EP0129088A1 - Cathode pour électrolyses aqueuses - Google Patents
Cathode pour électrolyses aqueuses Download PDFInfo
- Publication number
- EP0129088A1 EP0129088A1 EP84105859A EP84105859A EP0129088A1 EP 0129088 A1 EP0129088 A1 EP 0129088A1 EP 84105859 A EP84105859 A EP 84105859A EP 84105859 A EP84105859 A EP 84105859A EP 0129088 A1 EP0129088 A1 EP 0129088A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nickel
- cathode
- layer
- oxide
- ruthenium
- 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
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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
- 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 invention relates to a cathode for aqueous electrolysis, e.g. the electrolysis of aqueous solutions of alkali metal chlorides to obtain chlorine, alkali metal hydroxide solution and hydrogen, which consists of a support made of nickel or nickel-coated steel and a layer which at least partly covers the surface of the support and contains a metal of the platinum group.
- titanium anodes For the electrolysis of aqueous solutions at temperatures not significantly above room temperature, titanium anodes have become known which are coated with oxides from the group of platinum metals and mixtures containing passivable metals, for example a mixture of 30 mol% ruthenium oxide and 70 mol% titanium oxide ( DE-AS 16 71 422).
- the anodes have a comparatively low overvoltage and are easy to handle because the electrode spacing does not change during the electrolysis process.
- the cathodes are generally made of steel, nickel or nickel-plated steel, and it is also known to coat the cathodes with a platinum metal in order to improve the stability and reduce the hydrogen overvoltage, for example the coating of cathode bodies made of stainless steel or nickel with metallic ruthenium ( DE-OS 27 34 084), one enclosing the carrier body Bende metal layer is generated by electrodeposition or by a CVD process. In another method, a ruthenium-containing layer is produced on the carrier body by electroplating or by thermal decomposition of saline precipitates (DE-OS 28 11 472).
- the surface of the support is coated with a solution or suspension of a ruthenium compound, for example ruthenium hydroxide, ruthenium chloride, ruthenium oxide or ruthenium sulfide, the solvent or dispersant is evaporated and the compound is decomposed by heating in a non-oxidizing atmosphere to about 1200 ° C.
- a ruthenium compound for example ruthenium hydroxide, ruthenium chloride, ruthenium oxide or ruthenium sulfide
- the solvent or dispersant is evaporated and the compound is decomposed by heating in a non-oxidizing atmosphere to about 1200 ° C.
- the coating cathodic support structures with R utheniummetall not always satisfied because often increases the hydrogen overvoltage during prolonged use of the cathode and the overvoltage under many conditions comparatively too large.
- the invention is therefore based on the object of providing a coated cathode which is resistant to the electrolytes and the electrolysis products and has a smaller surge voltage against hydrogen.
- the object is achieved with a cathode of the type mentioned at the outset, which is provided with a layer containing ruthenium oxide and nickel oxide, which consists of several partial layers.
- anodes consisting of a titanium carrier body with a platinum metal oxide alone or as a mixture with other oxides.
- the anodic coatings were considered unusable for Cathodes, which were therefore coated with metallic platinum or a platinum group element.
- the primary coating of the cathode consisted of an oxidic or other salt-like compound, the compounds were reduced to metal by a special heat treatment (DE-OS 28 11 472).
- a carrier body made of nickel or nickel-coated steel coated with ruthenium oxide and nickel oxide has a lower hydrogen overvoltage and better resistance than metal-coated cathodes.
- the support of the cathode according to the invention consists of porous or solid plates, rods or tubes made of nickel or nickel-coated steel in accordance with the specified conditions of the electrolysis process.
- the layer of ruthenium oxide and nickel oxide deposited on the surface of the support and covering at least part of it consists of several partial layers which together form the coating.
- the quantitative ratio of the oxides in the individual sub-layers is different according to a preferred embodiment of the invention. By dividing the coating into several sub-layers, very good adhesion and a long service life are achieved.
- the sub-layer adjacent to the carrier expediently contains more nickel than ruthenium oxide and the sub-layer facing the electrolyte contains more ruthenium than nickel oxide.
- Partial layers with a content of 70 to 95% nickel oxide and 30 to 5% ruthenium oxide or 5 to 25% nickel oxide and 95 to 75% ruthenium oxide are preferred.
- the thickness of the coating is 1 to 10, preferably 2 to 5 / ⁇ m and the number of sub-layers 3 to 5, so that the average thickness of a sub-layer is approximately 0.2 to 3 / ⁇ m. In this area, the cathodic activity is particularly favorable, with good mechanical resistance of the layer.
- a support body from the group consisting of nickel and nickel-plated steel is coated with a solution containing a nickel and a ruthenium salt, for example with a hydrochloric acidic ethanolic solution of nickel nitrate and ruthenium chloride.
