EP0240413B1 - Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode - Google Patents

Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode Download PDF

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Publication number
EP0240413B1
EP0240413B1 EP87400662A EP87400662A EP0240413B1 EP 0240413 B1 EP0240413 B1 EP 0240413B1 EP 87400662 A EP87400662 A EP 87400662A EP 87400662 A EP87400662 A EP 87400662A EP 0240413 B1 EP0240413 B1 EP 0240413B1
Authority
EP
European Patent Office
Prior art keywords
nickel
cathode
substrate
layer
solution
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 - Lifetime
Application number
EP87400662A
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English (en)
French (fr)
Other versions
EP0240413A1 (de
Inventor
Jacques Clerc-Renaud
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
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Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT87400662T priority Critical patent/ATE56757T1/de
Publication of EP0240413A1 publication Critical patent/EP0240413A1/de
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Publication of EP0240413B1 publication Critical patent/EP0240413B1/de
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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
    • 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

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.
  • European patent application 0129374 describes cathodes carrying a coating consisting of a mixture of at least one platinum group metal and at least one oxide of a platinum group metal, the platinum group metal representing 2 to 30 % of the weight of said mixture.
  • British patent 1,511,719 describes a cathode comprising a metal substrate, a cobalt coating and a second ruthenium coating.
  • Japanese patent application published under the number 54-090080 describes a technique for manufacturing a cathode consisting of treating a ferrous substrate with perchloric acid and then coating this cathode by sintering active substances including ruthenium, iridium , iron and nickel in metallic or metal compound form.
  • Japanese patent application published under the number 54-110983 (US Patent No. 4,465,580) describes a cathode carrying a coating consisting of a dispersion of particles of nickel or a nickel alloy and an activator consisting of platinum, ruthenium, iridium, rhodium, palladium or osmium or an oxide of these metals.
  • Japanese patent application published under number 54-010036 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 d '' at least one platinum group metal.
  • European patent application 0129734 describes a cathode manufacturing technique, by depositing on a electroconductive substrate a coating solution comprising a metal oxide precursor and necessarily a pickling agent in order to dissolve the most soluble parts of the substrate and / or a coating layer already deposited, this technique further comprising an operation of removing the most volatile part of the coating solution, said part containing solubilized fractions of the substrate (op. cit. p. 14).
  • precious metals denotes ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the cathodes in accordance with the invention must comprise a layer a in contact with the substrate and a layer b in contact with the electrolyte and with a layer a, which means that they may have only one single layer a and single layer b or a succession of layers a and b, starting from the substrate, and ending with a layer b.
  • the layer a consists of at least one compound chosen from the group consisting of platinum, ruthenium, rhodium, oxides of ruthenium, of iridium, of rhodium, of platinum, the mixtures of the abovementioned oxides and of oxides of titanium or nickel, and in which layer b is made of nickel or cobalt.
  • the compound (s) constituting the layer a in contact with the substrate is (are) advantageously deposited (s) in an amount representing from 0.2 to 5 mg / cm z .
  • the compound (s) constituting layer b in contact with the electrolyte is (are) deposited in an amount representing 1 to 15 mg / cm 2 .
  • the amounts of compounds which may constitute the possible intermediate layers a and b are not critical but, in such a case, it is recommended to respect the respective values mentioned above.
  • 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, lattice, wire mesh or expanded metal, grids, said materials possibly having a planar, cylindrical shape or any other shape depending on 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, the layers of one or more compounds leading to the metals or compounds constituting the layers a and b (hereinafter precursors) and then subjecting the assembly to a treatment leading to the desired chemical form (metal, oxide).
