EP0033363A1 - Procédé de revêtement d'une électrode poreuse - Google Patents

Procédé de revêtement d'une électrode poreuse Download PDF

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Publication number
EP0033363A1
EP0033363A1 EP80107001A EP80107001A EP0033363A1 EP 0033363 A1 EP0033363 A1 EP 0033363A1 EP 80107001 A EP80107001 A EP 80107001A EP 80107001 A EP80107001 A EP 80107001A EP 0033363 A1 EP0033363 A1 EP 0033363A1
Authority
EP
European Patent Office
Prior art keywords
electrode
compounds
metals
platinum
dispersant
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
EP80107001A
Other languages
German (de)
English (en)
Other versions
EP0033363B1 (fr
Inventor
Günter Dr.rer.nat. Bewer
Hubertus Härle
Dieter Ing.Grad. Lieberoth
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.)
Sigri GmbH
Original Assignee
Sigri Elektrograhit 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 Elektrograhit GmbH filed Critical Sigri Elektrograhit GmbH
Publication of EP0033363A1 publication Critical patent/EP0033363A1/fr
Application granted granted Critical
Publication of EP0033363B1 publication Critical patent/EP0033363B1/fr
Expired legal-status Critical Current

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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
    • C25B11/055—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
    • 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
    • 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 method for coating a porous electrode for electrochemical processes with an activation layer which at least partially covers the electrode surface and contains metals or compounds of metals of the platinum group.
  • Electrodes for electrochemical processes for example anodes for chlor-alkali electrolysis, from a material which is resistant to the electrolysis products and forms a passivation layer under the conditions of the electrolysis, the main purpose of which is to produce a platinum metal or a platinum metal-containing one Anchoring connections in an electrochemically effective degree of dispersion mechanically firmly on the electrode or the electrode core.
  • DE-AS 11 55 762 it is known to galvanically coat degreased and etched titanium plates with a platinum metal and the plates in a first thermal cycle in an inert atmosphere and in a second cycle in an oxidizing atmosphere up to a temperature of to heat about 800 ° C.
  • This treatment gives a firmly adhering activation layer and at the same time improved protection of the electrode material by converting the titanium core, which is exposed in the pores of the activation layer and has a thin barrier layer made of titanium oxide, into rutile.
  • coating processes that have become less suitable are suitable for porous electrodes, for example for sintered electrodes according to DE-OS 23 05 175 or electrodes made of titanium suboxide according to DE-AS 24 05 010.
  • the adhesive strength of the activation layers is particularly favorable in the case of porous electrodes and is the case for numerous electrochemical processes large surface of the electrode is an advantage.
  • the invention has for its object to provide a coating method for porous electrodes that does not have the disadvantages described, especially the comparatively large need for activating agents, and results in highly effective activation layers with small amounts of platinum metals.
  • the object is achieved according to the invention by a process of the type mentioned at the outset, in that the electrode surface is coated with a fine-grained compounds of metals of the platinum group and a suspension containing the compounds which dissolve the compounds at an elevated temperature, the dispersed phase of the suspension by heating the coated electrode dissolved in the dispersing agent, deposited on the electrode surface by evaporation of the agent and decomposed by heating the electrode to a temperature between 250 and 350 C and that the cycle was repeated several times and the electrode was then heated to a temperature between 400 and 600 C in an oxygen-containing atmosphere heated.
