EP0094577B1 - Cathode pour l'électrolyse de chlorures alcalins et procédé pour sa fabrication - Google Patents

Cathode pour l'électrolyse de chlorures alcalins et procédé pour sa fabrication Download PDF

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Publication number
EP0094577B1
EP0094577B1 EP83104513A EP83104513A EP0094577B1 EP 0094577 B1 EP0094577 B1 EP 0094577B1 EP 83104513 A EP83104513 A EP 83104513A EP 83104513 A EP83104513 A EP 83104513A EP 0094577 B1 EP0094577 B1 EP 0094577B1
Authority
EP
European Patent Office
Prior art keywords
nickel
covering layer
aluminium
cathode
underlayer
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
EP83104513A
Other languages
German (de)
English (en)
Other versions
EP0094577A2 (fr
EP0094577A3 (en
Inventor
Peter Fabian
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.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektroden 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 Heraeus Elektroden GmbH filed Critical Heraeus Elektroden GmbH
Priority to AT83104513T priority Critical patent/ATE27188T1/de
Publication of EP0094577A2 publication Critical patent/EP0094577A2/fr
Publication of EP0094577A3 publication Critical patent/EP0094577A3/de
Application granted granted Critical
Publication of EP0094577B1 publication Critical patent/EP0094577B1/fr
Expired legal-status Critical Current

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    • 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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/046—Alloys
    • 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

Definitions

  • the invention relates to a process for the production of a cathode for chlor-alkali electrolysis, in particular according to the diaphragm or membrane process, with a nickel underlayer with a minimum thickness of 30 pm and a Raney nickel layer on a soft iron or steel support. Activation top layer, from which top layer the aluminum is then leached.
  • an electrode with an iron or iron alloy substrate with an electrolytically applied nickel underlayer which contains embedded porous nickel particles in an additionally applied nickel top layer; the porosity of the top layer is preferably between 35 and 85%.
  • the nickel particles are first embedded in the form of Raney nickel alloys and then their aluminum content is removed using lye.
  • the electrode is preferably used as a cathode in chlor-alkali electrolysis, using the membrane method, among others.
  • a nickel electrode with a porous surface in which a steel substrate is provided with an adhesion-promoting nickel sintered layer, onto which a nickel / zinc alloy is applied electrolytically; the zinc content is then leached out. From this publication it is also known to spray on the nickel layer by a plasma jet process when using beta-aluminum oxide substrates.
  • US Pat. No. 3,150,011 discloses the production of an electrode with iron as the substrate, which is coated with nickel and sintered. After applying and sintering a nickel Raney alloy in powder form, the aluminum portion is dissolved out by potassium hydroxide solution, so that a hydrogen diffusion electrode with sufficient porosity is created.
  • FR-OS 2 323 777 From FR-OS 2 323 777 it is known to apply a mixture of nickel and aluminum to a metal substrate by means of a plasma jet process, from which the aluminum portion is subsequently removed by leaching.
  • FR-OS 2 322 939 it is known from FR-OS 2 322 939 to apply nickel or nickel alloys to a metal substrate by means of a plasma jet process.
  • the invention has for its object to provide a cathode for chlor-alkali electrolysis, which has a high corrosion resistance to the electrolyte solution, very low hydrogen deposition potentials and also has a high adhesive strength of the activation layer on the carrier, even when the carrier is deformed.
  • a method for the production of a cathode for chlor-alkali electrolysis, in particular according to the diaphragm or membrane method, with an activation layer of Raney nickel applied to a carrier made of soft iron or steel, a method has proven particularly useful, according to which a 30 to 60 pm thick, dense nickel underlayer is sprayed on by means of the plasma jet process, onto which a 20 to 60 ⁇ m thick top layer of a nickel-aluminum mixture with an aluminum content of 10 to 50%, the rest of nickel, is then sprayed by means of the plasma jet process, from which subsequently the aluminum is leached out.
  • 1N NaOH is preferably used to leach the aluminum.
  • the method is particularly suitable for supports which are deformed into the desired cathode shape before being coated with the underlayer and the top layer.
  • a nickel powder with a grain size in the range from 10 to 60 ⁇ m is preferably used for spraying on the underlayer.
  • the use of a powder mixture on 50 parts of nickel and 50 parts of aluminum with a grain size in the range from 10 to 60 ⁇ m has proven useful for spraying on the top layer.
  • the cathodes produced according to the invention showed only extraordinarily minor corrosion damage when stored electrolessly in a diaphragm cell solution of the composition 150 g / l NaOH + 130 g / l NaCl for 3 weeks, while cathodes according to the prior art sometimes show strong detachments of the nickel layer, pitting and Had blistering through which the nickel layer partially removed burst.
  • the cathodes showed similar results under operating conditions.
  • the cathodes produced according to the invention have a potential which is about 50 to 100 mV lower at 10 kA / m 2 , which leads to considerable energy savings in use of the cathodes produced according to the invention in chlor-alkali electrolysis.
  • the low hydrogen potential of cathodes produced according to the invention which is about 1.25 V against saturated calomel electrode at 10 kA / m 2 , is probably due to the larger surface area of the porous Raney nickel cover layer.
  • the method according to the invention is not only suitable for the coating of planar supports, but in particular also for those supports which have already been deformed into the desired cathode shape before coating, because by spraying on both the bottom and the top layer by means of plasma spraying no difficulties arise since the plasma spray jet also safely reaches curved or bent surface parts of the carrier.
  • FIG. 1 shows a section of an exemplary embodiment of a cathode produced according to the invention, FIG. 1a showing a view and FIG. 1b a vertical section along the plane A-B.
  • the reference number 1 denotes the cathode in the figure. 1b, it consists of a support 2 made of soft iron or steel, the underlayer 3 applied to this support made of a nickel layer sprayed on by means of the plasma jet process and the porous cover layer 4 made of Raney nickel produced thereon by the process according to the invention. It can be clearly seen from the figures that the cover layer has a rough surface.
  • the cathode shown in the figure is produced, for example, as follows:
  • a steel beam is first cleaned on its surface by blasting with aluminum oxide powder.
  • the nickel underlayer is then sprayed on using a plasma torch, which works with argon as the carrier gas and hydrogen as the additional gas at a pressure of approximately 1.5 bar.
  • a commercially available powder with a grain size in the range from 10 to 60 ⁇ m is used as the nickel powder.
  • the supply of nickel powder is interrupted and the plasma torch is fed with a powder composed of a mixture of nickel and aluminum powder with 50 parts of nickel and 50 parts of aluminum, and this powder is sprayed on.
  • the coated support is treated with 1N NaOH to remove the aluminum, specifically by immersing the coated support in an alkaline bath until the aluminum portion has been removed from the covering layer. The cathode is then rinsed with water.
  • the powder mixture of nickel and aluminum other powder mixtures containing nickel, such as nickel / zinc, can also be used. It is important that the component added to the nickel can be removed from the sprayed top layer without attacking the nickel and the carrier. Potassium hydroxide solution can also be used instead of sodium hydroxide solution.
  • the thickness of the cover layer is advantageously 20 to 40 pm.

