EP0240413A1 - Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode - Google Patents

Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode Download PDF

Info

Publication number
EP0240413A1
EP0240413A1 EP87400662A EP87400662A EP0240413A1 EP 0240413 A1 EP0240413 A1 EP 0240413A1 EP 87400662 A EP87400662 A EP 87400662A EP 87400662 A EP87400662 A EP 87400662A EP 0240413 A1 EP0240413 A1 EP 0240413A1
Authority
EP
European Patent Office
Prior art keywords
nickel
cathode
layer
substrate
metal
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.)
Granted
Application number
EP87400662A
Other languages
English (en)
French (fr)
Other versions
EP0240413B1 (de
Inventor
Jacques Clerc-Renaud
Francis Leroux
Dominique Ravier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT87400662T priority Critical patent/ATE56757T1/de
Publication of EP0240413A1 publication Critical patent/EP0240413A1/de
Application granted granted Critical
Publication of EP0240413B1 publication Critical patent/EP0240413B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for

Definitions

  • the present invention relates to a new cathode usable in electrolysis. It also relates to a method of manufacturing this cathode. It relates very particularly to a cathode which can be used in the electrolysis of aqueous alkali metal halide solution which is remarkable in particular for the low value of its working potential and for the stability over time of its electrochemical performance.
  • This cathode belongs to the family of metallic cathodes, activated, obtained by coating a cathode substrate by means of various activation materials, the aim being essentially to reduce the hydrogen overvoltage in an alkaline medium.
  • European patent application 0129374 describes cathodes carrying a coating consisting of a mixture of at least one platinum group metal and at least one oxide of a platinum group metal, the platinum group metal representing 2 to 30 % of the weight of said mixture.
  • Japanese patent application published under No. 57-13189 describes a nickel or nickel alloy cathode carrying a coating consisting of a platinum group metal or an oxide of said metal.
  • British patent 1,511,719 describes a cathode comprising a metal substrate, a cobalt coating and a second ruthenium coating.
  • Japanese patent application published under the number 54-090080 describes a technique for manufacturing a cathode consisting of treating a ferrous substrate with perchloric acid and then coating this cathode by sintering active substances including ruthenium, iridium , iron and nickel in metallic or metal compound form.
  • a deposition technique on a substrate, for example made of nickel, of a coating made of a nickel-palladium alloy is also described in American patent 3,216,919 according to this patent, an alloy layer is applied to the substrate. powder form and then sintering said alloy powder.
  • Japanese patent application published under the number 54-110983 (US Patent No. 4,465,580) describes a cathode carrying a coating consisting of a dispersion of particles of nickel or a nickel alloy and an activator consisting of platinum , ruthenium, iridium, rhodium, palladium or osmium or an oxide of these metals.
  • Japanese patent application published under number 53-010036 describes a cathode having a valve metal substrate and a coating of an alloy of at least one platinum group metal and a valve metal and, optionally a surface coating d '' at least one platinum group metal.
  • European patent application 0129734 describes a technique for manufacturing a cathode, by depositing on a electroconductive substrate a coating solution comprising a metal oxide precursor and necessarily a pickling agent in order to dissolve the most soluble parts of the substrate and / or a coating layer already deposited, this technique further comprising an operation of removing the most volatile part of the coating solution, said part containing solubilized fractions of the substrate (op. cit. p. 14).
  • precious metals denotes ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the expression “covering power” designates the ratio (R) between the projected surface of the layer b and the projected surface of the substrate.
  • strong covering metal designates an R ratio greater than 95%.
