EP0129088B1 - Kathode für wässrige Elektrolysen - Google Patents

Kathode für wässrige Elektrolysen Download PDF

Info

Publication number
EP0129088B1
EP0129088B1 EP84105859A EP84105859A EP0129088B1 EP 0129088 B1 EP0129088 B1 EP 0129088B1 EP 84105859 A EP84105859 A EP 84105859A EP 84105859 A EP84105859 A EP 84105859A EP 0129088 B1 EP0129088 B1 EP 0129088B1
Authority
EP
European Patent Office
Prior art keywords
nickel
coating
cathode
oxide
component
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.)
Expired
Application number
EP84105859A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0129088A1 (de
Inventor
Heiner Dr.-Ing. Debrodt
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.)
ThyssenKrupp Industrial Solutions AG
Original Assignee
Sigri GmbH
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 Sigri GmbH filed Critical Sigri GmbH
Publication of EP0129088A1 publication Critical patent/EP0129088A1/de
Application granted granted Critical
Publication of EP0129088B1 publication Critical patent/EP0129088B1/de
Expired legal-status Critical Current

Links

Images

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. for the electrolysis of aqueous solutions of alkali metal chlorides for the production of chlorine, alkali metal hydroxide solution and hydrogen, which consists of a support made of nickel or nickel-coated steel and a coating which at least partially covers the surface of the support.
  • the coating is formed from several partial layers arranged one above the other and essentially consists of ruthenium oxide and nickel oxide.
  • 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 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), a metal layer enclosing the carrier body being produced by electrodeposition or by a CVD process.
  • 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.
  • fuel cells that are not used for electrolytic processes are known to provide the surface of the cathode with a layer that contains metallic ruthenium and a spinel.
  • the state of the art (Article 54 (3) EPC) is a cathode which is coated with nickel oxide and the oxide of a platinum metal, especially ruthenium oxide (EP-
  • the coating consists of several partial layers, which are applied to the carrier one after the other.
  • the coating solution contains an etchant with which less chemically stable components are removed from the partial layers before they are oxidized. Since the coating solutions for the individual partial layers of a coating are the same, the composition of the coating is essentially constant over its entire thickness.
  • the coating of cathodic support structures is not always satisfactory, since the hydrogen overvoltage often increases with prolonged use of the cathode and the overvoltage is comparatively too great under many conditions.
  • 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 lower overvoltage against hydrogen.
  • the object is achieved with a cathode of the type mentioned at the beginning, the coating of which is formed from partial layers of different composition, the relative proportion of nickel oxide from the partial layer adjacent to the support to the partial layer forming the surface of the coating decreasing from partial layer to partial layer and the relative proportion of ruthenium oxide increases accordingly in this direction.
  • 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 an element from the platinum group.
  • 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 support body made of nickel or nickel-coated steel coated with ruthenium oxide and nickel oxide, the coating of which has a concentration gradient has a lower overvoltage against hydrogen 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 carrier and covering at least part of it consists of several partial layers arranged one above the other, which together form the coating.
  • the quantitative ratio of the oxides in the individual sub-layers is different. By dividing the coating into several sub-layers, very good adhesion and a long service life are achieved.
  • the sublayer adjacent to the carrier contains more nickel than ruthenium oxide and that The electrolyte-facing partial layer forming the surface of the coating has 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 microns and the number of sub-layers 3 to 5, so that the average thickness of a sub-layer is about 0.2 to 3 microns.
  • 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 solutions containing nickel and ruthenium salt in various proportions, for example with hydrochloric acidic ethanolic solutions 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 partial 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 with solutions of different compositions, so that a coating consisting of three to five partial layers of different compositions 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 (N0 3 ) 2 and 2.6 mg RuCl 3 , corresponding to 80 wt. % Ni / 20% by weight Ru, 75 ⁇ l 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 minutes.
  • 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 70cC 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 also practically independent of the operating time, as measurements at a current density of 5 kA / m 2 show (FIG. 3), circular cathode according to example 1, triangular cathode according to example 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84105859A 1983-06-21 1984-05-23 Kathode für wässrige Elektrolysen Expired EP0129088B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833322169 DE3322169A1 (de) 1983-06-21 1983-06-21 Kathode fuer waesserige elektrolysen
DE3322169 1983-06-21

Publications (2)

Publication Number Publication Date
EP0129088A1 EP0129088A1 (de) 1984-12-27
EP0129088B1 true EP0129088B1 (de) 1987-05-20

Family

ID=6201896

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84105859A Expired EP0129088B1 (de) 1983-06-21 1984-05-23 Kathode für wässrige Elektrolysen

Country Status (4)