- the solvent is removed by drying and the body is heated in air to about 450 to 550 ° C.
- This forms a layer consisting essentially of nickel oxide and ruthenium oxide, the thickness of which is proportional to the amount of the solution applied to the carrier surface.
- the cycle is then repeated three to five times, so that a layer consisting of three to five sub-layers is formed.
- a sandblasted commercial nickel sheet 50 mm x 50 mm with a thickness of 1 mm was coated on one side with a solution, the composition of which was as follows: 15.6 mg Ni (NO 3 ) 2 and 2.6 mg RuCl 3 , corresponding to 80 wt. % Ni / 20% by weight Ru, 75 / ul ethanol and 50 ⁇ l conc. Hydrochloric acid.
- the sheet was dried and heated to 500 ° C. in a muffle furnace under atmospheric oxygen, the holding time was 10 min.
- a solution was applied containing 7.8 m g of Ni (N0 3 ) 2 and 15 mg of RuCl 3 , respectively 25% by weight Ni / 75% by weight Ru, in 75 ⁇ l ethanol and 25 ⁇ l conc. HCl.
- the sheet was dried and heated as described above.
- An expanded metal grid made of V4A steel was sandblasted and electroplated in a Watts electrolyte; the layer thickness was about 5 ⁇ m.
- Three partial layers of nickel oxide and ruthenium oxide were applied to the nickel-plated carrier body as described in Example 1.
- the potential of the cathodes according to Example 1 (circle) and 2 (triangle) was measured in a 20% aqueous solution of NaOH at 70 ° C as a function of the current density.
- the reference electrode was a saturated calomel electrode.
- the cathode potential of a sandblasted stainless steel sheet (1), a nickel sheet (2), a platinum sheet (3) and the coated nickel cathode was determined according to Example 1 (4) (FIG. 2).
- the small potential of the cathode according to the invention which increases comparatively slightly with increasing current density, requires no further explanation.
- the potential is practically independent of the operating time, as measurements at a current density of 5 kA / m 2 show. (F ig. 3).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3322169 | 1983-06-21 | ||
DE19833322169 DE3322169A1 (de) | 1983-06-21 | 1983-06-21 | Kathode fuer waesserige elektrolysen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0129088A1 true EP0129088A1 (fr) | 1984-12-27 |
EP0129088B1 EP0129088B1 (fr) | 1987-05-20 |
Family
ID=6201896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84105859A Expired EP0129088B1 (fr) | 1983-06-21 | 1984-05-23 | Cathode pour électrolyses aqueuses |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0129088B1 (fr) |
JP (1) | JPH0689469B2 (fr) |
DE (1) | DE3322169A1 (fr) |
NO (1) | NO161812C (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2579628A1 (fr) * | 1985-03-29 | 1986-10-03 | Atochem | Cathode pour electrolyse et un procede de fabrication de ladite cathode |
US5035789A (en) * | 1990-05-29 | 1991-07-30 | The Dow Chemical Company | Electrocatalytic cathodes and methods of preparation |
US5066380A (en) * | 1990-05-29 | 1991-11-19 | The Dow Chemical Company | Electrocatalytic cathodes and method of preparation |
US5164062A (en) * | 1990-05-29 | 1992-11-17 | The Dow Chemical Company | Electrocatalytic cathodes and method of preparation |
US5227030A (en) * | 1990-05-29 | 1993-07-13 | The Dow Chemical Company | Electrocatalytic cathodes and methods of preparation |
WO2011154094A1 (fr) * | 2010-06-11 | 2011-12-15 | Uhde Gmbh | Revêtement de substrat sur une ou plusieurs faces |
CN114643187A (zh) * | 2022-03-10 | 2022-06-21 | 宝鸡宝冶钛镍制造有限责任公司 | 一种离子膜电解槽镍阴极活性涂层及镍阴极表面处理方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3344416A1 (de) * | 1983-12-08 | 1985-12-05 | Sigri GmbH, 8901 Meitingen | Verfahren zur herstellung einer kathode fuer die waesserige elektrolyse |
FR2596776B1 (fr) * | 1986-04-03 | 1988-06-03 | Atochem | Cathode pour electrolyse et un procede de fabrication de ladite cathode |
DE3612790A1 (de) * | 1986-04-16 | 1987-10-22 | Sigri Gmbh | Kathode fuer waesserige elektrolysen |
JP2008124855A (ja) * | 2006-11-14 | 2008-05-29 | Funai Electric Co Ltd | スピーカ装置 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3990957A (en) * | 1975-11-17 | 1976-11-09 | Ppg Industries, Inc. | Method of electrolysis |
US4100049A (en) * | 1977-07-11 | 1978-07-11 | Diamond Shamrock Corporation | Coated cathode for electrolysis cells |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1195871A (en) * | 1967-02-10 | 1970-06-24 | Chemnor Ag | Improvements in or relating to the Manufacture of Electrodes. |
DE2734084A1 (de) * | 1976-08-02 | 1978-02-09 | Goodrich Co B F | Verfahren zur herstellung von chlor und phosphatsalzen durch elektrolyse |
DE2811472A1 (de) * | 1977-03-19 | 1978-09-21 | Tokuyama Soda Kk | Kathoden fuer elektrolytische zellen |
US4544473A (en) * | 1980-05-12 | 1985-10-01 | Energy Conversion Devices, Inc. | Catalytic electrolytic electrode |
JPS6022070B2 (ja) * | 1981-09-22 | 1985-05-30 | ペルメレツク電極株式会社 | 酸性溶液電解用陰極及びその製造方法 |
CA1246008A (fr) * | 1983-05-31 | 1988-12-06 | R. Neal Beaver | Electrode a substrat de nickel, et enrobage des composes metalliques des groupes nickel et platine |
-
1983
- 1983-06-21 DE DE19833322169 patent/DE3322169A1/de active Granted
-
1984
- 1984-05-23 EP EP84105859A patent/EP0129088B1/fr not_active Expired
- 1984-06-18 NO NO842443A patent/NO161812C/no not_active IP Right Cessation
- 1984-06-20 JP JP59127243A patent/JPH0689469B2/ja not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3990957A (en) * | 1975-11-17 | 1976-11-09 | Ppg Industries, Inc. | Method of electrolysis |
US4100049A (en) * | 1977-07-11 | 1978-07-11 | Diamond Shamrock Corporation | Coated cathode for electrolysis cells |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, Band 98, Nr. 26, 27. Juni 1983, Seite 543, Nr. 224177z, Columbus, Ohio, US; & JP - A - 57 207 183 (TOKUYAMA SODA CO., LTD.) 18.12.1982 * |
PATENTS ABSTRACTS OF JAPAN, Band 6, Nr. 78 (C-102)(956), 15. Mai 1982; & JP - A - 57 13188 (OSAKA SODA K.K.) 23.01.1982 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2579628A1 (fr) * | 1985-03-29 | 1986-10-03 | Atochem | Cathode pour electrolyse et un procede de fabrication de ladite cathode |
EP0198752A1 (fr) * | 1985-03-29 | 1986-10-22 | Elf Atochem S.A. | Cathode pour électrolyse et un procédé de fabrication de ladite cathode |
US5035789A (en) * | 1990-05-29 | 1991-07-30 | The Dow Chemical Company | Electrocatalytic cathodes and methods of preparation |
US5066380A (en) * | 1990-05-29 | 1991-11-19 | The Dow Chemical Company | Electrocatalytic cathodes and method of preparation |
EP0459410A1 (fr) * | 1990-05-29 | 1991-12-04 | The Dow Chemical Company | Cathodes électrocatalytiques et leurs méthodes de préparation |
US5164062A (en) * | 1990-05-29 | 1992-11-17 | The Dow Chemical Company | Electrocatalytic cathodes and method of preparation |
US5227030A (en) * | 1990-05-29 | 1993-07-13 | The Dow Chemical Company | Electrocatalytic cathodes and methods of preparation |
WO2011154094A1 (fr) * | 2010-06-11 | 2011-12-15 | Uhde Gmbh | Revêtement de substrat sur une ou plusieurs faces |
CN102933735A (zh) * | 2010-06-11 | 2013-02-13 | 蒂森克虏伯伍德公司 | 在一个或多个面上的基底涂层 |
CN102933735B (zh) * | 2010-06-11 | 2016-08-17 | 蒂森克虏伯伍德公司 | 在一个或多个面上的基底涂层 |
US10030300B2 (en) | 2010-06-11 | 2018-07-24 | Thyssenkrupp Industrial Solutions Ag | Substrate coating on one or more sides |
CN114643187A (zh) * | 2022-03-10 | 2022-06-21 | 宝鸡宝冶钛镍制造有限责任公司 | 一种离子膜电解槽镍阴极活性涂层及镍阴极表面处理方法 |
Also Published As
Publication number | Publication date |
---|---|
NO161812B (no) | 1989-06-19 |
NO161812C (no) | 1989-09-27 |
EP0129088B1 (fr) | 1987-05-20 |
DE3322169A1 (de) | 1985-01-10 |
JPH0689469B2 (ja) | 1994-11-09 |
NO842443L (no) | 1984-12-27 |
JPS6017086A (ja) | 1985-01-28 |
DE3322169C2 (fr) | 1990-06-13 |
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