  • metals corresponding to this definition By way of illustration of metals corresponding to this definition, mention will in particular be made of nickel, cobalt, iron and their alloys or alloys of the preceding containing less than 15 atomic% of phosphorus, boron or sulfur.
  • the cathodes in accordance with the invention must comprise a layer a in contact with the substrate and a layer b in contact with the electrolyte and with a layer a, which means that they may have only one single layer a and single layer b or a succession of layers a and b, starting from the substrate, and ending with a layer b.
  • the layer a consists of at least one compound chosen from the group consisting of platinum, ruthenium, rhodium, oxides of ruthenium, of iridium, of rhodium, of platinum, the mixtures of the abovementioned oxides and of titanium or nickel oxides, and in which the layer b consists of nickel or cobalt.
  • the compound (s) constituting the layer a in contact with the substrate is (are) advantageously deposited (s) in an amount representing from 0.2 to 5 mg / cm 2 .
  • the compound (s) constituting layer b in contact with the electrolyte is (are) deposited in an amount representing 1 to 15 mg / cm 2 .
  • the quantities of compounds which can constitute the any intermediate layers a and b are not critical but, in such a case, it is recommended to respect the respective values mentioned above.
  • the material constituting the substrate can be chosen from electrically conductive materials. It will advantageously be chosen from the group consisting of nickel, stainless steel and mild steel without this list being limiting.
  • the substrate may be in the form of a plate, sheet, lattice, wire mesh or expanded metal, grids, said materials being able to have a planar, cylindrical shape or any other shape depending on the technology employed.
  • the invention also relates to a method of manufacturing these cathodes.
  • This process essentially consists in depositing on the substrate, possibly subjected to an appropriate preliminary treatment, the layers of one or more compounds leading to the metals or compounds constituting the layers a and b (hereinafter precursors) and then subjecting the assembly to a treatment leading to the desired chemical form (metal, oxide).
  • the preliminary treatment of the substrate advantageously consists of a degreasing - if necessary - followed by a pickling, mechanical and / or chemical, according to techniques now well known.
  • the aforementioned precursors are deposited in the form of a solution or suspension.
  • a solvent or diluent such as water, a mineral or organic acid or an organic solvent.
  • An organic solvent is preferably used such as dimethylformamide, an alcohol and in particular ethanol, 2-propanol or ethyl - ..: -2 hexanol.
  • the atomic concentration of metal is between 3.10-2 and 3 moles / liter and preferably between 1 and 2 moles / liter.
  • the precursors which can be used in the invention generally consist of mineral or organic salts of metals, such as, for example, halides, nitrates, carbonates, sulfates, or even acetates, acetylacetonates.
  • the above-mentioned precursor layers can be deposited using conventional techniques: immersion of the substrates in the solution (s), coating with a brush, brush or the like, electrostatic spraying. Layers a and b can also be deposited galvanically. In the hypothesis of a deposition of layer b by chemical means, it may be advantageous to carry out sensitization of the layer a previously deposited. This treatment, which comprises a succession of sensitization / rinsing phases, is described for example in Modern Electroplating by F. LOWENHEIM - John Wiley & Sons 1974 pp. 644 to 646.
  • the preparation of solutions and the deposition of said solutions are generally carried out at ambient temperature and in air. Naturally, it is possible, if necessary, to raise the temperature in particular to facilitate the dissolution of certain precursors, and / or to work under an atmosphere of nitrogen or other inert gas with respect to the precursors.
  • the transformation of the precursors of the layer a is generally done by heat treatment.