Country Link
EP (1) EP0129088B1 (ko)
JP (1) JPH0689469B2 (ko)
DE (1) DE3322169A1 (ko)
NO (1) NO161812C (ko)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
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
FR2579628A1 (fr) * 1985-03-29 1986-10-03 Atochem Cathode pour electrolyse et un procede de fabrication de ladite cathode
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
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
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
JP2008124855A (ja) * 2006-11-14 2008-05-29 Funai Electric Co Ltd スピーカ装置
DE102010023418A1 (de) * 2010-06-11 2011-12-15 Uhde Gmbh Ein- oder mehrseitige Substratbeschichtung
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0129734A2 (en) * 1983-05-31 1985-01-02 The Dow Chemical Company Preparation and use of electrodes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
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.
US3990957A (en) * 1975-11-17 1976-11-09 Ppg Industries, Inc. Method of electrolysis
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
US4100049A (en) * 1977-07-11 1978-07-11 Diamond Shamrock Corporation Coated cathode for electrolysis cells
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0129734A2 (en) * 1983-05-31 1985-01-02 The Dow Chemical Company Preparation and use of electrodes

Also Published As

Publication number Publication date
EP0129088A1 (de) 1984-12-27
JPS6017086A (ja) 1985-01-28
NO842443L (no) 1984-12-27
DE3322169C2 (ko) 1990-06-13
NO161812C (no) 1989-09-27
DE3322169A1 (de) 1985-01-10
NO161812B (no) 1989-06-19
JPH0689469B2 (ja) 1994-11-09

Similar Documents

Publication Publication Date Title
DE2300422C3 (de) Verfahren zur Herstellung einer Elektrode
DE69308396T2 (de) Elektrode mit verbesserter Lebensdauer
DE1814576C2 (de) Elektrode zur Verwendung in elektrolytischen Prozessen und Verfahren zu deren Herstellung
EP0169301B1 (de) Verbundelektrode, Verfahren zu ihrer Herstellung und ihre Anwendung
DE10007448B4 (de) Aktivierte Kathode und Verfahren zu ihrer Herstellung
DE69115213T2 (de) Elektrode.
DE2936033C2 (ko)
DE2532553A1 (de) Anode fuer elektrolytische verfahren
EP0129088B1 (de) Kathode für wässrige Elektrolysen
DE2342663B2 (de) Elektrode
DE3717972A1 (de) Haltbare elektroden fuer die elektrolyse und verfahren zu deren herstellung
DE2418739C2 (de) Anode zur elektrolytischen Herstellung einer Hypochlorit-Lösung
DE2113676C2 (de) Elektrode für elektrochemische Prozesse
EP0384194A2 (de) Formstabile Anoden und deren Verwendung bei der Herstellung von Alkalidichromaten und Chromsäure
DD153397A5 (de) Elektrode mit einem elektrokatalytischen ueberzug
DE3872228T2 (de) Elektrode fuer die entwicklung von sauerstoff und deren herstellungsverfahren.
EP0042984B1 (de) Edelmetallfreie Elektrode und Verfahren zu ihrer Herstellung
EP0033363B1 (de) Verfahren zum Beschichten einer porösen Elektrode
DE3780075T2 (de) Niedrigueberspannungs-elektroden fuer alkalische elektrolyte.
EP0245201B1 (de) Anode für Elektrolysen
DE2645414A1 (de) Verfahren zur herstellung von metallanoden fuer die elektrolytische gewinnung von mangandioxid
DE2852136A1 (de) Verfahren zur herstellung einer unloeslichen elektrode
DE2114543C3 (de) Verfahren zur Herstellung einer Elektrode zur Verwendung in elektrolytischen Verfahren
DE2844558A1 (de) Elektrode fuer die verwendung in einem elektrolytischen verfahren
DE3612790C2 (ko)

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

AK Designated contracting states

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

17P Request for examination filed

Effective date: 19850129

17Q First examination report despatched

Effective date: 19860204

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SIGRI GMBH

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

ET Fr: translation filed
ITF It: translation for a ep patent filed
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
ITTA It: last paid annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: UHDE GMBH

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

NLS Nl: assignments of ep-patents

Owner name: UHDE GMBH TE DORTMUND, BONDSREPUBLIEK DUITSLAND.

ITPR It: changes in ownership of a european patent

Owner name: CESSIONE;UHDE GMBH

EAL Se: european patent in force in sweden

Ref document number: 84105859.7

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: CH

Payment date: 20020416

Year of fee payment: 19

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

Ref country code: NL

Payment date: 20020430

Year of fee payment: 19

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

Ref country code: SE

Payment date: 20020502

Year of fee payment: 19

Ref country code: GB

Payment date: 20020502

Year of fee payment: 19

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

Ref country code: FR

Payment date: 20020513

Year of fee payment: 19

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

Ref country code: BE

Payment date: 20020527

Year of fee payment: 19

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

Ref country code: GB

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

Effective date: 20030523

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

Ref country code: SE

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

Effective date: 20030524

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

Ref country code: LI

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

Effective date: 20030531

Ref country code: CH

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

Effective date: 20030531

Ref country code: BE

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

Effective date: 20030531

BERE Be: lapsed

Owner name: *UHDE G.M.B.H.

Effective date: 20030531

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

Ref country code: NL

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

Effective date: 20031201

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20030523

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: FR

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

Effective date: 20040130

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20031201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST