EP1125005A1 - Cathode for electrolysing aqueous solutions - Google Patents
Cathode for electrolysing aqueous solutionsInfo
- Publication number
- EP1125005A1 EP1125005A1 EP00958706A EP00958706A EP1125005A1 EP 1125005 A1 EP1125005 A1 EP 1125005A1 EP 00958706 A EP00958706 A EP 00958706A EP 00958706 A EP00958706 A EP 00958706A EP 1125005 A1 EP1125005 A1 EP 1125005A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- cathode according
- cathode
- precious metal
- zirconium
- 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
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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- 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
Definitions
- the present invention relates to a cathode which can be used for the electrolysis of aqueous solutions in which a water reduction reaction takes place.
- the present invention relates to an activated cathode usable for the electrolysis of aqueous alkaline solutions of alkali metal chlorides, and very particularly for the preparation of chlorine and sodium hydroxide.
- electrolytic cells each of them comprising several mild steel cathodes and several titanium anodes coated with a mixture of titanium and ruthenium oxides. They are generally supplied with an electrolytic solution consisting of approximately 200 to 300 g / l of sodium chloride.
- overvoltage is meant the difference between the thermodynamic potential of the redox couple concerned (H 2 0 / H 2 ) relative to a reference cathode and the potential actually measured in the medium concerned, compared to the same reference electrode.
- overvoltage will be used to denote the absolute value of the cathodic overvoltage.
- a cathode is described, the substrate of which is a plate of titanium, zirconium, niobium or an alloy essentially constituted by an association of these metals and on which a layer of metal oxide, essentially consisting of an oxide of one or more metals chosen from ruthenium, rhodium, palladium, osmium, iridium and platinum and optionally an oxide of one or more metals chosen from calcium , magnesium, strontium, barium, zinc, chromium, molybdenum, tungsten, selenium and tellurium.
- US Patent US 4,100,049 describes a cathode comprising a substrate made of iron, nickel, cobalt or an alloy of these metals and a coating of palladium oxide and zirconium oxide.
- a cathode consisting of an electrically conductive substrate of nickel, stainless steel or mild steel carrying a coating consisting of a plurality of layers of metal oxides, the surface layer consisting by a valve metal oxide, that is to say a metal chosen from groups 4b, 5b and 6b of the periodic table of the elements and the intermediate layer being constituted by a precious metal oxide from group VIII, it is ie ruthenium, rhodium, palladium, osmium, iridium and platinum.
- the intermediate and surface layers can be formed by the oxide of the only metal concerned or by a mixed oxide of the metal concerned and the second metal in small proportion.
- cathodes Although these cathodes have a satisfactory overvoltage, the applicant noted during the evaluation of said cathodes a modification of the polarization curve after the first scan showing a damage to the surface layer, which is detrimental for good protection of the substrate and therefore results in a limited lifetime of said electrodes.
- a cathode making it possible to reduce the overvoltage of the reaction for reducing water in an alkaline medium, characterized in that it is constituted by an electroconductive substrate coated with an intermediate layer of titanium-based oxides and a precious metal from group VIII of the periodic table of the elements and an outer layer of metal oxides comprising titanium, zirconium and a precious metal from group VIII of the periodic table of the elements.
- precious metal of group VIII of the periodic table of the elements is currently meant ruthenium, rhodium, palladium, osmium, iridium or platinum.
- ruthenium or iridium will be used and very particularly ruthenium.
- the intermediate layer contains oxides of titanium and ruthenium.
- the outer layer of metal oxides contains oxides of titanium, zirconium and ruthenium.
- the outer layer consists essentially of ZrTiO 4 accompanied by RuO 2 and possibly ZrO 2 and / or TiO 2 .
- the material constituting the substrate can be chosen from electrically conductive materials. It will advantageously be chosen from the group consisting of titanium, nickel, tantalum, zirconium, nobium, iron and their alloys.
- titanium, nickel, iron or their alloys will be used.
- the precious metal / titanium molar ratio in the intermediate layer is preferably between 0.4 and 2.4.
