WO1985000389A1 - Electrode, ses procedes de fabrication et son utilisation - Google Patents

Electrode, ses procedes de fabrication et son utilisation Download PDF

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Publication number
WO1985000389A1
WO1985000389A1 PCT/SE1984/000246 SE8400246W WO8500389A1 WO 1985000389 A1 WO1985000389 A1 WO 1985000389A1 SE 8400246 W SE8400246 W SE 8400246W WO 8500389 A1 WO8500389 A1 WO 8500389A1
Authority
WO
WIPO (PCT)
Prior art keywords
tin
coating
electrode
hydrogen
alloy
Prior art date
Application number
PCT/SE1984/000246
Other languages
English (en)
Inventor
Gunder Karlsson
Original Assignee
Electrocell Ab
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 Electrocell Ab filed Critical Electrocell Ab
Publication of WO1985000389A1 publication Critical patent/WO1985000389A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • An electrode processes for the manufacture thereof and use thereof.
  • the present invention relates to the field of electrolytic electrodes, the term electrolytic only meaning that the electrode is intended to be contacted with an electrolyte.
  • the electrode is useful in current-consuming as well as current-producing processes.
  • the electrode according to the invention is an energy-saving electrode in that it shows a low hydrogen overvoltage.
  • the invention also relates to processes for the manufacture of the electrode and to especially interesting uses thereof, at which its overvoltage-reducing properties are especially advantageous.
  • Patent specification 3,272,728 nickel-zinc alloys are disclosed which are deposited electrolytically and are leached and utilized as cathodes in electrolyzis of water.
  • DE OS 2,527,386 there is also disclosed a Raney method, wherein the preferred embodiment is a nickel-zinc alloy to be subjected to a leaching operation.
  • German specification anything to do with the present invention, since it works as in all prior art with just the combination of a noble basis metal and an ignoble base or sacrificing metal.
  • the present invention relates to something completely novel within the stated technical field. More specifically the invention makes it possible to manufacture in one single operational step a hydrogen overvoltage-reducing coating that does not need any further post or finishing treatment and that can be transported in a dry condition.
  • the coating layer can be made completely dense, which has been confirmed in connection with the invention by means of microscopy, and a good corrosion protection can be obtained concurrently with the coating, which is not the case with porous coatings of the Raney type.
  • the purpose of the invention is obtained by providing an electrically conducting, metallic substrate with a hydrogen overvoltage-reducing coating which essentially consists of an alloy from any of the iron metals, i.e. iron, cobalt or nickel, or any combination thereof, with tin, the percentage of tin of the alloy being between 0.01 and 10 percent by weight, based on said alloy.
  • a hydrogen overvoltage-reducing coating which essentially consists of an alloy from any of the iron metals, i.e. iron, cobalt or nickel, or any combination thereof, with tin, the percentage of tin of the alloy being between 0.01 and 10 percent by weight, based on said alloy.
  • the hydrogen overvoltage-reducing effect will be most pronounced if essentially the total area of the active part of the metallic substrate is coated, but no doubt some improved effect is obtained already when a minor part of said surface is coated with the alloy according to the invention, which means that the invention is not delimited to the coating of any special percentage of the surface.
  • the amount of tin in the alloy it has been shown that especially preferable results are obtained if said amount is within the range of 0.1 - 5 percent by weight, especially 0.5 - 4 percent by weight.
  • the invention also relates to especially preferable processes for the manufacture of the electrolytic electrode according to the invention. According to a first process aspect the electrode is then prepared by coating the substrate galvanically.
  • the coating containing a small amount of tin can be electro-plated with high efficiency and high current density from a plating bath that can be prepared by cheap chemicals.
  • the electrode according to the invention is manufactured by coating the substrate by thermal spraying, preferably by means of an arc spraying device.
  • the thermal spraying is performed by means of a wire having the desired composition, and the thermally sprayed layer obtained does not either require any post-treatment.
  • Other methods of preparing the electrode by means of an alloy having the desired composition are possible and within the field of what can be accomplished by a person skilled in the art with reference to the inventive idea now disclosed, but the above-mentioned methods are those methods which are to-day most preferable from an economical point of view.
  • the invention relates to especially interesting uses of the electrode, a first alternative being the use of the electrode as a cathode for hydrogen evolution in chlorate, chlorine-alkali or water electrolyzises.
  • the electrode is utilized as an anode in a hydrogen-oxygen or hydrogen-air fuel cell.
  • the alloy in the form of a powder by means of which the desired coating of the electrode has been accomplished, as it is possible to obtain a very high specific surface area by means of a powder.
  • the manufacture of the alloy in the form of a powder and the coating of the electrode therewith can be accomplished in any way that is well known to a person skilled in the art.
  • a plating bath having the following composition was prepared: 250 g of Ee SO 4 .7 H 2 O 42 g of Fe Cl 2 -4 H 2 O 20 g of NH 4 Cl
  • the above-mentioned ingredients were dissolved in distilled water up to a volume of 1 litre.
  • the solution was stirred with 1 g (5 ml. of H 2 SO 4 and 5 g of Fe-powder during one night.
  • the solution was filtered, and to the same there was added a solution prepared from: 1 g of Sn Cl 2 2 H 2 O 30 ml of 50 - gluconic acid 10 ml of distilled water.
  • the pH-value was adjusted to 2.95.
  • Platings were performed on four well cleaned copper plates, an iron plate being utilized as the anode of the plating bath. The plating operation was performed at room temperature and at varying plating current densities. Coatings with a layer thickness of about 30 ⁇ m were deposited. The electrodes were weighed after the plating operation and the current efficiency was calculated to more than 90 %.
  • the electrodes were analyzed by dissolving the layers in an acid (HCl) and determining the metal contents by means of atomic absorption.
  • the tin percentages obtained at different plating current densities are shown in table 1 below, and the connection between the tin percentage and the plating current density is shown graphically in Figure 1.
  • the electrodes were then tested as to evolution of hydrogen gas in 5M KOH, the potential being determined relative to a reference electrode in the form of Hg/HgO.
  • the potential at a current density of 1 kA/m 2 as a function of the previously measured tin percentage is shown in Table 2 below and shown graphically in Figure 2.
  • a plating bath which had previously been used for the plating of electrodes had been depleted on bivalent tin so that the "contents of bivalent tin had been reduced to 0.3 g per litre of solution.
  • a steel electrode was coated with a layer by plating in this bath at 80 mA/cm 2 .
  • This layer had a hydrogen evolution potential of -1230 mV relative to Hg/HgO at one kA/m 2 .
  • the contents of tin in the deposited layer was estimated to 0.4 percent by weight.
  • a plating bath prepared from stannic chloride does not give any active layers.
  • the amount of bivalent tin is simply monitored by iodometric titration. When the plating bath is not utilized it should be protected from air to prevent any unnecessary oxidation of the tin to inactive fourvalent tin.
  • a nickel bath which was equivalent to the iron bath of Example 1 was prepared by dissolution of: 250 g of NiSO 4 .7H 2 O
  • the most active layers were obtained at a high plating current density. More specifically, the hvdrogen evolution potential was -1170 mV relative to Hg/HgO for a layer deposited at 100 mA/cm 2 . It is true that the tin percentages were not analyzed in each single case, but they should be approximately similar to the percentages at the corresponding current densities in the iron bath. Thus, the tin is the nobler element in the iron bath as well as in the nickel bath. If the percentage of tin were the same as that of the iron, a plating operation would lead to the deposition of almost only tin. What is keeping the tin percentage down in the coating is the low percentage of tin of the solution.
  • the metal composition of the coating tends to be similar to that of the solution.
  • the percentage of tin in the coating is 1.2 % while the tin represents 0.8 % of the total metals of the solution. The same should be applicable to the nickel bath.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

Electrode électrolytique possédant un revêtement réduisant la surtension due à l'hydrogène, se composant essentiellement d'un alliage de fer, cobalt et/ou nickel avec de l'étain, le pourcentage d'étain de l'alliage se situant entre 0,01 et 10 pour cent en poids. L'électrode peut être fabriquée avantageusement en obtenant le revêtement par un procédé galvanique ou par un procédé de pulvérisation thermique. L'électrode est particulièrement indiquée pour être utilisée comme cathode pour mesurer le dégagement d'hydrogène dans l'électrolyse d'un chlorate, d'un composé de chlore-alcali ou d'eau, ou bien comme anode dans une cellule à combustible à hydrogène-oxygène ou hydrogène-air.
PCT/SE1984/000246 1983-07-01 1984-06-28 Electrode, ses procedes de fabrication et son utilisation WO1985000389A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8303788A SE8303788L (sv) 1983-07-01 1983-07-01 Energibesparnde elektrolytisk elektrod
SE8303788-7 1983-07-01

Publications (1)

Publication Number Publication Date
WO1985000389A1 true WO1985000389A1 (fr) 1985-01-31

Family

ID=20351858

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1984/000246 WO1985000389A1 (fr) 1983-07-01 1984-06-28 Electrode, ses procedes de fabrication et son utilisation

Country Status (3)

Country Link
EP (1) EP0149638A1 (fr)
SE (1) SE8303788L (fr)
WO (1) WO1985000389A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397207A1 (fr) * 1989-05-11 1990-11-14 Yoshida Kogyo K.K. Alliage catalytique pour l'oxydation de l'hydrogène
EP0770709A1 (fr) * 1995-10-25 1997-05-02 Tosoh Corporation Cathode présentant une basse surtension à l'hydrogène et son procédé de fabrication
EP0830464A1 (fr) * 1996-03-25 1998-03-25 Wilson Greatbatch Ltd. Electrode constituee d'une couche thermiquement diffusee et procede de fabrication

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111424290A (zh) * 2020-03-04 2020-07-17 中国船舶重工集团公司第七一八研究所 一种镍锡析氢电极

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2527386A1 (de) * 1974-07-17 1976-02-12 Hooker Chemicals Plastics Corp Kathodenoberflaechen mit niedrigen wasserstoffueberspannungen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2527386A1 (de) * 1974-07-17 1976-02-12 Hooker Chemicals Plastics Corp Kathodenoberflaechen mit niedrigen wasserstoffueberspannungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Vol. 53 (1959) abstracts No. 6830f, Kogyo Kagaku Zasshi 60, 383-6 (1957) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397207A1 (fr) * 1989-05-11 1990-11-14 Yoshida Kogyo K.K. Alliage catalytique pour l'oxydation de l'hydrogène
EP0770709A1 (fr) * 1995-10-25 1997-05-02 Tosoh Corporation Cathode présentant une basse surtension à l'hydrogène et son procédé de fabrication
US5827413A (en) * 1995-10-25 1998-10-27 Tosoh Corporation Low hydrogen over voltage cathode and process for production thereof
EP0830464A1 (fr) * 1996-03-25 1998-03-25 Wilson Greatbatch Ltd. Electrode constituee d'une couche thermiquement diffusee et procede de fabrication
EP0830464A4 (fr) * 1996-03-25 2002-05-08 Greatbatch W Ltd Electrode constituee d'une couche thermiquement diffusee et procede de fabrication

Also Published As

Publication number Publication date
SE8303788L (sv) 1985-01-02
SE8303788D0 (sv) 1983-07-01
EP0149638A1 (fr) 1985-07-31

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