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EP0235860A1 - Method for manufacturing an electrode, and electrode thus manufactured - Google Patents

Method for manufacturing an electrode, and electrode thus manufactured Download PDF

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Publication number
EP0235860A1
EP0235860A1 EP87200308A EP87200308A EP0235860A1 EP 0235860 A1 EP0235860 A1 EP 0235860A1 EP 87200308 A EP87200308 A EP 87200308A EP 87200308 A EP87200308 A EP 87200308A EP 0235860 A1 EP0235860 A1 EP 0235860A1
Authority
EP
European Patent Office
Prior art keywords
nickel
electrode
bath
salt
electrolysis
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Withdrawn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
EP87200308A
Other languages
German (de)
French (fr)
Inventor
Philippe Vermeiren
Roger Frans Rosa Leysen
René Cornelissen
Jan Baptist Hugo Vandenborre
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.)
Centre dEtude de lEnergie Nucleaire CEN
Original Assignee
Centre dEtude de lEnergie Nucleaire CEN
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
Priority claimed from BE2/60932A external-priority patent/BE904281A/en
Application filed by Centre dEtude de lEnergie Nucleaire CEN filed Critical Centre dEtude de lEnergie Nucleaire CEN
Publication of EP0235860A1 publication Critical patent/EP0235860A1/en
Withdrawn legal-status Critical Current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