- the zirconium / titanium molar ratio in the outer layer is generally between 0.25 and 9 and, preferably, between 0.5 and 2.
- the precious metal in the outer layer is at least equal to 10 mol%, preferably between 30% and 50 mol% relative to the metals used in the composition of this layer.
- the cathode according to the present invention can be prepared according to a method which consists in carrying out the following steps: a) pretreatment of a substrate to impart roughness characteristics to the surface, b) coating of the pretreated substrate using a solution A essentially containing titanium and a precious metal, followed by drying, then calcination of the substrate thus coated, c) coating of the substrate obtained in (b) using a solution B comprising titanium, zirconium and a metal valuable, followed by drying, and the calcination of the substrate thus coated.
- the pretreatment generally consists in subjecting the substrate, either to a sandblasting followed optionally by an acid washing, or to a pickling using an aqueous solution of oxalic acid, hydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, a mixture of hydrofluoric acid and glycerol, a mixture of hydrofluoric acid, nitric acid and glycerol or a mixture of hydrofluoric acid, nitric acid and hydrogen peroxide, followed by one or more washing (s) with degassed demineralized water.
- the substrate may be in the form of a solid plate, perforated plate, expanded metal or cathode basket made from the expanded or perforated metal.
- Solution A is generally prepared by bringing into contact at room temperature and with stirring, essentially a mineral or organic salt of titanium and a precious metal with water or in an organic solvent, optionally in the presence of an agent. chelating. The temperature can be raised above the ambient to facilitate the dissolution of the salts.
- a mineral or organic salt of titanium and a precious metal is brought into contact with water or in an organic solvent, optionally in the presence of a chelating agent. Titanium and the precious metal are preferably present in solution A at a concentration at most equal to 10 mole / l.
- Solution B is generally prepared by bringing into contact, at room temperature and with stirring, a mineral or organic salt of titanium, zirconium and a precious metal with water or in an organic solvent, optionally in the presence of 'a chelating agent.
- a mineral or organic salt of titanium, zirconium and a precious metal with water or in an organic solvent, optionally in the presence of 'a chelating agent.
- an ice bath is used to cool the reaction medium.
- a mineral or organic salt of titanium, zirconium and a precious metal is brought into contact with water or in an organic solvent, optionally in the presence of a chelating agent.
- the preferred titanium and precious metal salts are chlorides, oxychlorides, nitrates, oxynitrates, sulfates and alkoxides.
- the precious metal chlorides, ruthenium chlorides, titanium chlorides and titanium oxychlorides are used.
- zirconium salts there can be used chlorides, sulfates, zirconyl chloride, zirconyl nitrate, alkoxides such as butyl zirconate.
- Zirconium and zirconyl chlorides are particularly preferred.
- organic solvent there may be mentioned light alcohols, preferably isopropanol and ethanol, and better still isopropanol and absolute ethanol.
- Titanium and zirconium are generally present in solution B at a concentration ranging from 0.5 to 5 mol / l.
- concentration of precious metal in solution B is generally between 0.05 and 10 mole / l and preferably between 0.1 and 5 mole / l.
- Solution A can be deposited on the pretreated substrate using different techniques such as sol-gel, electrochemical deposition, galvanic plating, spraying or coating.
- the pretreated substrate is coated with solution A, for example using a brush.
- the substrate thus coated is then dried in air and / or in an oven at a temperature below 150 ° C.
- the substrate is calcined in air or in inert gases such as nitrogen, argon or else in inert gases enriched with oxygen at a temperature at least equal to 300 ° C. and preferably between 450 ° C and 550 ° C for a period ranging from 10 minutes to 2 hours.
- step (c) of the process the same deposition techniques can be used as well as the same operating conditions for drying and calcination as step (b) except that the deposition is carried out with solution B.
- Other techniques such as chemical vapor deposition
- CVD chemical vapor deposition
- PVD physical vapor deposition
- plasma spraying are also suitable for coating the pretreated substrate with an intermediate layer and an outer layer.
- Solution A can be deposited both on one side of the pretreated substrate and on both sides. It is also possible to deposit solution B on the two faces of the substrate coated with the intermediate layer.