  • the preliminary treatment of the substrate advantageously consists of degreasing-if necessary-followed by pickling, mechanical and / or chemical, according to techniques now well known.
  • the aforementioned precursors are deposited in the form of a solution or suspension.
  • a solvent or diluent such as water, a mineral or organic acid or an organic solvent.
  • An organic solvent is preferably used such as dimethylformamide, an alcohol and in particular ethanol, 2-propanol or 2-ethylhexanol.
  • the metal atom concentration is between 3.10- 2 and 3 mol / liter and preferably between 1 and 2 mol / liter.
  • the precursors which can be used in the invention generally consist of mineral or organic salts of metals, such as, for example, halides, nitrates, carbonates, sulfates, or alternatively acetates, acetylacetonates.
  • the above-mentioned precursor layers can be deposited using conventional techniques: immersion of the substrates in the solution (s), coating with a brush, brush or the like, electrostatic spraying. Layers a and b can also be deposited galvanically. In the hypothesis of a deposition of layer b by chemical means, it may be advantageous to carry out sensitization of the layer a previously deposited. This treatment, which comprises a succession of sensitization / rinsing phases, is described for example in Modem Electroplating by F. Lowenheim - John Wiley & Sons 1974 pp. 644 to 646.
  • the preparation of solutions and the deposition of said solutions are generally carried out at ambient 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 the precursors of the layer a 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 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 mm 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 with production of hydrogen in basic medium.
  • the cathode is very 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, by example in the electrolysis of aqueous potassium hydroxide solutions.
  • microporous diaphragms can be used as separators, but the cathodes according to the invention are of particular interest in membrane technology.
  • the nickel plate is coated with this solution.
  • the nickel plate coated according to a is successively immersed in solution A at ambient temperature for 1 min, in solution B at the temperature of 30 ° C for 1 min, then in 200 cm 3 of solution C maintained at 30 ° C for 60 nm.
  • a deposit of 2.29 mg / cm 2 of Ni is thus obtained in the form of a nickel / phosphorus alloy with less than 15 atomic% of phosphorus.
  • a layer of solution D is deposited on the nickel substrate first (coating / baking / heat treatment sequence of example 1), then after cooling 2 layers of solution E (also coating, baking, heat treatment sequence of the 'example 1).
  • a ruthenium metal deposition is carried out on the nickel substrate by electrolysis of solution F at a temperature of 30 ° C under a current density of 15 A / dm 2 for 60 min.
  • a layer of this solution is deposited on the nickel substrate according to the coating / baking / heat treatment sequence of Example 1.
  • the nickel plate coated according to a is successively immersed in solution A (of Example 1) at room temperature for 1 min, in solution B (of Example 1) at the temperature of 30 ° C for 1 min , then in 200 cm 3 of solution G maintained at 80 ° C for 20 min.
  • Example 1 The test of Example 1 is repeated using in the solution C 30 cm 3 / I of NH 4 OH, 20% by weight.
  • Example 1 c The working potential measured under the conditions of Example 1 c is -1240 mV relative to E.C.S.
  • a layer of this solution is deposited on the mild steel substrate according to the coating / baking / heat treatment sequence of Example 1.
  • a layer of this solution is deposited on the nickel substrate according to the coating / baking / heat treatment sequence of Example 1.
  • Example 1 On the nickel substrate surface-treated according to Example 1, a deposit of 2.2 mg / cm 2 of nickel is carried out according to the procedure described in Example 1-b.
  • This cathode tested in the soda of Example 1, has a working potential of ⁇ 1490 mV compared to E.C.S.
  • This cathode tested in the soda of Example 1, has a working potential of ⁇ 1480 mV compared to E.C.S.
  • Example 10 On the nickel substrate surface-treated according to Example 1, a deposit of 5 mg / cm 2 of nickel is carried out according to the procedure described in Example 10-b.
  • This cathode tested in the soda of example 1, has a working potential of ⁇ 1640 mV compared to E.C.S.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)

Claims (5)

1. Kathode, insbesondere für die Elektrolyse wäßriger Lösungen von Alkalihalogeniden, aus einem elektrisch leitenden Substrat und daurauf einem Überzug aus einem Edelmetall und/oder einer Edelmetallverbindung, dadurch gekennzeichnet, daß sich auf dem elektrisch leitenden Substrat ein heterogener Überzug aus zumindest zwei Schichten a und b befindet, wobei die auf dem Substrat aufliegende Schicht a zumindest einen Stoff aus folgender Gruppe enthält
-Metalle der Platingruppe
-Oxide der Platinmetalle und
-Gemische von Oxiden der Platinmetalle und zumindest eines Oxids von Nickel, Cobalt, Eisen, Titan, Hafnium, Niob, Tantal und Zirkonium
und die Schicht b auf der Schicht a in Berührung mit dem Elektrolyt gebildet wird durch ein Metall in Form von Nickel, Cobalt, Eisen oder deren Legierungen sowie diesen Legierungen enthaltend weniger als 15 Atom-% Phosphor, Bor oder Schwefel, wobei das Verhältnis zwischen der von der Schicht b projizierten Oberfläche zu der von dem Substrat projizierten Fläche über 95% beträgt.
2. Kathode nach Anspruch 1, dadurch gekennzeichnet, daß die Schicht b aus Nickel oder Cobalt besteht.
3. Kathode nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der (die) Stoff(e), der (die) die Schicht a bildet (bilden) und mit dem Substrat in Berührung steht (stehen), in einem Flächengewicht von 0,2 bis 55 mg/cm2 vorliegt (vorliegen).
4. Kathode nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der (die) Stoff(e), der (die) die Schicht b bildet (bilden) und mit dem Elektrolyt in Berührung steht (stehen), in einem Flächengewicht von 1 bis 15 mg/cm2 vorliegt (vorliegen).
5. Verfahren zur Herstellung der Kathoden nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man auf dem Substrat, gegebenenfalls nach einer Vorbehandlung, eine oder mehrere Schichten der Metalle oder Verbindungen entsprechend a und b aufbringt und dann das ganze einer Behandlung unterwirft, um die gewünschte chemische Form (Metall, Oxid) zu erhalten.
EP87400662A 1986-04-03 1987-03-25 Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode Expired - Lifetime EP0240413B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87400662T ATE56757T1 (de) 1986-04-03 1987-03-25 Kathode fuer elektrolyse und verfahren zur herstellung einer solchen kathode.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8604767A FR2596776B1 (fr) 1986-04-03 1986-04-03 Cathode pour electrolyse et un procede de fabrication de ladite cathode
FR8604767 1986-04-03

Publications (2)

Publication Number Publication Date
EP0240413A1 EP0240413A1 (de) 1987-10-07
EP0240413B1 true EP0240413B1 (de) 1990-09-19

Family

ID=9333848

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87400662A Expired - Lifetime EP0240413B1 (de) 1986-04-03 1987-03-25 Kathode für Elektrolyse und Verfahren zur Herstellung einer solchen Kathode

Country Status (9)

Country Link
US (1) US4798662A (de)
EP (1) EP0240413B1 (de)
JP (1) JPS62238385A (de)
KR (1) KR890002699B1 (de)
CN (1) CN1010234B (de)
AT (1) ATE56757T1 (de)
CA (1) CA1285903C (de)
DE (1) DE3764989D1 (de)
FR (1) FR2596776B1 (de)

Families Citing this family (21)

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Publication number Priority date Publication date Assignee Title
JPH0726240B2 (ja) * 1989-10-27 1995-03-22 ペルメレック電極株式会社 鋼板の電解酸洗又は電解脱脂方法
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
JP3628756B2 (ja) * 1995-04-28 2005-03-16 ペルメレック電極株式会社 ガス拡散電極
US5645930A (en) * 1995-08-11 1997-07-08 The Dow Chemical Company Durable electrode coatings
AU2663297A (en) * 1996-04-10 1997-11-12 George H Miley System, electrolytic cell and method for producing excess heat and for transmutation by electrolysis
WO1998003699A2 (en) * 1996-07-09 1998-01-29 Patterson James A Electrolytic nuclear transmuted elements having unnatural isotopic distributions
US5676816A (en) * 1996-07-12 1997-10-14 Patterson; James A. Catalytic particles electrolytic cell system and method for producing heat
WO1999016082A1 (en) * 1997-09-19 1999-04-01 Patterson James A Catalytic ceramic particles, electrolytic production of heat
US6315880B1 (en) * 1997-10-16 2001-11-13 Mary R. Reidmeyer Chemical plating method, electrolytic cell and automotive oxygen sensor using it
EP0935265A3 (de) 1998-02-09 2002-06-12 Wilson Greatbatch Ltd. Durch thermische Zerstäubung beschichtetes Substrat zur Verwendung in einer elektrischen Energiespeicheranordnung und Herstellungsverfahren
FR2775486B1 (fr) * 1998-03-02 2000-04-07 Atochem Elf Sa Cathode specifique, utilisable pour la preparation d'un chlorate de metal alcalin et son procede de fabrication
FR2852973B1 (fr) * 2003-03-28 2006-05-26 Atofina Procede de formation d'un revetement d'oxydes metalliques sur un substrat electroconducteur; cathode activee en resultant et son utilisation pour l'electrolyse de solutions acqueuses de chorures de meteaux alcalins.
ITMI20041006A1 (it) * 2004-05-20 2004-08-20 De Nora Elettrodi Spa Anodo per sviluppo ossigeno
EP2085501A1 (de) * 2008-01-31 2009-08-05 Casale Chemicals S.A. Hochleistungskathoden für Wasserelektrolyseure
ITMI20090880A1 (it) * 2009-05-19 2010-11-20 Industrie De Nora Spa Catodo per processi elettrolitici
US9145615B2 (en) 2010-09-24 2015-09-29 Yumei Zhai Method and apparatus for the electrochemical reduction of carbon dioxide
JP2013166994A (ja) * 2012-02-15 2013-08-29 Asahi Kasei Chemicals Corp 電解用電極、電解槽及び電解用電極の製造方法
CN108337894B (zh) * 2015-09-14 2020-08-25 哈佛学院院长及董事 碳固定系统和方法
WO2018009315A1 (en) 2016-07-06 2018-01-11 President And Fellows Of Harvard College Ammonia synthesis methods and systems
CN109894130B (zh) * 2019-04-01 2022-01-14 国能南京电力试验研究有限公司 一种脱汞催化剂及其制备方法

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Publication number Priority date Publication date Assignee Title
DE2113676C2 (de) * 1971-03-20 1985-09-12 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach Elektrode für elektrochemische Prozesse
US3941675A (en) * 1971-09-28 1976-03-02 Friedrich Uhde Gmbh Bipolar multiple electrolytic cell comprising a diaphragm and electrode for same
FR2265454A2 (en) * 1974-03-26 1975-10-24 Uhde Gmbh Friedrich Polyether-polycarbonate block copolymer films - esp for haemodialysis made by casting from soln
US4300992A (en) * 1975-05-12 1981-11-17 Hodogaya Chemical Co., Ltd. Activated cathode
GB2083837B (en) * 1980-08-18 1984-06-27 Diamond Shamrock Corp Manufacture of electrode with manganese dioxide coating valve metal base intermediate semiconducting layer
JPS6021232B2 (ja) * 1981-05-19 1985-05-25 ペルメレツク電極株式会社 耐久性を有する電解用電極及びその製造方法
JPS59100280A (ja) * 1982-12-01 1984-06-09 Toagosei Chem Ind Co Ltd 水素発生用陰極
US4530742A (en) * 1983-01-26 1985-07-23 Ppg Industries, Inc. Electrode and method of preparing same
DE3322169A1 (de) * 1983-06-21 1985-01-10 Sigri Elektrographit Gmbh, 8901 Meitingen Kathode fuer waesserige elektrolysen

Also Published As

Publication number Publication date
CA1285903C (fr) 1991-07-09
KR890002699B1 (ko) 1989-07-24
JPH021918B2 (de) 1990-01-16
FR2596776B1 (fr) 1988-06-03
DE3764989D1 (de) 1990-10-25
EP0240413A1 (de) 1987-10-07
FR2596776A1 (fr) 1987-10-09
CN1010234B (zh) 1990-10-31
ATE56757T1 (de) 1990-10-15
KR870010220A (ko) 1987-11-30
US4798662A (en) 1989-01-17
CN87102588A (zh) 1987-10-14
JPS62238385A (ja) 1987-10-19

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