Definitions

  • the invention relates to a method for manufactu­ring an electrode, more particularly for preparing H2 and O2 in alkaline media, which comprises electro-depositing a catalytic coating layer which contains at least Ni and S, on an electrical-conducting support.
  • a cathode is manufactured by first forming on a support, a thin layer of Ni and thereafter subjecting the electrode to an electrolysis inside a tank which contains nickel sulfate and thio-urea.
  • BE-A-865,396 a similar method for manufacturing an anode.
  • a support is first coated by electroplating with an amount of Ni,whereafter the formed electrode is activated by electrolysis in a bath wherein nickel sulfate and thio-urea are dissolved.
  • the electrolysis a portion of the nickel coating dissolves while sulfur is absorbed in the remaining portion of said coating.
  • the above-mentioned known methods pertain to manufacturing either an anode or a cathode.
  • the invention has for object to provide a method wherewith an electrode is obtained which can work as well as anode as as cathode inside a cell.
  • the support material is polarized as cathode inside an electrolysis cell with has as an anode, a soluble nickel plate and with a bath which contains a sulfur-releasing component and a salt from transition metal other than nickel.
  • Nickel from the anode dissolves and is deposited together with the other transition metal and sulfur on the sup­port, in such a way that an electrode is formed with a thin catalytic layer which contains nickel, another transition metal and sulfur.
  • the electrode By acting on the proportion of the nickel and the other transition metal in the catalytic layer, the electrode can be made better suitable as anode, or better suitable as cathode.
  • Preparing the anode and the cathode can occur with a single equipment.
  • an electrolysis cell with a bath which contains, besides a sulfur-releasing component and a salt from another transition metal than nickel, a nickel salt.
  • an electrolysis cell with a bath which contains as salt from another transition metal than nickel, a cobalt salt.
  • the thin catalytic layer comprises nickel, cobalt and sulfur. The more nickel it does contain, the better the electrode is suitable as cathode. The more cobalt it does contain, the better the electrode is suitable as anode.
  • use is made as support material of an electrolytically-­formed perforated nickel plate.
  • the support is first roughened,de-greased and then etched in boiling acid.
  • a thin layer of nickel is first deposited on the support before the latter is polarized as cathode.
  • the electrolysis bath pH is maintained approximately at 3.
  • the bath is retained during electrolysis,at a temperature of about 60°C.
  • the invention further pertains to an electrode manufactured by the method according to one of the above embo­diments.
  • an electrical-conducting support is coated by electro­lysis with a Ni-Co-S layer.
  • Use is made as support, of an electrolytically-­formed Ni plate, which is perforated for about 50% of the surface area thereof with conically-shaped holes with a mean diameter of about 1 mm.
  • the plate is roughened by means of a carborundum brush, it is de-greased with acetone and it is etched during 30 seconds in boiling HCl (15%).
  • the plate is brought thereafter in a bath which has the following composition : 240 g/l NiCl2 120 g/l Hcl.
  • the bath temperature is kept at 20°C.
  • the plate is first polarized as anode during 20 seconds and thereafter as cathode during 40 seconds.
  • Both said polarizing steps are performed with a current density of 60 mA.cm ⁇ 2 and with a Ni counter-electrode.
  • the thus pre-treated plate is arrange direct­ly inside an electrolysis cell the bath whereof has the following composition : 60 g/l CoSO4.7H2O 80 g/l Cs(NH2)2 1 ml/l concentrated H2SO4 4.5 g/l CH3COOH 2 g/l NaOH.
  • the bath pH is 3.
  • the bath temperature is kept at 60°C and the bath is stirred and filtered continuously.
  • the plate is polarized as cathode.
  • a soluble nickel electrode which is arranged five centimeters away from the plate.
  • the soluble nickel electrode is shielded with a bag of porous synthetic material.
  • the electrolysis is performed during 76 hours with a current density of 6mA/cm2.
  • Nickel from the anode is dissolved and is deposited together with Co and S on the cathode.
  • the plate is rinsed with water, whereafter it is blown dry with pressurized air.
  • one proceeds as above-described, with the exception that use is made of an electrolysis cell bath which contains,besides a sulfur-releasing component and a cobalt salt,also a nickel salt.
  • the bath has the following composition : 60 g/l CoSO4.7H2O 60 g/l NiSO4.6H2O 80 g/l Cs(NH2)2 4.5 g/l CH3COOH 2 g/l NaOH 1 ml/l concentrated H2SO4.
  • the ratio 60 g CoSO4/60 g NiSO4 gives a compro­mise proportion between both transition metals in the thin catalytic layer of the electrode,which makes said electrode suitable both as anode and as cathode.
  • Still another embodiment of the invention differs from the preceding one by making use of an electrolysis cell bath which contains instead of a cobalt salt, a salt from another transition metal.
  • the bath has the following composition : 60 g/l FeSO4.6H2O 60 g/l NiSO4.6H2O 80 g/l Cs(NH2)2 2 g/l NaOH 4.5 g/l CH3COOH.
  • use is made as iron salt of (NH4)2.Fe(SO4)2.6H2O instead of FeSO4. 6H2O.
  • the thus obtained electrodes have been tested as anode and as cathode in an electrolysis cell for water in alkaline media.
  • anode poten­tial lying between approximately + 0.50 V and + 0.60 V relative to a Hg/HgO reference electrode which was at room temperature.
  • cathode potentials lie between approximately - 1.05 V and - 1.15 V relative to a Hg/HgO reference electrode which was at room temperature.
  • the electrode prepared in the above-described way has for advantage that when being used as anode inside an electrolysis cell of bipolar type, it is stable with current interruptions, which is not the case with many other anodes which are manufactured from oxide material, when said latter ones are coupled with electrodes which can contain hydrogen.
  • the conically-shaped openings in the support material make possible a smooth discharge of the H2 or O2 bubbles.

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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)

Abstract

A catalytic covering layer containing at least Ni and S is electro-deposited on an electrical-conducting, electrolytically-formed perforated nickel plate by polarizing said nickel plate as cathode inside an electrolysis cell with a soluble nickel plate as anode and with a bath which contains a sulfur-releasing component, a salt from transition metal other than nickel such as a cobalt salt and preferably also a nickel salt.