- step (b) of the process can be repeated several times.
- step (c) of the process can be repeated several times.
- the mass of product deposited is at least equal to 2 g / m 2 , generally between 10 g / m 2 and 60 g / m 2 and, preferably, between 20 g / m 2 and 35 g / m 2 related to the geometric surface of the substrate.
- concentration of solution A is judiciously chosen so that this preferred deposited mass can be obtained by repeating step (b) a reasonable number of times and preferably between 1 and 10 times.
- the mass of product deposited is at least equal to 5 g / m 2 , generally between 5 g / m 2 and 70 g / m 2 and, preferably, between 25 g / m 2 and 50 g / m 2 , related to the geometric surface of the substrate.
- solution B is prepared so that its concentration makes it possible to obtain a preferred deposited mass by repeating step (c) at least 1 time and preferably between 2 and 10 times.
- the cathode of the present invention is particularly suitable for the electrolysis of aqueous solutions of alkali metal chlorides and in particular aqueous solutions of NaCl. The use of the cathode in combination with an anode makes it possible to electrolytically synthesize the chlorine and the hydroxide of an alkali metal with a high Faraday yield.
- DSA Dissionally Stable Anode
- anodes consisting of a titanium substrate coated with a layer of titanium and ruthenium oxides.
- the ruthenium / titanium molar ratio in this layer is advantageously between 0.4 and 2.4.
- the cathode of the present invention has the advantage of having a lower overvoltage than the cathodes of the prior art during operation in electrolysis.
- the cathode of the present invention does not undergo modification from the first characterization cycles and exhibits greater chemical stability with respect to aggressive alkaline media.
- the following examples illustrate the invention without limiting it. EXAMPLES 1. PREPARATION OF A CATHODE (according to the invention)
- a titanium plate 2 mm thick and 4 cm ⁇ 1 cm in size is sanded with corundum particles, to which a round rod for supplying current has been welded.
- a solution A is then prepared, containing ruthenium and titanium in an equimolar amount, by mixing at room temperature with stirring 2.45 g of RuCl 3 , of purity greater than or equal to 98%,
- the end of one of the faces of the pretreated plate is then coated with solution A using a brush, then it is left to air dry for 30 minutes. free and at room temperature.
- the coated plate is then dried additionally in an oven at 120 ° C for 30 minutes, then calcined in an oven in air at 500 ° C for 30 minutes.
- zirconium chloride or oxychloride, ruthenium chloride and titanium chloride or oxychloride are mixed with stirring with absolute ethanol.
- solution B is prepared cold and kept cold by a water / ice bath, with stirring, until use.
- solution B is prepared at 60 ° C and maintained at this temperature, with stirring, until its use.
- the coated plate is then coated in 1.1, with solution B using a brush.
- the coated plate is first dried
- polarization curve is meant the curve of variation of the cathode potential measured with respect to a reference electrode, for example a saturated calomel electrode (DHW), as a function of the current density.
- a reference electrode for example a saturated calomel electrode (DHW)
- the experimental setup consists of the cathode to be evaluated, a platinum counter electrode (surface 5 cm 2 ) and a DHW reference electrode elongated by a capillary, which is placed in the immediate vicinity of the cathode.
- Solution B is prepared by mixing, with stirring, in a glass bottle 1.07 g of RuCI 3 , 2.59 g of ZrOCI 2 , 8H 2 O, 1.55 ml of TiOCI 2 , 2HCI in 7 ml of absolute ethanol , or an overall molar composition of 0.3 Ru-0.7 (Ti, 2Zr).
- the plate coated with the intermediate layer is then coated with solution B thus prepared, then it is dried and calcined in air as indicated in the general procedure. These operations are repeated 8 times and at the end of the last calcination, the deposited mass is 39 g / m 2 related to the geometric surface of the plate.
- the cathode thus prepared was evaluated using the procedure described above.
- the cathodic potential is -1.375 V / DHW for a current density of -2 kA / m 2 .
