのルテニウム(Ru)ヒドロキシアセトクロリド錯体(RuHAC)溶液を調製した。BiCl3を10%塩酸水溶液に溶解させて、80g/LのBi溶液を調製した。Mn(NO3)2・6H2Oを10%酢酸水溶液に溶解させて、130g/LのMn溶液を調製した。RuHAC溶液、Mn溶液、SnHAC溶液、Bi溶液、及び10%酢酸水溶液を混合して、Ru:Mn:Sn:Bi=33:20:43:4(モル比)のコーティング液を調製した。前述の方法(A)によって、その表面に中間層を形成した基材の中間層に調製したコーティング液を刷毛塗りして塗布した後、60℃で10分間乾燥した。電気マッフル炉内で、空気雰囲気下、520℃で10分間焼成した後、室温まで空冷した。コーティング液の塗布から空冷までのサイクルを、コーティング量が10g/m2(Ru及びMnの質量換算)となるまで繰り返して、中間層上に触媒層を形成した。
RuHAC溶液、SnHAC溶液、Bi溶液、及び10%酢酸水溶液を混合して、Sn:Bi:Ru=95:2:3(モル比)のコーティング液を調製した。調製したコーティング液を触媒層に刷毛塗りして塗布した後、60℃で10分間乾燥した。電気マッフル炉内で、空気雰囲気下、520℃で10分間焼成した後、室温まで空冷した。コーティング液の塗布から空冷までのサイクルを、コーティング量が3g/m2(Snの質量換算)となるまで繰り返して触媒層層上にバリア層を形成し、酸素発生用電極を得た。
表2に示す層構成となるように各材料を用いるとともに、表2に示す条件で焼成等を実施したこと以外は、前述の実施例1と同様にして、酸素発生用電極を製造した。なお、ポストベークは、触媒層を形成後、電気マッフル炉内で、空気雰囲気下、520℃で1時間保持することで実施した。また、触媒層を形成するためのコーティング液に用いるタンタル(Ta)源、ランタン(La)源、ニオブ(Nb)源、及びイリジウム(Ir)源として、以下に示すものを用いた。
・タンタル(Ta)源:125g/LのTaCl5溶液
・ランタン(La)源:La(NO3)3・6H2O
・ニオブ(Nb)源:ニオブ(V)酸シュウ酸アンモニウム水和物
・イリジウム(Ir)源:20.5%の塩化イリジウム酸溶液
(電極電位の測定)
以下に示す方法により、製造した酸素発生用電極の酸素発生条件下での電極電位(V)を測定した。結果を表3に示す。
・電流遮断法
・電解液:150g/L硫酸水溶液
・電解液温度:50℃
・作用極面積:10mm×10mm
・対極:Zr板(20mm×70mm)
・参照極:硫酸第一水銀(Hg/Hg2SO4)
以下に示す条件にしたがって、酸素発生用電極(触媒層)の耐久性試験を行った。
・電解液:150g/L硫酸水溶液
・電解液温度:40℃
・陽極面積:20mm×50mm
・陰極:Zr板(30mm×70mm)
・陽極に印加した電流密度:300A/m2
2:基材
4:触媒層
6:中間層
8:バリア層
Claims (8)
- チタン又はチタン合金で形成された基材と、
前記基材上に配置される、混合金属酸化物で形成された触媒層と、を備え、
前記触媒層が、下記条件(1)及び条件(2)の少なくともいずれかを満たす酸素発生用電極。
条件(1):ルテニウム、スズ、及び3価以上(但し、4価を除く)の多価金属元素を含有する。
条件(2):ルテニウム及びスズを含有するとともに、ルテニウムの含有量が、ルテニウムとスズの合計含有量を基準として、40モル%以上である。 - 前記触媒層が、前記条件(1)を満たし、
前記触媒層中の前記多価金属元素の含有量が、前記触媒層中の全金属元素を基準として、2~20モル%である請求項1に記載の酸素発生用電極。 - 前記多価金属元素が、ビスマス、タンタル、ランタン、ニオブ、及びモリブデンからなる群より選択される少なくとも一種である請求項1又は2に記載の酸素発生用電極。
- 前記触媒層が、前記条件(1)を満たし、
前記触媒層中のルテニウムの含有量が、前記触媒層中の全金属元素を基準として、20~70モル%である請求項1~3のいずれか一項に記載の酸素発生用電極。 - 前記触媒層が、マンガンをさらに含有する請求項1~4のいずれか一項に記載の酸素発生用電極。
- 前記基材と前記触媒層の間に配置される中間層をさらに備える請求項1~5のいずれか一項に記載の酸素発生用電極。
- 前記触媒層上に配置されるバリア層をさらに備える請求項1~6のいずれか一項に記載の酸素発生用電極。
- 非鉄金属の電解採取プロセス用陽極として用いられる請求項1~7のいずれか一項に記載の酸素発生用電極。
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2021311153A AU2021311153B2 (en) | 2020-07-20 | 2021-05-26 | Oxygen-generating electrode |
US18/005,795 US20230279568A1 (en) | 2020-07-20 | 2021-05-26 | Oxygen-generating electrode |
KR1020237001513A KR20230024391A (ko) | 2020-07-20 | 2021-05-26 | 산소 발생용 전극 |
PE2023000093A PE20230701A1 (es) | 2020-07-20 | 2021-05-26 | Electrodo generador de oxigeno |
MX2023000834A MX2023000834A (es) | 2020-07-20 | 2021-05-26 | Electrodo generador de oxigeno. |
EP21846492.3A EP4183903A4 (en) | 2020-07-20 | 2021-05-26 | OXYGEN GENERATING ELECTRODE |
BR112022026946A BR112022026946A2 (pt) | 2020-07-20 | 2021-05-26 | Eletrodo que gera oxigênio |
CN202180060729.6A CN116209788A (zh) | 2020-07-20 | 2021-05-26 | 产氧用电极 |
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JP2020123597A JP2022020222A (ja) | 2020-07-20 | 2020-07-20 | 酸素発生用電極 |
JP2020-123597 | 2020-07-20 |
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US (1) | US20230279568A1 (ja) |
EP (1) | EP4183903A4 (ja) |
JP (1) | JP2022020222A (ja) |
KR (1) | KR20230024391A (ja) |
CN (1) | CN116209788A (ja) |
AU (1) | AU2021311153B2 (ja) |
BR (1) | BR112022026946A2 (ja) |
CL (1) | CL2023000174A1 (ja) |
MX (1) | MX2023000834A (ja) |
PE (1) | PE20230701A1 (ja) |
WO (1) | WO2022018962A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5026769A (ja) * | 1973-04-19 | 1975-03-19 | ||
JPS6130690A (ja) * | 1984-06-27 | 1986-02-12 | ヴエ−・ツエ−・ヘレウス・ゲゼルシヤフト・ミツト・ベシユレンクタ−・ハフツング | 複合電極、その製法及び使用方法 |
WO2005014885A1 (en) | 2003-07-28 | 2005-02-17 | De Nora Elettrodi S.P.A. | Electrode for electrochemical processes and method for producing the same |
CN1900368A (zh) * | 2006-06-30 | 2007-01-24 | 福州大学 | 高铈含量的含钌涂层钛阳极及其制备方法 |
WO2010055065A1 (en) | 2008-11-12 | 2010-05-20 | Industrie De Nora S.P.A. | Electrode for electrolysis cell |
JP2018524470A (ja) * | 2015-06-23 | 2018-08-30 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | 電解過程のための電極 |
-
2020
- 2020-07-20 JP JP2020123597A patent/JP2022020222A/ja active Pending
-
2021
- 2021-05-26 BR BR112022026946A patent/BR112022026946A2/pt unknown
- 2021-05-26 PE PE2023000093A patent/PE20230701A1/es unknown
- 2021-05-26 US US18/005,795 patent/US20230279568A1/en active Pending
- 2021-05-26 EP EP21846492.3A patent/EP4183903A4/en active Pending
- 2021-05-26 MX MX2023000834A patent/MX2023000834A/es unknown
- 2021-05-26 CN CN202180060729.6A patent/CN116209788A/zh active Pending
- 2021-05-26 WO PCT/JP2021/020007 patent/WO2022018962A1/ja active Application Filing
- 2021-05-26 KR KR1020237001513A patent/KR20230024391A/ko unknown
- 2021-05-26 AU AU2021311153A patent/AU2021311153B2/en active Active
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2023
- 2023-01-19 CL CL2023000174A patent/CL2023000174A1/es unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5026769A (ja) * | 1973-04-19 | 1975-03-19 | ||
JPS6130690A (ja) * | 1984-06-27 | 1986-02-12 | ヴエ−・ツエ−・ヘレウス・ゲゼルシヤフト・ミツト・ベシユレンクタ−・ハフツング | 複合電極、その製法及び使用方法 |
WO2005014885A1 (en) | 2003-07-28 | 2005-02-17 | De Nora Elettrodi S.P.A. | Electrode for electrochemical processes and method for producing the same |
CN1900368A (zh) * | 2006-06-30 | 2007-01-24 | 福州大学 | 高铈含量的含钌涂层钛阳极及其制备方法 |
WO2010055065A1 (en) | 2008-11-12 | 2010-05-20 | Industrie De Nora S.P.A. | Electrode for electrolysis cell |
JP2018524470A (ja) * | 2015-06-23 | 2018-08-30 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | 電解過程のための電極 |
Non-Patent Citations (3)
Title |
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JOURNAL OF APPLIED ELECTROCHEMISTRY, vol. 21, 1991, pages 335 - 345 |
PROCEEDINGS OF COPPER 2016 (ABSTRACTS, pages 2145 - 2152 |
See also references of EP4183903A4 |
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Publication number | Publication date |
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AU2021311153B2 (en) | 2024-06-13 |
CN116209788A (zh) | 2023-06-02 |
PE20230701A1 (es) | 2023-04-24 |
BR112022026946A2 (pt) | 2023-01-31 |
MX2023000834A (es) | 2023-02-14 |
CL2023000174A1 (es) | 2023-07-28 |
AU2021311153A1 (en) | 2023-02-02 |
EP4183903A1 (en) | 2023-05-24 |
EP4183903A4 (en) | 2024-08-07 |
JP2022020222A (ja) | 2022-02-01 |
US20230279568A1 (en) | 2023-09-07 |
KR20230024391A (ko) | 2023-02-20 |
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