AU2004277578B2 - Electrode - Google Patents
Electrode Download PDFInfo
- Publication number
- AU2004277578B2 AU2004277578B2 AU2004277578A AU2004277578A AU2004277578B2 AU 2004277578 B2 AU2004277578 B2 AU 2004277578B2 AU 2004277578 A AU2004277578 A AU 2004277578A AU 2004277578 A AU2004277578 A AU 2004277578A AU 2004277578 B2 AU2004277578 B2 AU 2004277578B2
- Authority
- AU
- Australia
- Prior art keywords
- electrode
- metal oxide
- coating layer
- precursors
- platinum group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 238000000576 coating method Methods 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 50
- 229910044991 metal oxide Inorganic materials 0.000 claims description 50
- 239000011247 coating layer Substances 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 37
- 150000004706 metal oxides Chemical class 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- -1 platinum group metal oxide Chemical class 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 16
- 229910052741 iridium Inorganic materials 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 12
- 229910052762 osmium Inorganic materials 0.000 claims description 10
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical group O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 46
- 239000002253 acid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910001924 platinum group oxide Inorganic materials 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic 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
- C25B11/055—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
- 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
Description
00 Electrode The present invention relates to an electrode, a method of preparing the Selectrode, and the use thereof.
;Z
(00 005 Backqround of the invention Electrodes coated with titanium oxide, iridium oxide, and ruthenium oxide are 00 commercially used today in electrolytic cells. Such electrodes can be prepared in r' accordance with EP 715002 B1 disclosing a method wherein an anhydrous solvent comprising precursors of mixed metal oxides are deposited on a substrate to form an i 10 electrocatalytic oxide coating. However, electrodes produced by this method have a fairly low activity resulting in ohmic losses and high cell voltages in electrolytic cells, which leads to increased electric energy consumption. A further problem of conventional electrodes are their relatively short service life. The present invention intends to solve these problems.
Description of the invention The present invention provides a method of preparing an electrode comprising providing an electrode substrate, depositing on said electrode substrate a first substantially aqueous coating solution comprising precursors of a valve metal oxide and of at least two platinum group metal oxides, treating the first coating solution to provide a first metal oxide coating layer on the electrode substrate, depositing directly on said first coating layer a second substantially organic coating solution comprising precursors of a valve metal oxide and of at least one platinum group metal oxide, wherein at least one of the precursors is in organic form, treating said second coating solution to provide a second metal oxide coating layer directly on the first coating layer.
The electrode substrate can be any valve metal or valve metal surfaced substrate such as titanium, tantalum, zirconium, niobium, tungsten, silicon or alloys thereof, preferably titanium. Valve metals are known as film-forming metals having the property, when connected as an electrode in the electrolyte in which the coated electrode is expected to operate, of rapidly forming a passivating oxide film which protects the underlying metal from corrosion by the electrolyte. The substrate can have any suitable shape such as a rod, tube, woven or knitted wire, perforated or non-perforated plate, louver, or mesh, e.g. an expanded mesh. Titanium or other valve metal clad on a conducting metal core or substrate can also be used. Preferably, the electrode substrate is perforated or has the shape of a mesh having openings with a diameter from about 1 to about 10, more preferably from about 2 to about 5 mm. Preferably, the electrode N:Melboume\Ceses\Patent\59000.59999\P59692AU\Specis\P59692AU Specification 2008-5-15 doc 18/06108 WO 2005/033367 PCT/SE2004/001428 2 substrate is roughened using chemicals means such as etching, e.g. acid etching, or mechanical such as blasting, e.g. sand blasting, grit blasting by means of e.g. aluminium oxide grits. It is preferred that the substrate surface has a roughness R, from about 2 to about 12, moie preferably from about 3 to about 6, and most preferably from about 4 to about 5 gm as measured using the SURFTEST 212 surface roughness tester (Mitutoyo, Japan). After 'the surface of the substrate has been roughened, it may be subjected to thermal oxidation by heating the substrate surface at an elevated temperature in an oxygen containing atmosphere for about 1 to about 3 hours. The temperature of such treatment is preferably from about 350 to about 600, more preferably from about 400 to about 500 °C.
The precursors of the platinum group metal oxides dissolved in the first coating solution preferably comprise at least two water-soluble compounds of platinum, iridium, palladium, rhodium, osmium, and ruthenium, more preferably ruthenium and at least one of iridium, palladium, platinum, rhodium, and osmium, and most preferably ruthenium and iridium. Suitable precursors include e:g. RuCI 3
H
2 RuCI 6 IrC1 3 and mixtures thereof.
Preferably, the precursors are soluble also in acidified aqueous solutions. Suitable valve metal oxide precursors include -water-soluble compounds of aluminium, zirconium, bismuth, tungsten, niobium, titanium, silicon and tantalum, preferably titanium, e.g. TiC 4 Preferably, the first coating solution is acidified, suitably by hydrochloric acid and/or other mineral acids to a pH of from about 0 to about 5, more preferably from about 0 to about 2.
Suitably, at least about 70, preferably at least about 90, and most preferably at least about 95 volume percent of the solvent in the substantially aqueous coating solution is comprised of water.
The first coating solution is suitably deposited on the substrate by applying the solution on the electrode substrate, preferably until the total loading of the first layer is from about 0.5 to about 10, more preferably from about 1 to about 6, and most preferably from about 1.5 to about 3 g metal /m 2 The process of depositing the coating solution can be repeated in order to obtain a thicker layer having the desired metal oxide content. It is desirable to let the coating air dry after each repetition at a temperature from about 20 to about 70, preferably from about 20 to about 50 The drying can take from about 10 to about 20 minutes, The coating solution can then be heat treated at a temperature from about 300 to about 600, preferably from about 450 to about 550 °C for suitably about to about 30. minutes in order to convert the precursors to their corresponding metal oxides.
Suitable platinum group oxide precursors of the second coating solution include organic compounds, such as organic salts and acids of ruthenium, osmium, rhodium, WO 2005/033367 PCT/SE2004/001428 1 3 iridium, palladium, and platinum, and mixtures thereof, preferably ruthenium and optionally at least one of iridium, palladium, rhodium, and osmium, and most preferably ruthenium and iridium. Suitable valve metal oxide precursors can include e.g. organic compounds such as organic salts and acids thereof include water-soluble compounds of aluminium, zirconium, bismuth, tungsten, niobium, titanium, silicon and tantalum, preferably titanium. However, it is sufficient that at least one of the precursor compounds is present in its organic form, i.e. includes organic compounds such as organic metal salts or acids such as e.g. titanium alcoxide, tetrabuthyl titanate, and/or tetrapentyl titanate.
It has been found that coating solutions for providing the second or outermost coating layer containing at least one precursor in organic form in a substantially organic coating solution results in an electrode having increased activity when deposited on the first coating layer.
Suitably, at least about 70, preferably at least about 90, and most preferably at least about 95 volume percent of the solvent in the substantially organic coating solution is comprised of organic solvent.
Preferred organic solvents of the second coating, solution include alcohols, preferably lower alcohols, more preferably acidified anhydrous, lower alkyl alcohols having from about 3 to about 5 carbons atoms, such as 1-buthanol, 1-propanol, 2propanol, 1-pentanol and 2-pentanol and 3-methyl-2-butanol. The second coating solutions preferably include a concentrated acid, such as a mineral acid, e.g. hydrochloric acid adjusting the pH to from about -1 to about 5, preferably from about -1 to about 2.
The second coating solution is suitably applied to the obtained first coating layer until the total metal loading of the second layer is from about 1 to about 10, preferably from about 1.5 to about 3.5 g metal/m2. The deposition process can be repeated in order to obtain a thicker second coating layer or a further coating layer on the second coating layer. In industrial use, the loading of the second coating solution is preferably from about 1 to about 10, most preferably from about 1.5 to about 3.5 g metal/m 2 Preferably, the second coating solution is air dried and heat treated in the same way as the first coating solution so as to form the second coating layer.
According to one preferred embodiment, precursors of the two platinum metal oxides are dissolved in the first coating solution in a mole ratio of about 1:2 to about 2:1, preferably from about 2:3 to about 3:2. According to one preferred embodiment, at least two precursors of platinum metal oxides are dissolved in the second coating solution in the same mole ratio as in the first coating solution. According to one preferred embodiment, precursors of the platinum and valve metal oxides are dissolved in the coating solutions in a mole ratio of valve metal to platinum metal(s) of about 1:2 to about 2:1, preferably from about 4:5 to about 1:1.
00 0 According to one preferred embodiment, precursors of iridium and ruthenium oxides are dissolved in at least one of the first and/or the second coating solutions in a Smole ratio of about 1:2 to about 2:1, preferably from about 2:3 to about 3:2. According to n one preferred embodiment, precursors of titanium, iridium and/or ruthenium are dissolved 00 5 in the coating solutions in a mole ratio of titanium to iridium and ruthenium of about 1:2 to about 2:1, preferably from about 4:5 to about 1:1.
00 Each coating solution is suitably deposited by immersion of the electrode substrate in the coating solution or by means of other suitable methods such as spraying, e.g. electrostatic spraying, rolling or brush painting. Even though a process providing two layers (with the defined coatings) is preferred, further layers may also be adhered.
The invention also provides an electrode obtained by the method as disclosed herein. The present invention further provides an electrode obtained by providing an electrode substrate, depositing on said electrode substrate a first substantially aqueous coating solution comprising precursors of a valve metal oxide and of at least two platinum group metal oxides, treating the first coating solution to provide a first metal oxide coating layer on the electrode substrate, depositing directly on said first coating layer a second substantially organic coating solution comprising precursors of a valve metal oxide and of at least one platinum group metal oxide, wherein at least one of the precursors is in organic form, treating said second coating solution to provide a second metal oxide coating layer directly on the first coating layer.
The invention still further provides an electrode comprising an electrode substrate, a first coating layer having a charge/projected area from about 10 to about 200, preferably from about 25 to about 200, and most preferably from about 25 to about 190 mC/cm 2 (mCoulomb/cm 2 said first coating layer comprising a valve metal oxide and at least two platinum group metal oxides deposited on said electrode substrate, and a second coating layer having a charge/projected area from about 210 to about 1000, more preferably from about 250 to about 1000, and most preferably from about 300 to about 800 mC/cm 2 said second layer comprising a valve metal oxide and at least one platinum group metal oxide deposited directly on the first coating layer.
The charge/projected area was measured by an electro-double layer measurement with cyclic voltammograms in sulphuric acid. The measuring condition of the cyclic voltammograms was 50mV/second at a sweep rate in the range of 0.3 to 1.1V (vs.
RHE (Reversible Hydrogen Electrode)) in 0.5M sulphuric acid. The measured values in mC/cm 2 are proportional to the active specific surface area of the electrodes. More information about this method can be found in L.D. Burke et al, Electroanal. Chem.
96(1976) 19-27 and R.F. Savinell et al, J. Electrochem. Soc. 137(1990) 489-494.
N \Melboume\Cases\Paten\59000-59999P59692 AU\SpecisP59692.AU Specification 2008-5-15 doc 18/06/08 00 It has been found that an electrode according to the invention shows a superior activity while providing higher stability and longer service life in view of existing electrodes.
Preferably, the electrode substrate is as described herein. Particularly, the nelectrode substrate is suitably perforated or has the shape of a mesh having openings with 00 5 a diameter from about 1 to about 10, more preferably from about 2 to about 5 mm. It has been found that the electrodes with openings within the defined ranges when immersed in 00 an operated cell produce small bubbles of evolved gas, which in turn results in an rincreased homogeneous current distribution and lower ohmic loss, particularly in a membrane cell.
The coating layers of the electrode may comprise platinum group metal oxides, such as oxides of iridium, palladium, rhodium, osmium, and ruthenium, preferably oxides of ruthenium and at least one of iridium, rhodium, osmium, more preferably oxides of ruthenium and iridium. The coating layers also comprise at least one valve metal oxide such as an oxide of titanium, tantalum, zirconium, niobium, tungsten, and silicon, preferably titanium.
Preferably, the roughness Ra of the electrode is from about 2 to about 12, more preferably from about 3 to about 6, and most preferably from about 4 to about 5 tIm.
The metal oxide layers preferably contain from about 40 to about 70 mole percent counted as valve metal, preferably as tantalum and/or titanium, from about 20 to about mole percent of ruthenium oxide counted as ruthenium, and from about 10 to about mole percent of another platinum group metal oxide counted as metal. The oxide coating on the electrode substrate is also effective in increasing the service life of the electrode by retarding the corrosion of the platinum group metals.
Even though a process providing two layers (with the defined coatings) is preferred, further layers optionally with same or similar chemical composition may also be adhered.
The invention also provides the use of the electrode in an electrolytic cell.
Preferably, the electrode is used as an anode, preferably as a dimensionally stable anode, particularly in an ion membrane cell for the production of e.g. alkali metal hydroxide, particularly sodium hydroxide.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the gist and scope of the present invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the claims. While the examples here below provide more specific details of the reactions, the following general principles may here be disclosed. The following example will further illustrate how the described invention may be performed without limiting the scope of it.
N:\Melboume\Cases\Patent\59000-59999\P59692.AU\Specis\P59692AU Specification 2008-5-15.doc 18/06/08 00
O
SAll parts and percentages refer to part and percent by weight, if not otherwise Sstated.
00 Example 1 00 A titanium expanded mesh having a thickness of 1 mm and length and width of and 24 mm respectively was used as electrode substrate after having been degreased N:\Melboume\Cases\Patentl59000-59999\P59692 AU\SpecsP59692.AU Specification 2008-5-15.doc 18/06/08 WO 2005/033367 PCT/SE2004/001428 6 and pickled in boiling hydrochloric acid. A first coating solution was deposited on the substrate having a molar ratio of Ti:Ru:lr of 2:1:1, in which the total Ir+Ru concentration was 50 g/l. The solution was prepared by dissolving ruthenium trichloride, iridium trichloride, and titanium tetrachloride in a hydrochloric acid based solution. The solution was then dried at 60 °C followed by thermal decomposition at 460 °C for 10 minutes. This deposition step was repeated three times. A second coating solution was then prepared by mixing hexachloro ruthenic acid and hexachloro iridic acid into a titanium solution comprising tetrabuthyl ortho titanate in n-propyl alcohol. 10 volume percent of HCI was added to the alcohol solution. The molar ratio of Ti:Ru:lr was 2:1:1. The total Ir+Ru concentration was 30 g/l. The deposition and thermal decomposition of the second coating solution on the substrate was made in the same way as the first coating solution.
The obtained electrode sample was then stabilised at 520 OC for 60 minutes. The chlorine evolution potential at 90 °C in a 300 g/l NaCI solution was tested at pH 2 for the electrode (used as anode) and for a comparative electrode produced in the same way as the first coating layer but with six repetitions instead of three. The current density was 40 A/dm 2 Table 1 below shows the difference between the two electrodes. An accelerated life test was also performed in a Na 2
SO
4 *10H 2 0 250 g/l electrolyte at 60 °C at a pH of 2. The current density was 50A/dm 2 The electrodouble layer measurement by cyclic voltammograms was performed in 0.5M sulphuric acid. Measuring conditions were 0.3 to 1.1V vs. RHE at a sweep rate of Table 1 Sample Cl2 evolution Accelerated life Cyclic voltammograms potential (V vs NHE) (hours at 50A/dm 2 the second (top) coatin layer (mC/cm 2 Electrode according 1.36 285 410 to invention Comparative 1.38 195 190 electrode As can be seen from table 1, a lower CI2 evolution potential is obtained for the electrode according to the invention, which means lower cell voltage, and lower electric energy consumption. As can be further seen, the service life of the electrode of the invention is far better than the comparative electrode. The charge/projected area of the electrode of the invention was shown to be far larger than the comparative electrode, which results in increased service life and lower C12 evolution (higher activity).