- Solution B is prepared by mixing, with stirring, in a glass flask 2.49 g RuCI 3 , 2.59 g of ZrOCI 2 , 8H 2 O, 1.55 ml of TiOCI 2 , 2HCI in 10 ml of absolute ethanol or an overall molar composition of 0.5 Ru-0.5 (Ti, 2Zr).
- the plate coated with the intermediate layer is then coated with solution B thus prepared, then it is dried and calcined in air as indicated in the general procedure. These operations are repeated 8 times and at the end of the last calcination, the external deposited mass is 41 g / m 2 relative to the geometric surface of the plate.
- the cathode thus prepared was evaluated using the procedure described above.
- the cathodic potential is -1.195 V / DHW for a current density of -2 kA / m 2 .
- EXAMPLE 3 (ACCORDING TO THE INVENTION):
- Solution B is prepared by mixing, with stirring, in a glass container, cooled using an ice bath, 2.49 g of RuCI 3 , 2.80 g of ZrCI 4 , 1.32 ml of TiCI 4 in 10 ml of absolute ethanol, ie an overall molar composition of 0.5 Ru-0.5, (Ti, Zr).
- the plate coated with the intermediate layer is then coated with solution B thus prepared, then it is dried and calcined in air as indicated in the general procedure. These operations are repeated 8 times and at the end of the last calcination, the deposited mass is 45 g / m 2 of the plate, related to the geometric surface of the plate.
- the cathode thus prepared was evaluated using the procedure described above.
- the cathodic potential is -1.190 V / DHW for a current density of -2 kA / m 2 in a 1 M NaOH solution.
- EXAMPLE 4 (NOT CONFORMING TO THE INVENTION) A cathode is prepared according to patent application EP 209 427 and its evaluation is carried out.
- the substrate consists of a plate of 4 x 1 x 0.2 cm, to which a round current supply rod has been welded.
- a surface treatment is carried out using corundum.
- a solution of 2 g of RuCl 3 in 2 ml of ethanol is prepared at room temperature.
- the control plate is coated with this solution.
- the plate is dried in air at 120 ° C. for 30 minutes, followed by calcination in air (500 ° C, 30 minutes).
- a deposit of 1 6 mg / m 2 of RuO 2 is obtained.
- a solution in 2 cm 3 of ethanol, of 2.6 ml of TiOCI 2 , HCl at 2.5 mol / l in Ti is prepared at room temperature.
- the same coating / steaming / calcination treatments are carried out in air. 8.5 g / m 2 of TiO 2 is thus deposited.
- the cathodic potential of this electrode is -1.240 V / DHW for a current density of -2 kA / m 2 evaluated according to the procedure described above.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9910659 | 1999-08-20 | ||
FR9910659A FR2797646B1 (en) | 1999-08-20 | 1999-08-20 | CATHODE FOR USE IN THE ELECTROLYSIS OF AQUEOUS SOLUTIONS |
PCT/FR2000/002341 WO2001014615A1 (en) | 1999-08-20 | 2000-08-18 | Cathode for electrolysing aqueous solutions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1125005A1 true EP1125005A1 (en) | 2001-08-22 |
EP1125005B1 EP1125005B1 (en) | 2005-04-06 |
Family
ID=9549257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00958706A Expired - Lifetime EP1125005B1 (en) | 1999-08-20 | 2000-08-18 | Cathode for electrolysing aqueous solutions |
Country Status (15)
Country | Link |
---|---|
US (1) | US6527924B1 (en) |
EP (1) | EP1125005B1 (en) |
JP (1) | JP4464023B2 (en) |
KR (1) | KR100735588B1 (en) |
CN (1) | CN1205359C (en) |
AT (1) | ATE292696T1 (en) |