Description

  • The invention relates to a method for manufactu­ring an electrode, more particularly for preparing H₂ and O₂ in alkaline media, which comprises electro-depositing a catalytic coating layer which contains at least Ni and S, on an electrical-conducting support.
  • A method of this kind is known from BE-A-­864,275.
  • According to said known method, a cathode is manufactured by first forming on a support,a thin layer of Ni and thereafter subjecting the electrode to an electrolysis inside a tank which contains nickel sulfate and thio-urea.
  • There is known from BE-A-865,396, a similar method for manufacturing an anode. A support is first coated by electroplating with an amount of Ni,whereafter the formed electrode is activated by electrolysis in a bath wherein nickel sulfate and thio-urea are dissolved.During the electrolysis, a portion of the nickel coating dissolves while sulfur is absorbed in the remaining portion of said coating.
  • The above-mentioned known methods pertain to manufacturing either an anode or a cathode.
  • The invention has for object to provide a method wherewith an electrode is obtained which can work as well as anode as as cathode inside a cell.
  • For this purpose,the support material is polarized as cathode inside an electrolysis cell with has as an anode,a soluble nickel plate and with a bath which contains a sulfur-releasing component and a salt from transition metal other than nickel.
  • Nickel from the anode dissolves and is deposited together with the other transition metal and sulfur on the sup­port, in such a way that an electrode is formed with a thin catalytic layer which contains nickel, another transition metal and sulfur.
  • By acting on the proportion of the nickel and the other transition metal in the catalytic layer, the electrode can be made better suitable as anode, or better suitable as cathode.
  • Preparing the anode and the cathode can occur with a single equipment.
  • In a particular embodiment of the invention, use is made of an electrolysis cell with a bath which contains, besides a sulfur-releasing component and a salt from another transition metal than nickel, a nickel salt.
  • In a remarkable embodiment of the invention, use is made of an electrolysis cell with a bath which contains as salt from another transition metal than nickel, a cobalt salt.
  • The thin catalytic layer comprises nickel, cobalt and sulfur. The more nickel it does contain, the better the electrode is suitable as cathode. The more cobalt it does contain, the better the electrode is suitable as anode.
  • In another particular embodiment of the invention, use is made as support material of an electrolytically-­formed perforated nickel plate.
  • In an advantageous embodiment of the invention, the support is first roughened,de-greased and then etched in boiling acid.
  • In a useful embodiment of the invention a thin layer of nickel is first deposited on the support before the latter is polarized as cathode.
  • In another useful embodiment of the invention, the electrolysis bath pH is maintained approximately at 3.
  • In another useful embodiment of the invention, the bath is retained during electrolysis,at a temperature of about 60°C.
  • The invention further pertains to an electrode manufactured by the method according to one of the above embo­diments.
  • Other features and advantages of the invention will stand out from the following description of a method for manufacturing an electrode and of a thus manufactured electrode, according to the invention; this description is only given by way of example and does limit the invention.
  • To manufacture an electrode according to the invention,an electrical-conducting support is coated by electro­lysis with a Ni-Co-S layer.
  • Use is made as support, of an electrolytically-­formed Ni plate, which is perforated for about 50% of the surface area thereof with conically-shaped holes with a mean diameter of about 1 mm.
  • The plate is roughened by means of a carborundum brush, it is de-greased with acetone and it is etched during 30 seconds in boiling HCl (15%).