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 Metals (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (6)

1. Procédé pour la fabrication d'une cathode pour l'électrolyse des chlorures alcalins, en particulier selon le procédé avec diaphragme ou membrane, comportant une sous-couche (3) de nickel d'une épaisseur minimale de 30 pm appliquée sur un support (2) en fer doux ou en acier et une couche de recouvrement d'activation (4) en nickel de Raney se trouvant par-desuss ladite sous-couche, l'aluminium étant ensuite extrait de ladite couche de recouvrement, dans lequel on applique par projection sur le support (2) une sous-couche (3) dense de nickel d'une épaisseur allant jusqu'à 60 pm, par-dessus celle-ci une couche de recouvrement (4) de 20 à 60 pm d'épaisseur d'un mélange en poudre de nickel et d'aluminium ayant une teneur en aluminium de 10 à 50%, chaque fois au moyen d'un procédé au jet de plasma, et la couche de recouvrement présente une porosité dans la gamme de 10 à 50%.
2. procédé selon la revendication 1, caractérisé en ce que l'on utilise pour la projection de la couche de recouvrement (4) un mélange de poudre de nickel et de poudre de zinc au lieu du mélange en poudre d'aluminium et de nickel.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on extrait l'aluminium de la couche de recouvrement (4) par la lessive de soude ou la lessive de potasse.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que le support (2) est façonné dans la forme de cathode désirée avant le revêtement.
5. Procédé selon la revendication 1, caractérisé en ce que l'on utilise pour la projection de sous-couche de nickel (3) des poudres d'une grosseur de grains de 10 à 60 µm.
6. Procédé selon la revendication 1, caractérisé en ce que l'on utilise pour la projection de la couche de recouvrement (4) un mélange de poudre de nickel et de poudre d'aluminium d'une grosseur de grains de 10 à 60 pm.
EP83104513A 1982-05-15 1983-05-07 Cathode pour l'électrolyse de chlorures alcalins et procédé pour sa fabrication Expired EP0094577B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83104513T ATE27188T1 (de) 1982-05-15 1983-05-07 Kathode fuer die chloralkali-elektrolyse und verfahren zu deren herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3218429A DE3218429C2 (de) 1982-05-15 1982-05-15 Verfahren zur Herstellung einer Kathode für die Chlor-Alkali-Elektrolyse
DE3218429 1982-05-15