Example 2
O
A second coating solution was prepared by mixing ruthenium chloride into a titanium Ssolution comprising tetrabuthyl ortho titanate in n-butyl alcohol. 10 volume percent of HCI was added to the alcohol solution. The molar ratio of Ti:Ru was 2:1. The total Ru concentration was 40 g/l. An electrode with a first oxide layer prepared according to 00 Example 1 was then coated with this second coating solution. The deposition and r thermal decomposition was made in the same way as in Example 1. Chlorine potential and electrodouble layer measurements, according to Example 1, were then performed 10 on the obtained electrode. Table 2 below shows the results of these measurements.
Table 2 Sample CI2 evolution Cyclic voltammograms of potential (V vs NHE) the second (top) coating layer (mC/cm 2 Electrode according 1.35 570 to the invention As can be seen from a comparison of tables 1 and 2, a substantially lower Cl 2 evolution potential is obtained for the electrode according to the invention with only one platinum group metal oxide in the second layer, which again means lower energy consumption.
The charge/projected area of the obtained electrode is also substantially higher than the comparative electrode.
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
N:VvelboumeCaseskPatent\59O00.59999IP59692AUkSpecsIP59692.AU Sped Amendments 2007-1O-24.doc
Claims (19)
1. A method of preparing an electrode comprising providing an electrode Ssubstrate, depositing on said electrode substrate a first substantially aqueous coating solution comprising precursors of a valve metal oxide and of at least two platinum group 00 metal oxides, treating the first coating solution to provide a first metal oxide coating layer on the electrode substrate, depositing directly on said first coating layer a second 00 substantially organic coating solution comprising precursors of a valve metal oxide and of Sat least one platinum group metal oxide, wherein at least one of the precursors is in organic form, treating said second coating solution to provide a second metal oxide coating layer directly on the first coating layer.
2. A method according to claim 1, wherein the precursors of the platinum group Smetal oxides comprise at least one soluble compound of iridium, palladium, platinum, rhodium, osmium, and ruthenium.
3. A method according to claim 1 or 2, wherein the precursor of the valve metal oxide is at least one soluble compound of aluminium, zirconium, bismuth, tungsten, niobium, titanium, silicon and tantalum.
4. A method according to any one of claims 1 to 3, wherein the precursors of the platinum group metal oxides comprise one soluble ruthenium compound and at least one soluble compound of iridium, palladium, platinum, rhodium, and osmium.
A method according to any one of claims 1 to 4, wherein the material of the electrode substrate comprises at least one valve metal of titanium, tantalum, zirconium, niobium, tungsten, and silicon.
6. A method according to any one of claims 1 to 5, wherein the precursors of the platinum and valve metal oxides are dissolved in the coating solutions in a mole ratio of valve metal to platinum metal(s) of about 1:2 to about 2:1.
7. An electrode obtained by providing an electrode substrate, depositing on said electrode substrate a first substantially aqueous coating solution comprising precursors of a valve metal oxide and of at least two platinum group metal oxides, treating the first coating solution to provide a first metal oxide coating layer on the electrode substrate, depositing directly on said first coating layer a second substantially organic coating solution comprising precursors of a valve metal oxide and of at least one platinum group metal oxide, wherein at least one of the precursors is in organic form, treating said second coating solution to provide a second metal oxide coating layer directly on the first coating layer.
8. An electrode comprising an electrode substrate, a first metal oxide coating layer having a charge/projected area from about from about 10 to about 200 mC/cm 2 N:\Mlboum\CaeS\Patn\59000-5 9999\P 599AU SpedsU'59692.AU Specificaon 2008-5-15 doc 9 said first coating layer comprising a valve metal oxide and at least two platinum group 00 0 metal oxides deposited on said electrode substrate, and a second metal oxide coating layer having a charge/projected area from about 210 to about 1000 mC/cm 2 comprising a Svalve metal oxide and at least one platinum group metal oxide deposited directly on said first layer. 00
9. An electrode according to claim 8, wherein the platinum group metal oxides comprise at least one oxide of iridium, platinum, palladium, rhodium, osmium, and 00 ruthenium.
An electrode according to claim 8, wherein the platinum group metal oxide is selected from ruthenium oxide and at least one oxide of iridium, platinum, palladium, rhodium, and osmium.
11. An electrode according to any one of claims 8 to 10, wherein the Scharge/projected area of the first coating layer is from about 25 to about 200 mC/cm 2
12. An electrode according to any one of claims 8 to 10, wherein the charge/projected area of the first coating layer is from about 25 to 190 mC/cm 2
13. An electrode according to any one of claims 8 to 10, wherein the charge/projected area of the second coating layer is from about 250 to 1000 mC/cm 2
14. An electrode according to any one of claims 8 to 10, wherein the charge/projected area of the first coating layer is from about 300 to 800 mC/cm 2
15. An electrode according to any one of claims 8 to 10, wherein the charge/projected area of the second coating layer is from about 300 to 800 mC/cm 2
16. A process of electrolytic production in an electrolytic cell in which an electrode as defined in claim 8 is arranged.
17. Use of an electrode of any one of claims 8 to 15 in an electrolytic cell.
18. An electrode obtained by the method of any one of claims 1 to
19. A method of preparing an electrode, an electrode obtained by the method or use of an electrode substantially as herein described with reference to the accompanying examples. An electrode obtained by providing an electrode substrate or an electrode comprising an electrode substrate substantially as herein described with reference to the accompanying examples. N2\MeboumeCases\Patent\5900OD59999NP59592.AU\Specis\P59692.AU Spedcfcauon 2008-5-15 doc
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03445107 | 2003-10-08 | ||
EP03445107.0 | 2003-10-08 | ||
PCT/SE2004/001428 WO2005033367A1 (en) | 2003-10-08 | 2004-10-06 | Electrode |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2004277578A1 AU2004277578A1 (en) | 2005-04-14 |
AU2004277578B2 true AU2004277578B2 (en) | 2008-07-17 |
Family
ID=34400645
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2004277578A Ceased AU2004277578B2 (en) | 2003-10-08 | 2004-10-06 | Electrode |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1670973B1 (en) |
JP (1) | JP5037133B2 (en) |
KR (1) | KR100787276B1 (en) |
CN (2) | CN1849414B (en) |
AU (1) | AU2004277578B2 (en) |
CA (1) | CA2541311C (en) |
PL (1) | PL1670973T3 (en) |
WO (1) | WO2005033367A1 (en) |
ZA (1) | ZA200601219B (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100812990B1 (en) * | 2006-11-08 | 2008-03-13 | 고등기술연구원연구조합 | Manufacturing method of mono-polar electrode |
EP2390385B1 (en) * | 2010-05-25 | 2015-05-06 | Permelec Electrode Ltd. | Anode for electrolysis and manufacturing method thereof |
JP5456744B2 (en) * | 2010-11-04 | 2014-04-02 | ペルメレック電極株式会社 | Electrolytic sampling method |
IT1403585B1 (en) * | 2010-11-26 | 2013-10-31 | Industrie De Nora Spa | ANODE FOR CHLORINE ELECTROLYTIC EVOLUTION |
CN102400203B (en) * | 2011-11-09 | 2014-06-18 | 广东达志环保科技股份有限公司 | Chromium plating anode of trivalent chromium chloride system |
ES2697901T3 (en) * | 2014-10-27 | 2019-01-29 | Industrie De Nora Spa | Electrode for electrochlorination processes and method of manufacturing them |
AR106068A1 (en) * | 2015-09-25 | 2017-12-06 | Akzo Nobel Chemicals Int Bv | ELECTRODE AND PROCESS FOR ITS MANUFACTURE |
AR106069A1 (en) * | 2015-09-25 | 2017-12-06 | Akzo Nobel Chemicals Int Bv | ELECTRODE AND PROCESS FOR ITS MANUFACTURE |
CN108299868A (en) * | 2016-08-25 | 2018-07-20 | 先丰通讯股份有限公司 | Catalyst coating and use its anode |
CN106367779A (en) * | 2016-11-07 | 2017-02-01 | 南昌专腾科技有限公司 | Titanium-based porous electrode material and preparation method thereof |