  • the invention is based on the knowledge that particles dispersed in a suspension cannot get into pores which are only accessible through narrow hoses or channels, whereas the dispersing agent fills these pores.
  • the particle diameter must therefore correspond to the pore diameter. If the electrode is heated after coating, the dispersing agent emerges from the pores and, because of the increasing solubility of the platinum group compounds used according to the invention, dissolves the particles concentrated at the pore inlets.
  • the solution which is present in a thin layer, has a relatively high toughness and is distributed evenly over the outer electrode surface and the surface of larger pores accessible from the outer surface without penetrating into narrow channel and tube pores.
  • the compounds deposited by evaporation of the solvent in a uniform layer thickness are then decomposed by heating the electrode to a temperature between 250 and 350 ° C., whereby a fissured metallic surface with a large specific surface Activation layer is formed.
  • the layer thickness of about 1 / um required for technical purposes is obtained by repeating the coating cycle several times.
  • the invention provides for the heating of the coated electrode in an oxidizing atmosphere, preferably in air, to a temperature between 400 and 600 ° C.
  • the purpose of the thermal treatment is primarily the passivation of the electrode surface exposed in the pores of the activation layer and the anchoring of the activation layer on this surface.
  • Partial oxidation of the platinum metals contained in the activation layer is not harmful, since the growth of the metal crystals is inhibited and finely dispersed layers have greater electrochemical activity.
  • the treatment temperature should therefore not fall below or exceed the temperature range of 400 to 600 ° C.
  • the heating time is expediently about 3 to 60 minutes and can be easily determined by simple experiments for each electrode material and each compound used as an activating agent.
  • compounds of non-platinum metals are dispersed in the dispersant in addition to compounds of metals from the platinum group.
  • Suitable non-platinum metals are tantalum, zirconium, niobium, aluminum and especially titanium.
  • the activation layer then contains a finely dispersed mixture of platinum metals, oxides of platinum metals and oxides of non-platinum metals.
  • thermally decomposable complex compounds which contain free acid, in particular compounds from the group oxolato, are used as compounds of metals of the platinum group and of non-platinum metals.
  • the dispersing agent used according to the invention dissolves the complex compounds at elevated temperature, with the electrode surface, in particular passivation layers, being formed by caustic solutions. Water and optionally aqueous oxalic acid solutions are particularly suitable for this purpose.
  • the primer is improved without the formation of corrosive and harmful vapors as in the known use of hydrochloric acid platinum metal chloride solutions.
  • electrodes In principle, all electrically conductive metals, alloys and compounds that are stable under the conditions of electrochemical processes are suitable as electrodes. Preferred are used, e.g. as an anode for the chlor-alkali electrolysis, metals forming passivation layers, such as titanium, tantalum, zirconium and niobium and, according to the invention, preferably electrodes which at least partly consist of titanium suboxide.
  • the electrodes according to the invention have a porosity of about 10 to 50% and are generally produced by sintering moldings from a metal powder or an oxide powder.
  • the electrode plate was then tested as an anode in an amalgam test cell.
  • the conditions were:
  • the anode potential was measured with a Luggin capillary against the saturated calomel electrode.
  • Composite panels as in Example 2 were made with a slurry of 66 parts H 2 [Ru (C 2 O 4 ) 2 ]. 2, 5H 2 0, 70 parts of H 2 [Ir (C2 O4) 3], 100 parts of Ti 2 (C 2 O 4). 3 10 H 2 0 coated in 1,000 parts of water and 50 parts of oxalic acid, annealed and the potentials measured.

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)
EP80107001A 1980-02-05 1980-11-13 Procédé de revêtement d'une électrode poreuse Expired EP0033363B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3004080A DE3004080C2 (de) 1980-02-05 1980-02-05 Verfahren zum Beschichten einer porösen Elektrode
DE3004080 1980-02-05

Publications (2)

Publication Number Publication Date
EP0033363A1 true EP0033363A1 (fr) 1981-08-12
EP0033363B1 EP0033363B1 (fr) 1983-08-24

Family

ID=6093754

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80107001A Expired EP0033363B1 (fr) 1980-02-05 1980-11-13 Procédé de revêtement d'une électrode poreuse

Country Status (3)

Country Link
US (1) US4431686A (fr)
EP (1) EP0033363B1 (fr)
DE (1) DE3004080C2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205631A1 (fr) * 1985-05-08 1986-12-30 SIGRI GmbH Procédé de revêtement d'une électrode poreuse

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530742A (en) * 1983-01-26 1985-07-23 Ppg Industries, Inc. Electrode and method of preparing same
DE3472979D1 (en) * 1983-06-28 1988-09-01 Bbc Brown Boveri & Cie Process for manufacturing a depassivating layer and depassivating layer on an electrode for an electrochemical cell
JPS60159185A (ja) * 1984-01-31 1985-08-20 Permelec Electrode Ltd 電極の製造方法
US4912286A (en) * 1988-08-16 1990-03-27 Ebonex Technologies Inc. Electrical conductors formed of sub-oxides of titanium
EP0696813B1 (fr) * 1994-08-11 2002-10-02 Canon Kabushiki Kaisha Utilisation d'une solution pour la fabrication des dispositifs émetteur d'électrons et méthode de fabrication des dispositifs émetteur d'électrons
JPH11111273A (ja) * 1997-09-29 1999-04-23 Furukawa Battery Co Ltd:The リチウム二次電池用極板の製造法及びリチウム二次電池
US20060255692A1 (en) * 2005-03-22 2006-11-16 Motohiro Yasui Piezoelectric Actuator, Ink-Jet Head, Method Of Producing Piezoelectric Actuator, And Method Of Producing Ink-Jet Head
US20140161972A1 (en) * 2012-12-09 2014-06-12 National Sun Yat-Sen University Method for forming conductive film at room temperature

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT223209B (de) * 1959-04-27 1962-09-10 Ici Ltd Verfahren zur Herstellung eines Verbundkörpers, der aus einem Trägerkörper aus Titan und einem Überzug aus Platinmetallen besteht
DE1467221B2 (de) * 1959-04-27 1970-10-01 Imperial Chemical Industries Ltd., London Verfahren zur Herstellung einer für die Chloralkali-Elektrolyse geeigneten Elektrode
US3778307A (en) * 1967-02-10 1973-12-11 Chemnor Corp Electrode and coating therefor
AT314481B (de) * 1970-01-09 1974-04-10 Solvay Verfahern zur Herstellung einer Elektrode für elektrochemische Verfahren
DE2800193A1 (de) * 1977-01-27 1978-08-03 Tdk Electronics Co Ltd Elektrode und verfahren zur herstellung derselben

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US28820A (en) * 1860-06-19 wright
USRE28820E (en) 1965-05-12 1976-05-18 Chemnor Corporation Method of making an electrode having a coating containing a platinum metal oxide thereon
GB1195871A (en) * 1967-02-10 1970-06-24 Chemnor Ag Improvements in or relating to the Manufacture of Electrodes.
US3562008A (en) * 1968-10-14 1971-02-09 Ppg Industries Inc Method for producing a ruthenium coated titanium electrode
US4070504A (en) * 1968-10-29 1978-01-24 Diamond Shamrock Technologies, S.A. Method of producing a valve metal electrode with valve metal oxide semi-conductor face and methods of manufacture and use
US3684543A (en) * 1970-11-19 1972-08-15 Patricia J Barbato Recoating of electrodes
US3924025A (en) * 1972-02-02 1975-12-02 Electronor Corp Method of making an electrode having a coating of cobalt metatitanate thereon
US4032427A (en) * 1975-11-03 1977-06-28 Olin Corporation Porous anode separator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT223209B (de) * 1959-04-27 1962-09-10 Ici Ltd Verfahren zur Herstellung eines Verbundkörpers, der aus einem Trägerkörper aus Titan und einem Überzug aus Platinmetallen besteht
DE1467221B2 (de) * 1959-04-27 1970-10-01 Imperial Chemical Industries Ltd., London Verfahren zur Herstellung einer für die Chloralkali-Elektrolyse geeigneten Elektrode
US3778307A (en) * 1967-02-10 1973-12-11 Chemnor Corp Electrode and coating therefor
AT314481B (de) * 1970-01-09 1974-04-10 Solvay Verfahern zur Herstellung einer Elektrode für elektrochemische Verfahren
DE2800193A1 (de) * 1977-01-27 1978-08-03 Tdk Electronics Co Ltd Elektrode und verfahren zur herstellung derselben

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205631A1 (fr) * 1985-05-08 1986-12-30 SIGRI GmbH Procédé de revêtement d'une électrode poreuse

Also Published As

Publication number Publication date
US4431686A (en) 1984-02-14
DE3004080C2 (de) 1986-03-20
DE3004080A1 (de) 1981-08-13
EP0033363B1 (fr) 1983-08-24

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