EP0042984B1 - Electrode sans métaux nobles et son procédé de fabrication - Google Patents

Electrode sans métaux nobles et son procédé de fabrication Download PDF

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Publication number
EP0042984B1
EP0042984B1 EP81104207A EP81104207A EP0042984B1 EP 0042984 B1 EP0042984 B1 EP 0042984B1 EP 81104207 A EP81104207 A EP 81104207A EP 81104207 A EP81104207 A EP 81104207A EP 0042984 B1 EP0042984 B1 EP 0042984B1
Authority
EP
European Patent Office
Prior art keywords
spinel
electrode
plasma
spinels
cobalt
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
Application number
EP81104207A
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German (de)
English (en)
Other versions
EP0042984A1 (fr
Inventor
Hans Dr. Roos
Hugo Boehn
Knut Dr. Bittler
Volker Dr. Kiener
Gerd Dr. Wunsch
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0042984A1 publication Critical patent/EP0042984A1/fr
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Publication of EP0042984B1 publication Critical patent/EP0042984B1/fr
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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

  • titanium anodes with active metal-containing active layers or graphite electrodes are generally used today. These so-called dimensionally stable titanium anodes have the advantage over the graphite electrodes that the external dimensions do not change during operation.
  • the disadvantage of these anodes is the relatively high production costs due to the use of noble metal in the active layer.
  • magnetite can be used as an anode material for the separation of chlorine, but this material has a very high overvoltage with regard to chlorine, so that its use has been discontinued for a long time due to the high energy consumption.
  • an electrode consisting predominantly of trivalent iron oxide with additions of one or more metal oxides is described.
  • an oxide mixture is obtained from an iron salt solution via a carrier precipitation, which is then pressed and sintered in an oxygen-containing atmosphere.
  • Titanium dioxide, zirconium dioxide and / or tin dioxide are mentioned as additional oxides.
  • this electrode has a separation potential for chlorine of 1.65 V GKE (measured against saturated calomel electrode) at a current density of 1 kA / m 2 , which corresponds to a chlorine separation voltage of 1.9 V based on the normal hydrogen potential.
  • the deposition potential increases considerably, so that this electrode achieves an impermissibly high deposition potential at the current densities of 1.5 to 2.0 kA / m 2 that are currently used in technical systems.
  • DE-OS 2 320 883 describes anodes which consist of sintered bodies with a spinel structure of the general formula M x Fe 3 - x 0 4 and are said to be suitable as chlorine anodes.
  • M means a metal from the group consisting of manganese, nickel, cobalt, magnesium, copper, zinc and / or cadmium and x stands for 0.05 to 0.4.
  • electrodes which consist of an electrically conductive substrate to which a single metal spinel of the formula C 03 0 4 is applied as an electrochemically active substance, and additionally modifying oxides of groups IIIB -VIIB, IIIA-VA, and may contain lanthanides or actinides.
  • the deposition potential of these electrodes also does not meet the technical requirements.
  • the object of the present invention was to provide electrodes whose electrochemically active layer contains spinels which are particularly suitable as anodes for the separation of chlorine in electrolysis cells and which, in addition to good corrosion resistance to the electrolyte and the electrolysis products, combined with a long service life , have a low separation voltage for chlorine.
  • the electrode according to the invention contains the two spinels as individual spinels and that they do not form a mixed spinel.
  • the presence of the two substances next to one another can be proven in a known manner by means of an X-ray fine structure analysis.
  • the active layer preferably has the two spinels in a weight ratio of Fe 3 0 4 to Co 3 0 4 of 40:60 to 70:30.
  • the active layer can be on an electrically conductive carrier, e.g. B. a valve metal, graphite, magnetite.
  • an electrically conductive carrier e.g. B. a valve metal, graphite, magnetite.
  • H the entire thickness of the electrode consists of the active layer.
  • the electrodes according to the invention are produced under conditions such that mixed spinel formation cannot take place, special conditions being observed since C 03 0 4 tends to be slightly divalent in cobalt oxide and conversely Fe 3 0 4 has a tendency to be slightly trivalent Iron oxide to form a cobalt-iron mixing spinel.
  • a suitable method to achieve this goal is the plasma spraying process.
  • the two powdered spinels are mixed thoroughly before processing. You should expediently have grain sizes of 10 to 200 microns, preferably ⁇ 125 microns.
  • the mixture is then placed in the reservoir of a plasma spray gun, moving towards it It is important to ensure that no segregation occurs both during metering and during transport.
  • a conventional plasma spraying system can be used for the coating, with either argon alone or argon in a mixture with up to 10% by volume hydrogen being considered as carrier gas. It is also essential that the plasma spraying system is operated in a low energy range, ie that values of 30 kW are not exceeded, with a minimum amount of 6 kW being adhered to for design reasons.
  • the body to be coated should be degreased in a known manner beforehand and then the surface by sandblasting, pickling and the like. be prepared.
  • the distance between the plasma flame and the body to be coated should suitably be 7 to 12 cm.
  • the plasma flame is moved back and forth in front of the body to be coated until the spray layer has reached the desired thickness.
  • the active layer is effective even with a relatively small thickness of 20 to 30 ⁇ m, although of course much thicker layers are permissible, up to electrodes which consist exclusively of the electrochemically active material.
  • a powder of a valve metal can also be added to the spinel mixture to be sprayed.
  • other substances can also be added if special properties are desired and if these other substances do not impair the electrochemical activity of the spinel layer.
  • the electrodes according to the invention show a chlorine separation potential of 1395 mV at current densities of 0.15 kA / m 2 , based on the normal H 2 electrode, ie the overvoltage is only approx. 35 mV.
  • the electrodes are characterized by a low overvoltage, with the deposition potential at 1.5 kA / m 2 depending on the substrate between approximately 1450 and maximum are around 1600 mV.
  • the electrodes according to the invention are notable for good chemical and mechanical resistance, and even if graphite is used as the substrate, practically no erosion can be ascertained even with longer standing times.
  • the anodes produced in this way are subjected to a voltage test under the operating conditions of the chlor-alkali electrodes.
  • the following deposition potentials are measured (against H z normal electrode):
  • An active layer of Fe 3 0 4 to C 03 0 4 (weight ratio 70:30) is applied to a base body made of electrographite with the dimensions of the electrode area of 20 x 15 x 10 mm.
  • Argon serves as the carrier gas, the injection energy is 18 kW and the distance of the plasma flame from the electrographite base body is 9 cm.
  • a powder mixture of Fe 3 O 4 to CO 3 O 4 im is placed on an aluminum sheet of size 20 x 15 x 1.5 mm with the help of a plasma flame with argon as carrier gas with an injection energy of 17 kW, at a distance of 10 cm from the plasma flame / base body weight ratio of 66 2/3: 33 1/3, the 70 wt .-% of titanium powder was added sprayed on. After a layer thickness of 1.5 mm has been reached, the coating process is stopped, the sprayed-on layer is detached from the aluminum and the negative mold thus produced is measured as an electrode. The following separation potentials are determined:
  • a comparison of these deposition voltages measured at 1.5 kA / m 2 with the deposition voltages measured in Examples 1 to 4 in the electrodes according to the invention shows a difference of more than 250 mV.
  • This electrode also has a deposition potential increased by approximately 200 mV at 1.5 kA / m 2 compared to the electrodes according to the invention.
  • the anode is produced as described in Example 1, argon being used as the plasma gas at an injection energy of 32 kW.
  • the weight ratio Fe 3 0 4 to C 03 0 4 (grain size ⁇ 125 ⁇ m) is 70:30.
  • the deposition potential is determined under the same conditions as in Examples 1 to 4. The following values are determined:

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)
  • Coating By Spraying Or Casting (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (6)

1. Electrode dont au moins la couche extérieure, électrochimiquement active, contient des spinelles, caractérisée en ce que les spinelles sont constitués par un mélange des spinelles individuels du fer et du cobalt, avec cette condition que le rapport de poids du spinelle de fer au spinelle de cobalt se situe entre 30 : 70 et 90 : 10.
2. Electrode selon la revendication 1, caractérisée en ce que le rapport de poids du spinelle de fer au spinelle de cobalt se situe entre 40 : 60 et 70 : 30.
3. Procédé pour la fabrication des électrodes selon la revendication 1 ou 2, caractérisé en ce qu'on applique sur un support, au moyen du procédé de pulvérisation de plasma, un mélange pulvérulent homogène de spinelle de fer et de spinelle de cobalt, en utilisant l'argon comme gaz de plasma et en appliquant une énergie de pulvérisation de 6 à 30 kW.
4. Procédé selon la revendication 3, caractérisé en ce que le gaz de plasma contient jusqu'à 10% en volume d'hydrogène.
5. Procédé selon la revendication 3 ou 4, caractérisé en ce que la distance entre la flamme à plasma et le support est comprise entre 7 et 12 cm.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on détache le support après avoir appliqué la couche de spinelles.
EP81104207A 1980-06-28 1981-06-02 Electrode sans métaux nobles et son procédé de fabrication Expired EP0042984B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3024611 1980-06-28
DE19803024611 DE3024611A1 (de) 1980-06-28 1980-06-28 Edelmetallfreie elektrode