Publications (3)

Publication Number Publication Date
EP0094577A2 EP0094577A2 (fr) 1983-11-23
EP0094577A3 EP0094577A3 (en) 1984-03-07
EP0094577B1 true EP0094577B1 (fr) 1987-05-13

Family

ID=6163756

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83104513A Expired EP0094577B1 (fr) 1982-05-15 1983-05-07 Cathode pour l'électrolyse de chlorures alcalins et procédé pour sa fabrication

Country Status (5)

Country Link
EP (1) EP0094577B1 (fr)
JP (1) JPS5941485A (fr)
KR (1) KR840004795A (fr)
AT (1) ATE27188T1 (fr)
DE (2) DE3218429C2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595468A (en) * 1984-07-19 1986-06-17 Eltech Systems Corporation Cathode for electrolysis cell
JP2644617B2 (ja) * 1990-08-24 1997-08-25 日本碍子株式会社 静圧気体軸受け及びその製造法
EP0762517A3 (fr) * 1995-09-11 1999-10-20 Texas Instruments Incorporated Améliorations relatives aux composants semi-conducteurs
RU2110619C1 (ru) * 1996-09-09 1998-05-10 Закрытое акционерное общество "Техно-ТМ" Электрод для электрохимических процессов и способ его изготовления
KR100772326B1 (ko) * 2000-02-15 2007-10-31 오투 마이크로, 인코포레이티드 휴대용 전자 장치용 오디오 컨트롤러
DE102005011047A1 (de) 2005-03-08 2006-09-14 Bayer Technology Services Gmbh Katalysatorformkörper, insbesondere zur Verwendung als Katalysatoren bei der Hydrierung
DE102024135929B3 (de) 2024-12-03 2026-02-26 Ks Gleitlager Gmbh Elektrode für die alkalische Wasserelektrolyse, Verwendung einer solchen Elektrode, Elektrolysezelle umfassend eine solche Elektrode sowie Verfahren zur Herstellung einer solchen Elektrode

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2418027A1 (fr) * 1978-02-24 1979-09-21 Asahi Glass Co Ltd Procede de preparation d'une electrode

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1233834B (de) * 1958-03-05 1967-02-09 Siemens Ag Elektrode fuer Elektrolyseure und Brennstoff-elemente mit oberflaechlicher Doppelskelett-Katalysator-Struktur
US4049841A (en) * 1975-09-08 1977-09-20 Basf Wyandotte Corporation Sprayed cathodes
US4024044A (en) * 1975-09-15 1977-05-17 Diamond Shamrock Corporation Electrolysis cathodes bearing a melt-sprayed and leached nickel or cobalt coating
US4116804A (en) * 1976-11-17 1978-09-26 E. I. Du Pont De Nemours And Company Catalytically active porous nickel electrodes
DE2914094C2 (de) * 1979-04-07 1983-02-10 Kernforschungsanlage Jülich GmbH, 5170 Jülich Poröse Nickelelektrode für alkalische Elektrolysen, Verfahren zur Herstellung derselben und deren Verwendung
EP0067975B1 (fr) * 1981-06-01 1987-08-19 Asahi Glass Company Ltd. Procédé pour l'électrolyse de l'eau

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2418027A1 (fr) * 1978-02-24 1979-09-21 Asahi Glass Co Ltd Procede de preparation d'une electrode

Also Published As

Publication number Publication date
EP0094577A2 (fr) 1983-11-23
EP0094577A3 (en) 1984-03-07
JPS5941485A (ja) 1984-03-07
KR840004795A (ko) 1984-10-24
DE3218429C2 (de) 1987-03-19
DE3218429A1 (de) 1983-12-01
DE3371544D1 (en) 1987-06-19
ATE27188T1 (de) 1987-05-15

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