  • This treatment is advantageously preceded by an air drying intended to totally or partially remove the solvent or diluent.
  • This steaming can be done at a temperature of up to 200 ° C, the temperature range from 100 to 150 ° C being particularly recommended.
  • the duration of this treatment is a few tens of minutes.
  • the actual treatment is generally carried out in air at a temperature varying, depending on the precursors used, between 200 and 1000 ° C. Preferably, one operates at a temperature between 400 and 750 ° C.
  • the duration of this heat treatment is generally between 15 min and 1 h per layer. This heat treatment can be carried out after each baking or after the last baking in the case of the deposition of several layers.
  • the cathode of the invention is suitable for use in electrolysis cells with production of hydrogen in basic medium.
  • the cathode is particularly suitable for the electrolysis of aqueous solutions of alkali metal chlorides and in particular aqueous solutions of sodium chloride and for the electrolysis of water, for example in the electrolysis of aqueous solutions of potassium hydroxide .
  • microporous diaphragms can be used as separators, but the cathodes according to the invention are of particular interest in membrane technology.
  • the substrate consists of a nickel plate of 200 x 10 x 1 mm.
  • a surface treatment is carried out using corundum (average equivalent grain diameter: 250 ⁇ m)
  • the nickel plate is coated with this solution.
  • the nickel plate coated according to a is successively immersed in solution A at room temperature for 1 min, in solution B at the temperature of 30 ° C for 1 min, then in 200 cm 3 of solution C maintained at 30 ° C for 60 min.
  • a deposit of 2.29 mg / cm 2 of Ni is thus obtained in the form of a nickel / phosphorus alloy with less than 15 atomic% of phosphorus.
  • This cathode tested in sodium hydroxide at 450 g / 1, at 85 ° C and under 50 A / dm 2 has a working potential of -1220 mV compared to the saturated calomel electrode (ECS).
  • a nickel substrate is used which has undergone a surface treatment under the conditions of Example 1.
  • This double-coated cathode has a working potential of -1310 mV compared to E.C.S. (test in soda of example 1).
  • a nickel substrate treated as in Example 1 is used.
  • a coating of the nickel plate is carried out using a Pd (NO 3 ) 2 solution , containing approximately 16% by weight of palladium metal.
  • a deposit of 3.4 mg / cm 2 of nickel is obtained in the form of a nickel / phosphorus alloy.
  • This double-coated cathode has a working potential of -1235 mV compared to E.C.S. (test in soda of example 1).
  • a nickel substrate treated as in Example 1 is used.
  • a deposit of 4.85 mg / cm 2 of nickel is obtained in the form of a nickel / phosphorus alloy.
  • This cathode, carrying a double coating, has a working potential of -1290 mV compared to E.C.S. (test in soda of example 1).
  • a nickel substrate treated as in Example 1 is used.
  • a layer of this solution is deposited on the nickel substrate, according to the coating / baking / heat treatment sequence of Example 1.
  • a deposit of 1.4 mg / cm 2 of RuO 2 and TiO 2 is obtained.
  • a deposit of 2.55 mg / cm 2 of nickel is obtained in the form of a nickel / phosphorus alloy.
  • This cathode, carrying a double coating, has a working potential of -1230 mV compared to E.C.S. (test in soda of example 1).
  • a nickel substrate is used which has undergone a surface treatment under the conditions of Example 1.
  • a layer of solution D is deposited on the nickel substrate first (coating / baking / heat treatment sequence of example 1), then after cooling 2 layers of solution E (also coating, steaming, heat treatment sequence of Example 1).
  • a deposit of 1.94 mg / cm 2 of Ru0 2 and NiO is obtained (weight ratio 1/1 of oxide).
  • a deposit of 2.4 mg / cm 2 of nickel is obtained in the form of a nickel / phosphorus alloy.
  • This cathode, carrying a triple coating, has a working potential of -1225 mV compared to E.C.S. (test in the soda of Example 1).
  • a nickel substrate treated as in Example 1 is used.
  • a deposit of 2.9 mg / cm 2 of nickel is obtained in the form of a nickel / phosphorus alloy.