Publications (2)

Publication Number Publication Date
EP0042984A1 EP0042984A1 (fr) 1982-01-06
EP0042984B1 true EP0042984B1 (fr) 1983-08-17

Family

ID=6105944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81104207A Expired EP0042984B1 (fr) 1980-06-28 1981-06-02 Electrode sans métaux nobles et son procédé de fabrication

Country Status (4)

Country Link
US (1) US4411761A (fr)
EP (1) EP0042984B1 (fr)
JP (1) JPS5739184A (fr)
DE (2) DE3024611A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4546058A (en) * 1984-12-12 1985-10-08 Energy Research Corporation Nickel electrode for alkaline batteries
US5356674A (en) * 1989-05-04 1994-10-18 Deutsche Forschungsanstalt Fuer Luft-Raumfahrt E.V. Process for applying ceramic coatings using a plasma jet carrying a free form non-metallic element
US7247229B2 (en) * 1999-06-28 2007-07-24 Eltech Systems Corporation Coatings for the inhibition of undesirable oxidation in an electrochemical cell
US7235161B2 (en) * 2003-11-19 2007-06-26 Alcoa Inc. Stable anodes including iron oxide and use of such anodes in metal production cells
TWI433964B (zh) 2010-10-08 2014-04-11 Water Star Inc 複數層之混合金屬氧化物電極及其製法
NO2751376T3 (fr) 2014-02-13 2018-03-24
DE102015010083A1 (de) 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox-Flow-Zelle zur Speicherung elektrischer Energie und deren Verwendung
DE102015014828A1 (de) 2015-11-18 2017-05-18 Friedrich-Schiller-Universität Jena Hybrid-Flow-Zelle zur Speicherung elektrischer Energie und deren Verwendung
US11668017B2 (en) 2018-07-30 2023-06-06 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3706644A (en) * 1970-07-31 1972-12-19 Ppg Industries Inc Method of regenerating spinel surfaced electrodes
US3711397A (en) * 1970-11-02 1973-01-16 Ppg Industries Inc Electrode and process for making same
DD98838A1 (fr) 1972-01-06 1973-07-12
GB1433805A (en) 1972-04-29 1976-04-28 Tdk Electronics Co Ltd Methods of electrolysis using complex iron oxide electrodes
IT978528B (it) * 1973-01-26 1974-09-20 Oronzio De Nora Impianti Elettrodi metallici e procedimen to per la loro attivazione
US3977958A (en) * 1973-12-17 1976-08-31 The Dow Chemical Company Insoluble electrode for electrolysis
US4169028A (en) * 1974-10-23 1979-09-25 Tdk Electronics Co., Ltd. Cathodic protection
JPS5541815Y2 (fr) * 1975-02-18 1980-09-30
US4024044A (en) * 1975-09-15 1977-05-17 Diamond Shamrock Corporation Electrolysis cathodes bearing a melt-sprayed and leached nickel or cobalt coating
DE2652293C2 (de) * 1976-11-17 1978-09-14 Uranit Uran-Isotopentrennungs- Gesellschaft Mbh, 5170 Juelich Verfahren zur Bildung einer korrosionsverhütenden, oxidischen Schutzschicht auf Stählen, insbesondere Maragingstählen
US4142005A (en) * 1976-02-27 1979-02-27 The Dow Chemical Company Process for preparing an electrode for electrolytic cell having a coating of a single metal spinel, Co3 O4
US4061549A (en) * 1976-07-02 1977-12-06 The Dow Chemical Company Electrolytic cell anode structures containing cobalt spinels
IL50217A (en) * 1976-08-06 1980-01-31 Israel State Electrocatalytically acitve spinel type mixed oxides
FR2434213A1 (fr) * 1978-08-24 1980-03-21 Solvay Procede pour la production electrolytique d'hydrogene en milieu alcalin

Also Published As

Publication number Publication date
JPS5739184A (en) 1982-03-04
EP0042984A1 (fr) 1982-01-06
DE3160766D1 (en) 1983-09-22
US4411761A (en) 1983-10-25
DE3024611A1 (de) 1982-01-28

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