EP0198752A1 - Kathode für Elektrolyse und deren Herstellungsverfahren - Google Patents

Kathode für Elektrolyse und deren Herstellungsverfahren Download PDF

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Publication number
EP0198752A1
EP0198752A1 EP86400657A EP86400657A EP0198752A1 EP 0198752 A1 EP0198752 A1 EP 0198752A1 EP 86400657 A EP86400657 A EP 86400657A EP 86400657 A EP86400657 A EP 86400657A EP 0198752 A1 EP0198752 A1 EP 0198752A1
Authority
EP
European Patent Office
Prior art keywords
cathode
coating
substrate
oxides
metals
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.)
Withdrawn
Application number
EP86400657A
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English (en)
French (fr)
Inventor
Francis Leroux
Dominique Ravier
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.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
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 Atochem SA, Elf Atochem SA filed Critical Atochem SA
Publication of EP0198752A1 publication Critical patent/EP0198752A1/de
Withdrawn legal-status Critical Current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
    • C25B11/073—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 new cathode usable in electrolysis. It also relates to a method of manufacturing this cathode. It relates very particularly to a cathode which can be used in the electrolysis of aqueous alkali metal halide solution which is remarkable in particular for the low value of its working potential and for the stability over time of its electrochemical performance.
  • This cathode belongs to the family of metallic cathodes, activated, obtained by coating a cathode substrate by means of various activation materials, the aim being essentially to reduce the hydrogen overvoltage in an alkaline medium.
  • One of the techniques that can be used commonly called “large area nickel”, consists of forming a coating of microporous nickel on a ferrous substrate by first depositing a nickel-zinc alloy and then removing the zinc.
  • Other techniques consist in depositing certain metal alloys on the substrate, such as nickel-molybdenum alloys (English patent 992350).
  • European patent application 0129374 describes cathodes carrying a coating consisting of a mixture of at least one metal of the platinum group and at least one oxide of a metal of the metal group, the platinum of the platinum group representing 2 to 30 % of the weight of said mixture.
  • Japanese patent application published under No. 5713189 describes a nickel or nickel alloy cathode bearing a coating consisting of a platinum group metal or an oxide of said metal.
  • British patent 1511719 describes a cathode comprising a metal substrate, a cobalt coating and a second ruthenium coating.
  • Japanese patent application published under the number 54090080 describes a technique for manufacturing a cathode consisting in treating a ferrous substrate with perchloric acid and then in coating this cathode by sintering with active substances comprising ruthenium, iridium, iron and nickel in metallic form or as a metal compound.
  • a deposition technique on a substrate, for example made of nickel, of a coating made of a nickel-palladium alloy is also described in American patent 3216919: according to this patent, an alloy layer is applied to the substrate. of powder then proceeds to sintering said alloy powder.
  • the Japanese patent application published under the number 54110983 (American patent n ° 4465580) describes a cathode carrying a coating constituted by a dispersion of particles of nickel or a nickel alloy and an activator constituted by platinum, ruthenium, iridium , rhodium, palladium or osmium or an oxide of these metals.
  • Japanese patent application published under number 53010036 describes a cathode having a valve metal substrate and a coating of an alloy of at least one platinum group metal and a valve metal and, optionally a surface coating of at least minus a platinum group metal.
  • European patent application 0129734 describes a cathode manufacturing technique, by depositing on an electroconductive substrate a coating solution comprising a metal oxide precursor and, necessarily, a pickling agent in order to dissolve the most soluble in the substrate and / or a coating layer previously deposited. This technique further comprises an operation of removing the most volatile part of the coating solution, said part containing the solubilized fractions of the substrate (op. Cit. Page 14).
  • the invention proposes a new cathode, usable in particular in the electrolysis of aqueous solutions of alkali metal halides, said cathode being constituted by an electrically conductive substrate carrying a coating based on a metal oxide of the platinum group , this cathode being characterized in that it carries a coating consisting of at least two metal oxides from group VIII of the periodic table of the elements, chosen respectively among the precious metals and among the non-precious metals of said group VIII.
  • the invention relates most particularly to cathodes comprising an electrically conductive substrate and a coating, the said coating consisting of ruthenium oxide (Ru 0 2 ) associated with one or more oxides of iron, cobalt or nickel and, optionally with one or several other Group VIII precious metal oxides.
  • Ru 0 2 ruthenium oxide
  • the invention especially relates to those in the coating of which the ruthenium oxide has a microcrystalline structure and the oxides of non-precious metals a crystal structure.
  • the invention particularly relates to cathodes in the coating of which all or part of the above-mentioned oxides are in the form of scales.
  • tortoiseshell designates a film of planar shape, of portion of cylinder or sphere or the combination of said shapes, the thickness of which is less than one tenth of the average of the two dimensions of the quadrilateral in which said tortoiseshell can be entered, the average value of said dimensions can be between 1 and 100 microns and more precisely between 3 and 30 microns.
  • the coating consists wholly or partially of at least one oxide of a precious metal, that is to say ruthenium, rhodium, palladium, osmium, iridium and platinum. Preference is given in the invention to ruthenium oxide or to a combination of said oxide with one or more other precious metal oxides.
  • the molar ratio of the oxides of precious and non-precious metals is generally between 10/1 and 1/10 and preferably between 1/5 and 5 / l.
  • the material constituting the substrate can be chosen from electrically conductive materials. It will advantageously be chosen from the group consisting of nickel, stainless steel and mild steel without this list being limiting.
  • the substrate may be in the form of a plate, sheet, with or without a certain number of orifices or perforations, lattice, metallic canvas or expanded metal, grids, the said materials being able to have a planar, cylindrical shape or any other shape according to the technology employed.
  • the invention also relates to a method of manufacturing these cathodes.
  • This process essentially consists in depositing on the substrate, possibly subjected to an appropriate preliminary treatment, one or more layers of one or more salts of metals of each category (precious metals - non-precious metals) of group VIII, then subjecting the together with a heat treatment leading to the oxidized form.
  • the preliminary treatment of the substrate advantageously consists of a degreasing - if necessary - followed by a pickling, mechanical and / or chemical, according to techniques now well known.
  • the metal salts or precursors of the oxides
  • these precursors can also be deposited separately in the form of successive layers.
  • the foregoing description is voluntarily schematic for the purpose of simplification, but it is easily understood that all combinations of precursors are possible and that in particular the same precursor may be present in several layers, either alone or associated with the same precursor in the different layers or to different precursors from one layer to another.
  • the above-mentioned precursors are deposited in the form of a solution or suspension.
  • the solvent or diluent may consist of water, mineral or organic acid or even an organic solvent.
  • An organic solvent is preferably used such as dimethylformamide, an alcohol and in particular ethanol or 2-ethyl hexanol.
  • the atomic concentration of metal is between 3.10 and 3 mole / liter and preferably between 1 and 2 mole / liter.
  • the oxide precursors which can be used in the invention generally consist of the inorganic or organic salts of metals, such as for example halides, nitrates, carbonates, sulfates, or acetates, acetylacetonates.
  • metals such as for example halides, nitrates, carbonates, sulfates, or acetates, acetylacetonates.
  • platinum and ruthenium oxides hexachloroplatinic acid hexahydrate and ruthenium chloride hydrate will advantageously be used.
  • the aforementioned layers of precursors can be deposited using conventional techniques: immersion of the substrates in the solution (s), coating with a brush, brush or the like, electrostatic spraying.
  • the preparation of solutions and the deposition of said solutions are generally done at room temperature and in air. Naturally, it is possible, if necessary, to raise the temperature in particular to facilitate the dissolution of certain precursors, and / or to work under an atmosphere of nitrogen or other inert gas with respect to the precursors.
  • the transformation of precursors into oxides is generally done by heat treatment.
  • This treatment is advantageously preceded by an air drying intended to totally or partially remove the solvent or diluent.
  • This steaming can be carried out at a temperature of up to 200 ° C, the temperature range from 100 to 150 ° C being particularly recommended.
  • the duration of this treatment is generally a few tens of minutes.
  • the actual treatment is generally carried out in air at a temperature varying, depending on the precursors used, between 200 and 1000 ° C. Preferably one operates at a temperature between 400 and 750 ° C.
  • the duration of this heat treatment is generally between 15 min and 1 h per layer. This heat treatment can be carried out after each baking or after the last baking in the case of the deposition of several layers.
  • the cathode of the invention is suitable for use in electrolysis cells in which water or aqueous solution is electrolyzed with production of hydrogen by electrolysis, released at the cathode.
  • the cathode is particularly suitable for the electrolysis of aqueous solutions of alkali metal chlorides and in particular aqueous solutions of sodium chloride and for the electrolysis of water, for example in the electrolysis of aqueous solutions of potassium hydroxide .
  • microporous diaphragms can be used as separators, but the cathodes according to the invention are of particular interest in membrane technology.
  • the substrate consists of a nickel plate of 200 x 10 x 1 mm.
  • a surface treatment is carried out using corundum (average diameter of the beads 250 ⁇ m).
  • the nickel plate is coated with this solution. Steaming is carried out in air (120 ° C, 30 min), followed by a heat treatment in air (500 ° C, 30 min). After cooling, the coating / baking / heat treatment sequence is repeated twice.
  • a deposit of 1.7 mg / cm 2 is obtained of a mixture essentially in the form of scales of average dimensions of between 3 and 30 ⁇ m, and having in X-ray radiography the structures of Ru 0 2 and NiO.
  • Ruthenium oxide has a microcrystalline structure and nickel oxide has a crystalline structure.
  • This cathode tested in soda at 450 g / 1, at 85 ° C and under 50 A / dm 2 has a working potential of - 1160 mV compared to the saturated calomel electrode (ECS).
  • an 80 mm diameter disc consisting of a mesh of expanded and rolled nickel, coated with Ru O 2 / NiO using the process described above, is used as the cathode of a solution electrolysis cell aqueous sodium chloride - membrane technology.
  • a nickel substrate is used which has undergone a surface treatment under the conditions of Example 1.
  • the nickel substrate and the two solutions A and B of Example 2 are used.
  • a first layer of solution A is deposited on the nickel (coating / baking / heat treatment sequence of Example 1) and then, after cooling, 2 layers of solution B (also coating / baking / heat treatment sequence of Example 1). 'example 1).
  • This cathode, carrying a double coating comprising Ru 0 2 and N10 has a working potential of ⁇ 1190 relative to ECS (test in the soda of example 1).
  • This cathode which has a NiO coating (2.2 mg / cm 2 ), has a working potential (test in soda of example 1) of - 1430 mV compared to DHW
  • a nickel substrate treated as in Example 1 is used.
  • a deposit of 2.2 mg / cm 2 of a mixture is obtained which exhibits the structures of Ru O 2 and Fe 2 0 3 on X-ray.
  • This cathode tested in sodium hydroxide as in Example 1, has a working potential of - 1180 mV compared to E.C.S.
  • a nickel substrate treated as in Example 1 is used.
  • a deposit of 2.3 mg / cm 2 is obtained of a mixture exhibiting on X-ray the structures of Ru O 2 and Co 3 O 4 .
  • This cathode tested in sodium hydroxide as in Example 1, has a working potential of - 1180 mV compared to E.C.S.

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  • 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)
EP86400657A 1985-03-29 1986-03-27 Kathode für Elektrolyse und deren Herstellungsverfahren Withdrawn EP0198752A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8504738 1985-03-29
FR8504738A FR2579628A1 (fr) 1985-03-29 1985-03-29 Cathode pour electrolyse et un procede de fabrication de ladite cathode

Publications (1)

Publication Number Publication Date
EP0198752A1 true EP0198752A1 (de) 1986-10-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86400657A Withdrawn EP0198752A1 (de) 1985-03-29 1986-03-27 Kathode für Elektrolyse und deren Herstellungsverfahren

Country Status (5)

Country Link
US (1) US4900585A (de)
EP (1) EP0198752A1 (de)
JP (1) JPS61243189A (de)
CN (1) CN86102066A (de)
FR (1) FR2579628A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5387525A (en) * 1993-09-03 1995-02-07 Ciba Corning Diagnostics Corp. Method for activation of polyanionic fluorescent dyes in low dielectric media with quaternary onium compounds
JP3612365B2 (ja) * 1995-04-26 2005-01-19 クロリンエンジニアズ株式会社 活性陰極及びその製造法
US20040101718A1 (en) * 2002-11-26 2004-05-27 Lixin Cao Metal alloy for electrochemical oxidation reactions and method of production thereof
DE102007044171A1 (de) * 2007-09-15 2009-03-19 Bayer Materialscience Ag Verfahren zur Herstellung von Graphitelektroden für elektrolytische Prozesse
ES2844524T3 (es) * 2014-12-26 2021-07-22 Asahi Chemical Ind Cátodo de electrólisis y método de fabricación para el mismo, y tanque de electrólisis
EP4056735A1 (de) * 2021-03-09 2022-09-14 Studiengesellschaft Kohle mbH Verfahren zur herstellung einer elektrode für elektrolytische anwendungen
CN117737784B (zh) * 2023-01-09 2025-02-14 兰州大学 贵金属催化剂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0129088A1 (de) * 1983-06-21 1984-12-27 SIGRI GmbH Kathode für wässrige Elektrolysen
EP0129734A2 (de) * 1983-05-31 1985-01-02 The Dow Chemical Company Herstellung und Anwendung von Elektroden

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4157943A (en) * 1978-07-14 1979-06-12 The International Nickel Company, Inc. Composite electrode for electrolytic processes
US4214970A (en) * 1979-01-15 1980-07-29 Diamond Shamrock Technologies, S.A. Novel electrocatalytic electrodes
US4311569A (en) * 1980-04-21 1982-01-19 General Electric Company Device for evolution of oxygen with ternary electrocatalysts containing valve metals
DE3106587C2 (de) * 1981-02-21 1987-01-02 Heraeus Elektroden GmbH, 6450 Hanau Elektrode und deren Verwendung
US4584085A (en) * 1983-05-31 1986-04-22 The Dow Chemical Company Preparation and use of electrodes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0129734A2 (de) * 1983-05-31 1985-01-02 The Dow Chemical Company Herstellung und Anwendung von Elektroden
EP0129088A1 (de) * 1983-06-21 1984-12-27 SIGRI GmbH Kathode für wässrige Elektrolysen

Also Published As

Publication number Publication date
CN86102066A (zh) 1986-10-08
JPS61243189A (ja) 1986-10-29
US4900585A (en) 1990-02-13
FR2579628A1 (fr) 1986-10-03

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