  • This cathode, carrying a double coating, has a working potential of -1300 mV compared to E.C.S. (test in the soda of Example 1).
  • a nickel substrate treated as in Example 1 is used.
  • a ruthenium metal deposition is carried out on the nickel substrate by electrolysis of solution F at a temperature of 30 ° C under a current density of 15 A / dm 2 for 60 min.
  • This cathode, carrying a double coating, has a working potential of -1200 mV compared to E.C.S. (test in soda of example 1).
  • a nickel substrate treated as in Example 1 is used.
  • a layer of this solution is deposited on the nickel substrate according to the coating / baking / heat treatment sequence of Example 1.
  • a solution G containing 30 g / l of CoCl 2 , 6H 2 O is prepared at 23 ° C; 20 g / 1 of Na H 2 P0 2 , H 2 0; 29.6 g / 1 sodium citrate; 50.0 g / 1 NH 4 Cl; 30 cm 3/1 NH 4 OH 20% by weight.
  • the nickel plate coated according to a is successively immersed in solution A (of Example 1) at room temperature for 1 min, in solution B (of Example 1) at the temperature of 30 ° C for 1 min , then in 200 cm 3 of solution G maintained at 80 ° C for 20 min.
  • a deposit of 2 mg / cm 2 of cobalt is obtained in the form of a cobalt / phosphorus alloy with less than 15 atomic% of phosphorus.
  • a nickel substrate is used which has undergone a surface treatment under the conditions of Example 1.
  • a deposition of galvanic Ni is carried out on the substrate coated according to a, by electrolysis of an aqueous solution of nickel chloride 300 g / 1 + H 3 B0 3 38 g / 1 at a temperature of 60 ° C at a density of current of 5A / dm 2 for 30 min (volume of the solution: 400 cm 3 ).
  • a deposit of 4.3 mg / cm 2 of nickel metal is obtained.
  • This cathode, carrying a double coating, has a working potential of -1200 mV compared to E.C.S. (test in soda of example 1).
  • Example 1 The test of Example 1 is repeated using in the solution C 30 cm 3 / l of IIH 4 OH, 20% by weight.
  • Example 1 c The working potential measured under the conditions of Example 1 c is - 1240 mV relative to E.C.S.
  • Example 1 The test of Example 1 is repeated by replacing the nickel substrate with a mild steel substrate, treated as in this Example 1.
  • a layer of this solution is deposited on the mild steel substrate according to the coating / baking / heat treatment sequence of Example 1.
  • a deposit of 3.2 mg / cm 2 of nickel is obtained in the form of an Ni-P alloy with less than 15 atomic% of phosphorus.
  • This double-coated cathode has a working potential of -1240 mV compared to E.C.S. (test in soda of example 1).
  • a nickel substrate is used which has undergone a surface treatment under the conditions of Example 1.
  • a layer of this solution is deposited on the nickel substrate according to the coating / steaming / heat treatment sequence of Example 1.
  • This double-coated cathode has a working potential of -1200 mV compared to E.C.S. (test in soda of example 1).
  • Example 1 On the nickel substrate surface-treated according to Example 1, a deposit of 2.2 mg / cm 2 of nickel is carried out according to the procedure described in Example 1-b.
  • This cathode tested in the soda of example 1, has a working potential of ⁇ 1490 mV compared to E.C.S.
  • This cathode tested in the soda of Example 1, has a working potential of ⁇ 1480 mV compared to E.C.S.
  • Example 10 On the nickel substrate surface-treated according to Example 1, a deposit of 5 mg / cm 2 of nickel is carried out according to the procedure described in Example 10-b.
  • This cathode tested in the soda of Example 1, has a working potential of -1640 mV compared to E.C.S.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Chemically Coating (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)
  • Electroplating Methods And Accessories (AREA)
EP87400662A 1986-04-03 1987-03-25 Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode Expired - Lifetime EP0240413B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87400662T ATE56757T1 (de) 1986-04-03 1987-03-25 Kathode fuer elektrolyse und verfahren zur herstellung einer solchen kathode.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8604767 1986-04-03
FR8604767A FR2596776B1 (fr) 1986-04-03 1986-04-03 Cathode pour electrolyse et un procede de fabrication de ladite cathode

Publications (2)

Publication Number Publication Date
EP0240413A1 true EP0240413A1 (de) 1987-10-07
EP0240413B1 EP0240413B1 (de) 1990-09-19

Family

ID=9333848

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87400662A Expired - Lifetime EP0240413B1 (de) 1986-04-03 1987-03-25 Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode

Country Status (9)

Country Link
US (1) US4798662A (de)
EP (1) EP0240413B1 (de)
JP (1) JPS62238385A (de)
KR (1) KR890002699B1 (de)
CN (1) CN1010234B (de)
AT (1) ATE56757T1 (de)
CA (1) CA1285903C (de)
DE (1) DE3764989D1 (de)
FR (1) FR2596776B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2775486A1 (fr) * 1998-03-02 1999-09-03 Atochem Elf Sa Cathode specifique, utilisable pour la preparation d'un chlorate de metal alcalin et son procede de fabrication

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0726240B2 (ja) * 1989-10-27 1995-03-22 ペルメレック電極株式会社 鋼板の電解酸洗又は電解脱脂方法
US5227030A (en) * 1990-05-29 1993-07-13 The Dow Chemical Company Electrocatalytic cathodes and methods of preparation
US5035789A (en) * 1990-05-29 1991-07-30 The Dow Chemical Company Electrocatalytic cathodes and methods of preparation
JP3628756B2 (ja) * 1995-04-28 2005-03-16 ペルメレック電極株式会社 ガス拡散電極
US5645930A (en) * 1995-08-11 1997-07-08 The Dow Chemical Company Durable electrode coatings
AU4644097A (en) * 1996-07-09 1998-02-10 James A. Patterson Nuclear transmuted elements having unnatural isotopic distributions by electrolysis and method of production
US5676816A (en) * 1996-07-12 1997-10-14 Patterson; James A. Catalytic particles electrolytic cell system and method for producing heat
AU4427997A (en) * 1997-09-19 1999-04-12 James A. Patterson Catalytic ceramic particles, electrolytic production of heat
US6315880B1 (en) * 1997-10-16 2001-11-13 Mary R. Reidmeyer Chemical plating method, electrolytic cell and automotive oxygen sensor using it
EP0935265A3 (de) 1998-02-09 2002-06-12 Wilson Greatbatch Ltd. Durch thermische Zerstäubung beschichtetes Substrat zur Verwendung in einer elektrischen Energiespeicheranordnung und Herstellungsverfahren
FR2852973B1 (fr) * 2003-03-28 2006-05-26 Atofina Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur; cathode activee en resultant et son utilisation pour l'electrolyse de solutions acqueuses de chorures de meteaux alcalins.
ITMI20041006A1 (it) * 2004-05-20 2004-08-20 De Nora Elettrodi Spa Anodo per sviluppo ossigeno
EP2085501A1 (de) * 2008-01-31 2009-08-05 Casale Chemicals S.A. Hochleistungskathoden für Wasserelektrolyseure
ITMI20090880A1 (it) * 2009-05-19 2010-11-20 Industrie De Nora Spa Catodo per processi elettrolitici
US9145615B2 (en) 2010-09-24 2015-09-29 Yumei Zhai Method and apparatus for the electrochemical reduction of carbon dioxide
JP2013166994A (ja) * 2012-02-15 2013-08-29 Asahi Kasei Chemicals Corp 電解用電極、電解槽及び電解用電極の製造方法
WO2017048773A1 (en) * 2015-09-14 2017-03-23 President And Fellows Of Harvard College Carbon fixation systems and methods
JP6972038B2 (ja) 2016-07-06 2021-11-24 プレジデント アンド フェローズ オブ ハーバード カレッジ アンモニア合成法及びシステム
CN109894130B (zh) * 2019-04-01 2022-01-14 国能南京电力试验研究有限公司 一种脱汞催化剂及其制备方法
JP7786869B2 (ja) * 2020-03-30 2025-12-16 旭化成株式会社 水素発生用陰極

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2265454A2 (en) * 1974-03-26 1975-10-24 Uhde Gmbh Friedrich Polyether-polycarbonate block copolymer films - esp for haemodialysis made by casting from soln
FR2311108A1 (fr) * 1975-05-12 1976-12-10 Hodogaya Chemical Co Ltd Cathode activee pour electrolyse

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2113676C2 (de) * 1971-03-20 1985-09-12 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach Elektrode für elektrochemische Prozesse
US3941675A (en) * 1971-09-28 1976-03-02 Friedrich Uhde Gmbh Bipolar multiple electrolytic cell comprising a diaphragm and electrode for same
GB2083837B (en) * 1980-08-18 1984-06-27 Diamond Shamrock Corp Manufacture of electrode with manganese dioxide coating valve metal base intermediate semiconducting layer
JPS6021232B2 (ja) * 1981-05-19 1985-05-25 ペルメレツク電極株式会社 耐久性を有する電解用電極及びその製造方法
JPS59100280A (ja) * 1982-12-01 1984-06-09 Toagosei Chem Ind Co Ltd 水素発生用陰極
US4530742A (en) * 1983-01-26 1985-07-23 Ppg Industries, Inc. Electrode and method of preparing same
DE3322169A1 (de) * 1983-06-21 1985-01-10 Sigri Elektrographit Gmbh, 8901 Meitingen Kathode fuer waesserige elektrolysen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2265454A2 (en) * 1974-03-26 1975-10-24 Uhde Gmbh Friedrich Polyether-polycarbonate block copolymer films - esp for haemodialysis made by casting from soln
FR2311108A1 (fr) * 1975-05-12 1976-12-10 Hodogaya Chemical Co Ltd Cathode activee pour electrolyse

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2775486A1 (fr) * 1998-03-02 1999-09-03 Atochem Elf Sa Cathode specifique, utilisable pour la preparation d'un chlorate de metal alcalin et son procede de fabrication
WO1999045175A1 (fr) * 1998-03-02 1999-09-10 Atofina Cathode specifique, utilisable pour la preparation d'un chlorate de metal alcalin, et son procede de fabrication

Also Published As

Publication number Publication date
CA1285903C (fr) 1991-07-09
JPS62238385A (ja) 1987-10-19
KR890002699B1 (ko) 1989-07-24
KR870010220A (ko) 1987-11-30
FR2596776B1 (fr) 1988-06-03
DE3764989D1 (de) 1990-10-25
FR2596776A1 (fr) 1987-10-09
US4798662A (en) 1989-01-17
ATE56757T1 (de) 1990-10-15
EP0240413B1 (de) 1990-09-19
CN87102588A (zh) 1987-10-14
JPH021918B2 (de) 1990-01-16
CN1010234B (zh) 1990-10-31

Similar Documents

Publication Publication Date Title
EP0240413B1 (de) Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode
CA2347728C (fr) Cathode utilisable pour l'electrolyse de solutions aqueuses
US4331528A (en) Coated metal electrode with improved barrier layer
CA2665569C (en) Cathode for electrolytic processes
FR2480795A1 (fr) Cathode pour reactions electrochimiques et procede de fabrication
JPH0694597B2 (ja) 電気化学的工程において使用する電極とその製造方法
FR2460343A1 (fr) Cathode pour la production electrolytique d'hydrogene
EP0715002B1 (de) Stabile Beschichtungslösungen zur Bildung von elektrokatalytischen Beschichtungen aus gemischten Oxyden auf Metall oder metallisierten Trägern und Verfahren zur Herstellung von dimensionstabilen Anoden unter Verwendung dieser Lösungen
JP2019119930A (ja) 塩素発生用電極
EP0027051B1 (de) Beschichtete Metallelektrode mit Sperrschicht und Verfahren zu deren Herstellung und Verwendung
EP1608795B1 (de) Verfahren zur herstellung einer metalloxidbeschichtung auf einem leitfähigen substrat, aktivierte kathode davon und ihre verwendung zur elektrolyse von wässriger alkalichlorid-lösungen
EP0198752A1 (de) Kathode für Elektrolyse und deren Herstellungsverfahren
EP0209427A1 (de) Kathode für Elektrolyse und Herstellungsverfahren dieser Kathode

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19870328

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19890720

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19900919

REF Corresponds to:

Ref document number: 56757

Country of ref document: AT

Date of ref document: 19901015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3764989

Country of ref document: DE

Date of ref document: 19901025

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ITTA It: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19911111

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911223

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19920311

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920316

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19920319

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920326

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920331

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920430

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920512

Year of fee payment: 6

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19930325

Ref country code: AT

Effective date: 19930325

Ref country code: GB

Effective date: 19930325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19930331

Ref country code: BE

Effective date: 19930331

Ref country code: LI

Effective date: 19930331

BERE Be: lapsed

Owner name: ATOCHEM

Effective date: 19930331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19931001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19931130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19931201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 87400662.0

Effective date: 19931008