AU (1) | AU7014300A (en) |
CA (1) | CA2347728C (en) |
DE (1) | DE60019256T2 (en) |
ES (1) | ES2240152T3 (en) |
FR (1) | FR2797646B1 (en) |
MX (1) | MXPA01003960A (en) |
NO (1) | NO322413B1 (en) |
PT (1) | PT1125005E (en) |
WO (1) | WO2001014615A1 (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2852973B1 (en) * | 2003-03-28 | 2006-05-26 | Atofina | PROCESS FOR FORMING A COATING OF METAL OXIDES ON AN ELECTROCONDUCTIVE SUBSTRATE; RESULTING ACTIVE CATHODE AND USE THEREOF FOR THE ELECTROLYSIS OF ACQUEUS SOLUTIONS OF ALKALINE COIL CHORIDES. |
FR2853329B1 (en) * | 2003-04-02 | 2006-07-14 | Onera (Off Nat Aerospatiale) | PROCESS FOR FORMING ON METAL A PROTECTIVE COATING CONTAINING ALUMINUM AND ZIRCONIUM |
BRPI0409985B1 (en) * | 2003-05-07 | 2014-05-20 | Eltech Systems Corp | Metal article of a valve metal substrate for use in electrocatalytic processes and process for producing said metal article |
ITMI20061974A1 (en) * | 2006-10-16 | 2008-04-17 | Industrie De Nora Spa | ANODE FOR ELECTROLYSIS |
EP1923487B1 (en) * | 2006-11-20 | 2010-12-22 | Permelec Electrode Ltd. | Method of reactivating electrode for electrolysis |
TW200846499A (en) * | 2007-05-24 | 2008-12-01 | Liung Feng Ind Co Ltd | Method of generating hydrogen using dissimilar metal |
EP2085501A1 (en) * | 2008-01-31 | 2009-08-05 | Casale Chemicals S.A. | High performance cathodes for water electrolysers |
JP5456744B2 (en) * | 2010-11-04 | 2014-04-02 | ペルメレック電極株式会社 | Electrolytic sampling method |
ITMI20102354A1 (en) * | 2010-12-22 | 2012-06-23 | Industrie De Nora Spa | ELECTRODE FOR ELECTROLYTIC CELL |
CN102352517B (en) * | 2011-10-21 | 2014-04-30 | 重庆大学 | High-activity cathode and preparation method thereof |
FI2823079T3 (en) | 2012-02-23 | 2023-05-04 | Treadstone Tech Inc | Corrosion resistant and electrically conductive surface of metal |
CN102677092B (en) * | 2012-05-30 | 2015-01-14 | 浙江大学 | Preparation method of titanium anode |
CN102719859A (en) * | 2012-07-07 | 2012-10-10 | 西安泰金工业电化学技术有限公司 | Titanium mesh anode for electrodeposited nickel and preparing method thereof |
ITMI20122030A1 (en) * | 2012-11-29 | 2014-05-30 | Industrie De Nora Spa | CATODO FOR ELECTROLYTIC EVOLUTION OF HYDROGEN |
CN104973661B (en) * | 2014-04-10 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of composite cathode electrode and its preparation method and application |
KR101949517B1 (en) * | 2017-07-12 | 2019-02-19 | 경북대학교 산학협력단 | Electrodes for electrochemical water treatment comprising mixed metal oxide coating layer, fabrication method thereof and water treatment method using the same |
KR102043423B1 (en) * | 2018-06-12 | 2019-11-11 | 경북대학교 산학협력단 | Composite metal oxide coated, electrically conductivite membrane filters for water treatment and method of fabricating the same |
CN109097790B (en) * | 2018-06-19 | 2020-04-21 | 重庆大学 | Preparation method of bulk phase hydrogen evolution electrode and water electrolysis hydrogen production reactor |
US11668017B2 (en) | 2018-07-30 | 2023-06-06 | Water Star, Inc. | Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes |
US11075435B2 (en) * | 2018-10-25 | 2021-07-27 | International Business Machines Corporation | Electroplating of niobium titanium |
CN109553224A (en) * | 2018-12-07 | 2019-04-02 | 杭州水处理技术研究开发中心有限公司 | A kind of chemical nickle-plating wastewater processing equipment and its method |