CN107142496A (en) * | 2017-04-10 | 2017-09-08 | 广东卓信环境科技股份有限公司 | Active masking liquid of a kind of internal layer and preparation method thereof |
WO2019031753A1 (en) * | 2017-08-11 | 2019-02-14 | 주식회사 엘지화학 | Electrolytic electrode and manufacturing method therefor |
KR101950465B1 (en) | 2017-08-11 | 2019-05-02 | 주식회사 엘지화학 | Electrode for electrolysis and preparation method thereof |
CN108070877B (en) * | 2017-11-09 | 2020-07-07 | 江苏安凯特科技股份有限公司 | Cathode for electrolytic production and preparation method thereof |
CN108048862B (en) * | 2017-11-16 | 2020-04-28 | 江苏安凯特科技股份有限公司 | Anode for chlorine evolution and preparation method thereof |
CN108048865B (en) * | 2017-11-17 | 2020-04-28 | 江苏安凯特科技股份有限公司 | Electrode and preparation method and application thereof |
CA3091306A1 (en) * | 2018-02-26 | 2019-08-29 | T&W Engineering A/S | Electrode for detecting bioelectrical signals |
KR102347982B1 (en) * | 2018-06-12 | 2022-01-07 | 주식회사 엘지화학 | Anode for electrolysis and preparation method thereof |
EP3808449A4 (en) * | 2018-06-12 | 2022-03-30 | Japan Science and Technology Agency | Catalyst and method of use thereof |
KR102503040B1 (en) * | 2018-12-21 | 2023-02-23 | 주식회사 엘지화학 | Anode Comprising Metal Phosphide Complex and Preparation Method thereof |
EP3748042A1 (en) | 2019-06-03 | 2020-12-09 | Permascand Ab | Electrode assembly for electrochemical processes and method of restoring the same |
CN113151885B (en) * | 2021-03-15 | 2023-03-21 | 广州鸿葳科技股份有限公司 | Titanium anode for electroplating and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6217729B1 (en) * | 1999-04-08 | 2001-04-17 | United States Filter Corporation | Anode formulation and methods of manufacture |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4070504A (en) * | 1968-10-29 | 1978-01-24 | Diamond Shamrock Technologies, S.A. | Method of producing a valve metal electrode with valve metal oxide semi-conductor face and methods of manufacture and use |
GB1294373A (en) * | 1970-03-18 | 1972-10-25 | Ici Ltd | Electrodes for electrochemical processes |
BR8006373A (en) * | 1979-10-08 | 1981-04-14 | Diamond Shamrock Corp | ELECTRODE FOR USE IN ELECTRIC PROCESSES, PROCESS FOR ITS MANUFACTURING, AND USE OF THE ELECTRODE |
GB2083837B (en) * | 1980-08-18 | 1984-06-27 | Diamond Shamrock Corp | Manufacture of electrode with manganese dioxide coating valve metal base intermediate semiconducting layer |
JPS5861286A (en) * | 1981-10-08 | 1983-04-12 | Tdk Corp | Electrode for electrolysis and its production |
JPH0660427B2 (en) * | 1988-05-31 | 1994-08-10 | ティーディーケイ株式会社 | Oxygen generating electrode and method for manufacturing the same |
JPH05209299A (en) * | 1992-01-28 | 1993-08-20 | Nippon Steel Corp | Insoluble electrode and its production |
US5503663A (en) * | 1994-11-30 | 1996-04-02 | The Dow Chemical Company | Sable coating solutions for coating valve metal anodes |
US5587058A (en) * | 1995-09-21 | 1996-12-24 | Karpov Institute Of Physical Chemicstry | Electrode and method of preparation thereof |
EP0867527B1 (en) * | 1997-02-27 | 2001-03-21 | Aragonesas Industrias Y Energia, S.A. | Electrode with catalytic coating for electrochemical processes and manufacture thereof |
JP3725685B2 (en) * | 1997-11-21 | 2005-12-14 | ペルメレック電極株式会社 | Hydrogen peroxide production equipment |
CN1179068C (en) * | 2000-08-22 | 2004-12-08 | 黄永昌 | Titanium base iridium dioxide electrode with tin-antiomony intermediate layer |
-
2004
- 2004-10-06 CA CA2541311A patent/CA2541311C/en not_active Expired - Fee Related
- 2004-10-06 AU AU2004277578A patent/AU2004277578B2/en not_active Ceased
- 2004-10-06 WO PCT/SE2004/001428 patent/WO2005033367A1/en active Application Filing
- 2004-10-06 KR KR1020067006852A patent/KR100787276B1/en not_active IP Right Cessation
- 2004-10-06 JP JP2006532238A patent/JP5037133B2/en not_active Expired - Fee Related
- 2004-10-06 EP EP04775517.8A patent/EP1670973B1/en active Active
- 2004-10-06 CN CN2004800264108A patent/CN1849414B/en not_active Expired - Fee Related
- 2004-10-06 PL PL04775517T patent/PL1670973T3/en unknown
- 2004-10-06 CN CN2010102936821A patent/CN101942673A/en active Pending
- 2004-10-06 ZA ZA200601219A patent/ZA200601219B/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6217729B1 (en) * | 1999-04-08 | 2001-04-17 | United States Filter Corporation | Anode formulation and methods of manufacture |
Also Published As
Publication number | Publication date |
---|---|
JP5037133B2 (en) | 2012-09-26 |
KR100787276B1 (en) | 2007-12-20 |
KR20060085676A (en) | 2006-07-27 |
WO2005033367A1 (en) | 2005-04-14 |
AU2004277578A1 (en) | 2005-04-14 |
JP2007507612A (en) | 2007-03-29 |
CA2541311C (en) | 2010-06-01 |
CN1849414B (en) | 2011-01-26 |
WO2005033367A8 (en) | 2006-04-06 |
CN1849414A (en) | 2006-10-18 |
CA2541311A1 (en) | 2005-04-14 |
ZA200601219B (en) | 2007-05-30 |
CN101942673A (en) | 2011-01-12 |
EP1670973B1 (en) | 2018-04-11 |
EP1670973A1 (en) | 2006-06-21 |
PL1670973T3 (en) | 2018-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2004277578B2 (en) | Electrode | |
CA2744764C (en) | Multi-layer mixed metal oxide electrode and method for making same | |
Devilliers et al. | Cr (III) oxidation with lead dioxide-based anodes | |
Moradi et al. | Addition of IrO2 to RuO2+ TiO2 coated anodes and its effect on electrochemical performance of anodes in acid media | |
Chen et al. | Corrosion resistance mechanism of a novel porous Ti/Sn-Sb-RuOx/β-PbO2 anode for zinc electrowinning | |
JP3810043B2 (en) | Chrome plating electrode | |
US20120103828A1 (en) | Electrode for electrolytic chlorine production | |
US6527924B1 (en) | Cathode for electrolyzing aqueous solutions | |
JPS592753B2 (en) | How to get the job done | |
US20130087461A1 (en) | Catalyst coating and process for producing it | |
MXPA05003643A (en) | Coatings for the inhibition of undesirable oxidation in an electrochemical cell. | |
JP3883597B2 (en) | Novel stable coating solutions for producing improved electrocatalytic mixed oxide coatings on metal substrates or metal-coated conductive substrates, and dimensionally stable anodes produced from such solutions | |
US3986942A (en) | Electrolytic process and apparatus | |
US7566389B2 (en) | Electrode | |
CN101338437A (en) | Method for preparing graded multicomponent metal mixing oxide anode | |
CN107075702A (en) | Electrode with duplex coating, its use and preparation method | |
KR20110139126A (en) | Electrode for electrolytic production of chlorine | |
JPS6160147B2 (en) | ||
JP2019119930A (en) | Chlorine generating electrode | |
US4223049A (en) | Superficially mixed metal oxide electrodes | |
US4849085A (en) | Anodes for electrolyses | |
JP2836840B2 (en) | Electrode for chlorine generation and method for producing the same | |
JPH0343353B2 (en) | ||
JP3868513B2 (en) | Electrode for seawater electrolysis and method for producing the same | |
KR20200007306A (en) | Electrode for electrolysis, method for producing the same, and electrochemical cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FGA | Letters patent sealed or granted (standard patent) | ||
MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |