ZA200601219B - Electrode - Google Patents
Electrode Download PDFInfo
- Publication number
- ZA200601219B ZA200601219B ZA200601219A ZA200601219A ZA200601219B ZA 200601219 B ZA200601219 B ZA 200601219B ZA 200601219 A ZA200601219 A ZA 200601219A ZA 200601219 A ZA200601219 A ZA 200601219A ZA 200601219 B ZA200601219 B ZA 200601219B
- Authority
- ZA
- South Africa
- Prior art keywords
- electrode
- metal oxide
- platinum
- coating layer
- precursors
- Prior art date
Links
- 238000000576 coating method Methods 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 30
- 239000011247 coating layer Substances 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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 17
- 239000010410 layer Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229910052741 iridium Inorganic materials 0.000 claims description 16
- -1 platinum group metal oxide Chemical class 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 238000000151 deposition Methods 0.000 claims description 8
- 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
- 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
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 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 compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 43
- 239000002253 acid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 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
- 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
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 238000000354 decomposition 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
- 238000004519 manufacturing process Methods 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
- 239000011780 sodium chloride 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electroluminescent Light Sources (AREA)
- Chemically Coating (AREA)
- Hybrid Cells (AREA)
Description
Vv 1
Co : Electrode
The present invention relates to an electrode, a. method of preparing the electrode, and the use thereof. | Background of the invention oo Electrodes coated with titanium oxide, iridium oxide, and ruthenium oxide are commercially used today in electrolytic cells. Such electrodes can be prepared In "accordance with EP 715 002 B1 disclosing a method wherein an anhydrous solvent comprising precursors of mixed metal oxides are deposited on a substrate to form an 410 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. } The invention :
The present invention relates to 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 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 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 fim-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 § mm. Preferably, the electrode 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, more preferably from about 3 to about 6, and most preferably from about 4 to about 5 pm as measured using the SURFTEST 212 surface roughness tester (Mitutoyo, co | 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. RuCls, HzRuClg, IrCls, 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. TiCls.
Preferably, the first coating solution is acidified, suitably by hydrochloric acid h 20 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 soivent in the substantially aqueous coating solution oe 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?. 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 °C. 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 10 to about 30. minutes in order to convert the precursors to their corresponding metal oxides. :
IE Suitable platinum group oxide precursors of the second coating solution include organic compounds, such as organic salts and acids of ruthenium, osmium, rhodium,
X 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. i it has been found that coating solutions for providing the second or outermost . - 10 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, 2- propanol, 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/m* 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? 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 metai(s) of about 1:2 to about 2:1, preferably from about 4:5 to about 1:1.
: s
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
E mole ratio of about 1:2 to about 2:1, preferably from about 2:3 to about 3:2. According to , } one preferred embodiment, precursors of titanium, iridium and/or ruthenium are dissolved ol "5 in the coating solutions in a mole ratio of titanium to iridium and ruthenium of about 1:2 to-
Co about 2:1, preferably from about 4:5 to about 1:1.
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 . 10 layers (with the defined coatings) is preferred, further layers may also be adhered.
The invention also relates to an electrode obtainable by the method as disclosed © herein. :
Lo The invention also relates to 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 mClem? (mCoulomb/cm?), 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 mClcm?, said second layer comprising a valve metal oxide and at least one platinum group metal oxide deposited on the first coating layer.
The chargelprojected 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 0.3t0 1.1V (vs. RHE (Reversible Hydrogen Electrode)) in 0.5M sulphuric acid. The measured values in mCl/cm? 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.
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 electrode substrate is suitably 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 § mm. It has been found that the electrodes with openings within the defined ranges when immersed in an operated cell produce small bubbles of evolved gas, which in turn results
. in an increased 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 siicon, 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 um.
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 30 mole percent of ruthenium oxide counted as ruthenium, and from about 10 to about 30 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 aiso be adhered. ) The invention also relates to the use of the electrode in an electrolytic cell. . 20 Preferably, the electrode is used as an anode, preferably as a dimensionally stable ancde, 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.
All parts and percentages refer to part and percent by weight, if not otherwise stated.
Example 1 . A titanium expanded mesh having a thickness of 1 mm and length and width of 80 and 24 mm respectively was used as electrode substrate after having been degreased
Co 5 : } and pickled in boiling hydrochloric acid. A first coating solution was deposited on the substrate having a molar ratio of Ti:Ru:ir of 2:1:1, in which the total Ir+Ru concentration oo was 50 g/l. The solution was prepared by dissolving ruthenium trichloride, iridium hE trichloride, and titanium tetrachloride in a hydrochloric acid based solution. The ‘solution "5 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 tetrabuthy! 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 © 10 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 °C for 60 minutes. The chlorine evolution potential at 90 °C in a 300 g/l NaCl 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 Adm?
Table 1 below shows the difference between the two electrodes, An accelerated life test was also performed in a Na;SO4*10H,0 250 g/l electrolyte at 60 °C at a pH of 2. The : current density was 50A/dm% 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 50mV/second.
Table 1 ‘ Cl, evolution | Accelerated life | Cyclic voltammograms « : layer (mC/cm?)
Electrode according | 1.36 285 410 pres RA
Comparative 1.38 195 ©1190 fren
As can be seen from table 1, a lower Cl, 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 resuits in increased service life and lower Cl, evolution (higher activity).
A second coating solution was prepared by mixing ruthenium chloride .into a titanium solution: comprising tetrabuthyl ortho titanate in n-butyl alcohol. 10 volume percent of HCI . 5 was added to the alcohol solution. The molar ratio of Ti:Ru was 21. The total Ru concentration was 40 g/l. An electrode with a first oxide layer prepared according to ‘ - Example 1 was then coated with this second coating solution. The deposition and thermal i. decomposition was made in the same way as in Example 1. Chlorine potential and electrodouble layer measurements, according to Example 1, were then performed on the obtained electrode. Table 2 Below shows the results of these measurements. ‘ Sample Cl; evolution | Cyclic voltammograms of potential (V vs NHE) | the second (top) coating ee
Electrode according | 1.35 570 pee]
As can be seen from a comparison of tables 1 and 2, a substantially lower Cl, 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. :
Claims (12)
1. 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 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 on the 10° first coating layer. : SERRE
2. Method according to claim 1, wherein the precursors of the platinum group - ’ metal oxides comprise at least one soluble compound of iridium, palladium, platinum, . rhodium, osmium, and ruthenium.
3. 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, Method according to any of claims 1-3, 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.
5. Method according to any of claims 1-4, wherein the material of the electrode - substrate comprises at least one valve metal of titanium, tantalum, zirconium, niobium, tungsten, and silicon. ] ~~
6. Electrode obtainable by the method according to any of claims 1-5. : - :
7. 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?, 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 metal oxide coating layer having a charge/projected area from about 210 to about 1000 mC/cm? comprising a valve metal oxide and at least one platinum group metal oxide deposited on said first layer. }
8. Electrode according to claim 7, wherein the platinum group metal oxides comprise at least one oxide of iridium, platinum, palladium, rhodium, osmium, and ruthenium.
9. Electrode according to claim 7 or 8, wherein the platinum group metal oxide - is selected from ruthenium oxide and at least one oxide of iridium, platinum, palladium, rhodium, and osmium. . 10. Use of an electrode according to any of claims 6-8 in an electrolytic cell.
W02005/033367 PCT/SE2004/001428
11. A method according to claim 1, substantially as herein described with reference to any one of Example 1 or 2.
12. An electrode according to claim 7, substantially as herein described with reference to Example 1 or 2. AMENDED SHEET ~~ 2006 -11- 24
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03445107 | 2003-10-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200601219B true ZA200601219B (en) | 2007-05-30 |
Family
ID=34400645
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200601219A ZA200601219B (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 |
WO2016066544A1 (en) * | 2014-10-27 | 2016-05-06 | Industrie De Nora S.P.A. | Electrode for electrochlorination processes and method of manufacturing thereof |
AR106069A1 (en) * | 2015-09-25 | 2017-12-06 | Akzo Nobel Chemicals Int Bv | ELECTRODE AND PROCESS FOR ITS MANUFACTURE |
AR106068A1 (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 |
KR101950465B1 (en) | 2017-08-11 | 2019-05-02 | 주식회사 엘지화학 | Electrode for electrolysis and preparation method thereof |
EP3492631B1 (en) * | 2017-08-11 | 2021-03-03 | LG Chem, Ltd. | Electrolytic electrode and manufacturing method therefor |
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 |
EP3758582A1 (en) * | 2018-02-26 | 2021-01-06 | T&W Engineering A/S | Electrode for detecting bioelectrical signals |
EP3808449A4 (en) * | 2018-06-12 | 2022-03-30 | Japan Science and Technology Agency | Catalyst and method of use thereof |
KR102347982B1 (en) * | 2018-06-12 | 2022-01-07 | 주식회사 엘지화학 | Anode for electrolysis and preparation method 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 |
Family Cites Families (13)
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 |
US6217729B1 (en) * | 1999-04-08 | 2001-04-17 | United States Filter Corporation | Anode formulation and methods of manufacture |
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 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 CN CN2004800264108A patent/CN1849414B/en not_active Expired - Fee Related
- 2004-10-06 AU AU2004277578A patent/AU2004277578B2/en not_active Ceased
- 2004-10-06 PL PL04775517T patent/PL1670973T3/en unknown
- 2004-10-06 JP JP2006532238A patent/JP5037133B2/en not_active Expired - Fee Related
- 2004-10-06 CA CA2541311A patent/CA2541311C/en not_active Expired - Fee Related
- 2004-10-06 EP EP04775517.8A patent/EP1670973B1/en active Active
- 2004-10-06 ZA ZA200601219A patent/ZA200601219B/en unknown
- 2004-10-06 CN CN2010102936821A patent/CN101942673A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CN1849414A (en) | 2006-10-18 |
EP1670973B1 (en) | 2018-04-11 |
WO2005033367A8 (en) | 2006-04-06 |
PL1670973T3 (en) | 2018-09-28 |
CA2541311A1 (en) | 2005-04-14 |
JP2007507612A (en) | 2007-03-29 |
KR100787276B1 (en) | 2007-12-20 |
EP1670973A1 (en) | 2006-06-21 |
WO2005033367A1 (en) | 2005-04-14 |
AU2004277578B2 (en) | 2008-07-17 |
CN101942673A (en) | 2011-01-12 |
CA2541311C (en) | 2010-06-01 |
KR20060085676A (en) | 2006-07-27 |
JP5037133B2 (en) | 2012-09-26 |
AU2004277578A1 (en) | 2005-04-14 |
CN1849414B (en) | 2011-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2004277578B2 (en) | Electrode | |
CA2744764C (en) | Multi-layer mixed metal oxide electrode and method for making same | |
Chen et al. | Corrosion resistance mechanism of a novel porous Ti/Sn-Sb-RuOx/β-PbO2 anode for zinc electrowinning | |
Song et al. | Structure and properties of PbO2–CeO2 anodes on stainless steel | |
Chen et al. | Ti/RuO2–Sb2O5–SnO2 electrodes for chlorine evolution from seawater | |
Moradi et al. | Addition of IrO2 to RuO2+ TiO2 coated anodes and its effect on electrochemical performance of anodes in acid media | |
Devilliers et al. | Cr (III) oxidation with lead dioxide-based anodes | |
US4331528A (en) | Coated metal electrode with improved barrier layer | |
US7332065B2 (en) | Electrode | |
Huang et al. | Electrochemical behavior of IrO2-Ta2O5/Ti anodes prepared with different surface pretreatments of Ti substrate | |
US6251254B1 (en) | Electrode for chromium plating | |
JP4464023B2 (en) | Cathode that can be used for electrolysis of aqueous solutions | |
JPS592753B2 (en) | How to get the job done | |
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 | |
CA2529190C (en) | Electrode with electroconductive titanium oxide and process for manufacturing same | |
US7566389B2 (en) | Electrode | |
EP0027051B1 (en) | Coated metal electrode with improved barrier layer and methods of manufacture and use thereof | |
KR20110139126A (en) | Electrode for electrolytic production of chlorine | |
JPH04231491A (en) | Electric catalyzer cathode and its manufacture | |
JP2019119930A (en) | Chlorine generating electrode | |
CA2030092C (en) | Electrocatalytic coating | |
JPH0343353B2 (en) | ||
JP3868513B2 (en) | Electrode for seawater electrolysis and method for producing the same | |
JPH06306670A (en) | Production of electrode for generating oxygen |