  • The plate is brought thereafter in a bath which has the following composition :
    240 g/l NiCl₂
    120 g/l Hcl.
  • The bath temperature is kept at 20°C.
  • The plate is first polarized as anode during 20 seconds and thereafter as cathode during 40 seconds.
  • Both said polarizing steps are performed with a current density of 60 mA.cm⁻² and with a Ni counter-electrode.
  • The thus pre-treated plate is arrange direct­ly inside an electrolysis cell the bath whereof has the following composition : 60 g/l CoSO₄.7H₂O
    80 g/l Cs(NH₂)₂
    1 ml/l concentrated H₂SO₄
    4.5 g/l CH₃COOH
    2 g/l NaOH.
  • The bath pH is 3. The bath temperature is kept at 60°C and the bath is stirred and filtered continuously.
  • The plate is polarized as cathode.
  • Use is made as anode for the electrolysis cell, of a soluble nickel electrode which is arranged five centimeters away from the plate. The soluble nickel electrode is shielded with a bag of porous synthetic material.
  • The electrolysis is performed during 76 hours with a current density of 6mA/cm².
  • Nickel from the anode is dissolved and is deposited together with Co and S on the cathode.
  • After the electrolysis, the plate is rinsed with water, whereafter it is blown dry with pressurized air.
  • Due to this electrolysis, there is obtained on the perforated nickel support, a thin layer with a 40µm thick­ness with as composition :
    15 atom-% Co
    40 atom-% S
    45 atom-% Ni.
  • In another embodiment of the invention, one proceeds as above-described, with the exception that use is made of an electrolysis cell bath which contains,besides a sulfur-releasing component and a cobalt salt,also a nickel salt.
  • The bath has the following composition :
    60 g/l CoSO₄.7H₂O
    60 g/l NiSO₄.6H₂O
    80 g/l Cs(NH₂)₂
    4.5 g/l CH₃COOH
    2 g/l NaOH
    1 ml/l concentrated H₂SO₄.
  • The ratio 60 g CoSO₄/60 g NiSO₄ gives a compro­mise proportion between both transition metals in the thin catalytic layer of the electrode,which makes said electrode suitable both as anode and as cathode.
  • Still another embodiment of the invention differs from the preceding one by making use of an electrolysis cell bath which contains instead of a cobalt salt, a salt from another transition metal. The bath has the following composition :
    60 g/l FeSO₄.6H₂O
    60 g/l NiSO₄.6H₂O
    80 g/l Cs(NH₂)₂
    2 g/l NaOH
    4.5 g/l CH₃COOH.
  • In a variant of this latter embodiment,use is made as iron salt of (NH₄)₂.Fe(SO₄)₂.6H₂O instead of FeSO₄. 6H₂O.
  • The thus obtained electrodes have been tested as anode and as cathode in an electrolysis cell for water in alkaline media.
  • The over-voltages measured at 120°C and with a current density of 1 A/cm² did lie markedly lower than with uncatalysed pure nickel electrodes.
  • Various electrodes prepared according to the above-described way, have been tested in alkaline media, some of them during a time period up to 10,000 hours.
  • Depending on the composition of the catalytic layer of the electrode, there has been measured an anode poten­tial lying between approximately + 0.50 V and + 0.60 V relative to a Hg/HgO reference electrode which was at room temperature.
  • Under the same conditions, cathode potentials have been measured lying between approximately - 1.05 V and - 1.15 V relative to a Hg/HgO reference electrode which was at room temperature.
  • The electrode prepared in the above-described way has for advantage that when being used as anode inside an electrolysis cell of bipolar type, it is stable with current interruptions, which is not the case with many other anodes which are manufactured from oxide material, when said latter ones are coupled with electrodes which can contain hydrogen.
  • The conically-shaped openings in the support material make possible a smooth discharge of the H₂ or O₂ bubbles.
  • The invention is in no way limited to the above-­described embodiments and within the scope of the patent appli­cation, many changes might be brought to the described embodi­ments, notably as regards the shape, the composition, the arrangement and the number of the components which are being used to embody the invention.

Claims (12)

1. Method for manufacturing an electrode, more particularly for preparing H₂ and O₂ in alkaline media, which comprises electro-depositing a catalytic covering layer which contains at least Ni and S,on an electrical-conducting support, characterized in that the support is polarized as cathode in an electrolysis cell with as anode, a soluble nickel plate and with a bath which contains a sulfur-releasing component and a salt from a transition metal other than nickel.
2. Method according to claim 1, characterized in that use is made of an electrolysis cell with a bath which contains, besides a sulfur-releasing component and a salt from transition metal other than nickel,a nickel salt.
3. Method according to either one of claims 1 and 2, characterized in that use is made of an electrolysis cell with a bath which contains as salt from transition metal other than nickel,a cobalt salt.
4. Method according to any one of claims 1 to 3, characterized in that use is made as support, of an electro­lytically-formed perforated nickel plate.
5. Method according to claim 4, characterized in that use is made as support, of a nickel plate which is provided over approximately 50% of the surface area thereof, with conically-shaped openings.
6. Method according to any one of claims 1 to 5, characterized in that the support is first roughened, de-grea­sed and thereafter etched in boiling acid.
7. Method according to any one of claims 1 to 5,characterized in that a thin layer of nickel is deposited onto the support before the latter is polarized as cathode.
8. Method according to any one of claims 1 to 7, characterized in that the electrolysis bath pH is retained at about 3.
9. Method according to any one of claims 1 to 8,characterized in that the temperature of the electrolysis bath is retained at about 60°C during the electrolysis.
10. Method according to any one of claims 1 to 9, characterized in that the electrolysis is performed with a current density of about 6 mA/cm².
11. Method for manufacturing an electrode as described hereinabove.
12. Electrode, manufactured by the method according to any one of the preceding claims.
EP87200308A 1986-02-26 1987-02-24 Method for manufacturing an electrode, and electrode thus manufactured Withdrawn EP0235860A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE2060932 1986-02-26
BE2/60932A BE904281A (en) 1986-02-26 1986-02-26 Electrodes for electrolytic prodn. of oxygen and hydrogen - made by electrodeposition of catalytic layer contg. nickel, another transition metal and sulphur onto electroconductive support

Publications (1)

Publication Number Publication Date
EP0235860A1 true EP0235860A1 (en) 1987-09-09

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EP87200308A Withdrawn EP0235860A1 (en) 1986-02-26 1987-02-24 Method for manufacturing an electrode, and electrode thus manufactured

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NO (1) NO870708L (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017167373A1 (en) * 2016-03-31 2017-10-05 Siemens Aktiengesellschaft A technique for in-situ anode activation by a cathode in an alkaline water electrolytic cell
WO2022243438A1 (en) 2021-05-19 2022-11-24 Hydrogenpro As A method for producing electrodes for electrolysis

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1162878A (en) * 1913-12-26 1915-12-07 Marvin E Quant Storage-casing for refuse-receptacles.
US4422920A (en) * 1981-07-20 1983-12-27 Occidental Chemical Corporation Hydrogen cathode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1162878A (en) * 1913-12-26 1915-12-07 Marvin E Quant Storage-casing for refuse-receptacles.
US4422920A (en) * 1981-07-20 1983-12-27 Occidental Chemical Corporation Hydrogen cathode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 103, no. 14, October 1985, page 491, abstract no. 112236h, Columbus, Ohio, US; & US-A-1 162 878 (INSTITUTE OF ELECTROCHEMISTRY, ACADEMY OF SCIENCES, U.S.S.R.) 23-06-1985 *
PATENT ABSTRACTS OF JAPAN, vol. 9, no. 130 (C-284)[1853], 5th June 1985; & JP-A-60 17 096 (TOYO SODA KOGYO K.K.) 28-01-1985 *
SOVIET INVENTIONS ILLUSTRATED, Section Chemical, week b30, abstract no. 55951, 5th September 1979, Derwent Publications Ltd, London, GB; & SU-A-627 183 (MOSC POWER INST) 04-09-1978 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017167373A1 (en) * 2016-03-31 2017-10-05 Siemens Aktiengesellschaft A technique for in-situ anode activation by a cathode in an alkaline water electrolytic cell
CN109072461A (en) * 2016-03-31 2018-12-21 西门子股份公司 The technology of anode activation in situ is carried out by the cathode in alkaline water electrolytic pond
WO2022243438A1 (en) 2021-05-19 2022-11-24 Hydrogenpro As A method for producing electrodes for electrolysis
WO2022243441A1 (en) 2021-05-19 2022-11-24 Hydrogenpro As A method for producing electrodes for electrolysis

Also Published As

Publication number Publication date
NO870708D0 (en) 1987-02-23
NO870708L (en) 1987-08-27

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Inventor name: VANDENBORRE, JAN BAPTIST HUGO