US20220243338A1 (en) * | 2019-06-12 | 2022-08-04 | Olin Corporation | Electrode coating |
US11735802B2 (en) | 2020-04-27 | 2023-08-22 | International Business Machines Corporation | Electroplated metal layer on a niobium-titanium substrate |
CN114250454B (en) * | 2021-11-22 | 2023-08-04 | 广东省科学院资源利用与稀土开发研究所 | Titanium matrix protective coating for metal oxide electrode and preparation method thereof |
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US4530742A (en) * | 1983-01-26 | 1985-07-23 | Ppg Industries, Inc. | Electrode and method of preparing same |
MX169643B (en) * | 1985-04-12 | 1993-07-16 | Oronzio De Nora Impianti | ELECTRODE FOR ELECTROCHEMICAL PROCESSES, PROCEDURE FOR ITS PRODUCTION AND ELECTROLYSIS TANK CONTAINING SUCH ELECTRODE |
JPH09120820A (en) * | 1990-02-09 | 1997-05-06 | Osaka Gas Co Ltd | Electrode for solid electrolyte fuel cell and its manufacture |
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JPH1021898A (en) * | 1996-07-04 | 1998-01-23 | Nippon Glass Fiber Co Ltd | Lithium battery |
FR2775486B1 (en) * | 1998-03-02 | 2000-04-07 | Atochem Elf Sa | SPECIFIC CATHODE FOR USE IN THE PREPARATION OF AN ALKALINE METAL CHLORATE AND METHOD FOR THE PRODUCTION THEREOF |
-
1999
- 1999-08-20 FR FR9910659A patent/FR2797646B1/en not_active Expired - Fee Related
-
2000
- 2000-08-18 JP JP2001518480A patent/JP4464023B2/en not_active Expired - Fee Related
- 2000-08-18 AU AU70143/00A patent/AU7014300A/en not_active Abandoned
- 2000-08-18 AT AT00958706T patent/ATE292696T1/en active
- 2000-08-18 MX MXPA01003960A patent/MXPA01003960A/en active IP Right Grant
- 2000-08-18 PT PT00958706T patent/PT1125005E/en unknown
- 2000-08-18 KR KR1020017004951A patent/KR100735588B1/en not_active IP Right Cessation
- 2000-08-18 WO PCT/FR2000/002341 patent/WO2001014615A1/en active IP Right Grant
- 2000-08-18 US US09/807,915 patent/US6527924B1/en not_active Expired - Fee Related
- 2000-08-18 EP EP00958706A patent/EP1125005B1/en not_active Expired - Lifetime
- 2000-08-18 CN CNB00802314XA patent/CN1205359C/en not_active Expired - Fee Related
- 2000-08-18 ES ES00958706T patent/ES2240152T3/en not_active Expired - Lifetime
- 2000-08-18 CA CA2347728A patent/CA2347728C/en not_active Expired - Fee Related
- 2000-08-18 DE DE60019256T patent/DE60019256T2/en not_active Expired - Lifetime
-
2001
- 2001-04-19 NO NO20011931A patent/NO322413B1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
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See references of WO0114615A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU7014300A (en) | 2001-03-19 |
CA2347728A1 (en) | 2001-03-01 |
ES2240152T3 (en) | 2005-10-16 |
FR2797646B1 (en) | 2002-07-05 |
KR20010083919A (en) | 2001-09-03 |
CN1348510A (en) | 2002-05-08 |
FR2797646A1 (en) | 2001-02-23 |
US6527924B1 (en) | 2003-03-04 |
ATE292696T1 (en) | 2005-04-15 |
DE60019256T2 (en) | 2006-03-09 |
JP4464023B2 (en) | 2010-05-19 |
KR100735588B1 (en) | 2007-07-04 |
EP1125005B1 (en) | 2005-04-06 |
CN1205359C (en) | 2005-06-08 |
PT1125005E (en) | 2005-08-31 |
MXPA01003960A (en) | 2002-04-24 |
NO322413B1 (en) | 2006-10-02 |
NO20011931D0 (en) | 2001-04-19 |
CA2347728C (en) | 2010-10-19 |
NO20011931L (en) | 2001-05-28 |
JP2003507580A (en) | 2003-02-25 |
DE60019256D1 (en) | 2005-05-12 |
WO2001014615A1 (en) | 2001-03-01 |
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