EP0059902B1 - Electrode en poudre de nickel à haute porosité pressée à chaud destinée aux cellules pour l'électrolyse alcaline de l'eau - Google Patents

Electrode en poudre de nickel à haute porosité pressée à chaud destinée aux cellules pour l'électrolyse alcaline de l'eau Download PDF

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Publication number
EP0059902B1
EP0059902B1 EP82101509A EP82101509A EP0059902B1 EP 0059902 B1 EP0059902 B1 EP 0059902B1 EP 82101509 A EP82101509 A EP 82101509A EP 82101509 A EP82101509 A EP 82101509A EP 0059902 B1 EP0059902 B1 EP 0059902B1
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EP
European Patent Office
Prior art keywords
electrode
nickel
nickel powder
solution
sintered
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
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EP82101509A
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German (de)
English (en)
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EP0059902A1 (fr
Inventor
Henning Prof. Dr. Ewe
Eduard W. Prof. Dr. Justi
Peter Dr. Brennecke
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.)
Schnapka Herbert Dr
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Schnapka Herbert Dr
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Publication date
Application filed by Schnapka Herbert Dr filed Critical Schnapka Herbert Dr
Priority to AT82101509T priority Critical patent/ATE14323T1/de
Publication of EP0059902A1 publication Critical patent/EP0059902A1/fr
Application granted granted Critical
Publication of EP0059902B1 publication Critical patent/EP0059902B1/fr
Expired legal-status Critical Current

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    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound

Definitions

  • the invention relates to a highly porous electrode hot-pressed from nickel powder for alkaline water electrolysers, in particular an electrode which is covered on its inner and outer surface with a 0.0025-0.1 ⁇ m thick oxide layer, and to processes for its production.
  • a high corrosion resistance in strongly alkaline electrolytes is achieved due to the layer consisting almost entirely of nickel oxide.
  • the nickel support structure is protected in particular by the nickel oxide layer against oxidation to form voluminous oxides or hydroxides. This significantly extends the service life of the electrode.
  • the O 2 deposition is catalyzed by this nickel oxide layer (DE-OS 29 03 407).
  • the object of the invention is to provide an electrode of the type mentioned at the outset, which has an improved (“doctoralized •) catalytic effect and in which the H 2 and O 2 deposition take place even at high current densities with low polarizations.
  • the long-term stability should be increased by reducing the oxidation of the nickel of the electrode body, since the oxidation continues slowly even when the surface is essentially made of nickel oxide.
  • the surface layer consists of a nickel-titanium mixed oxide.
  • a method for producing the electrode is characterized in that the electrode is hot pressed or sintered from a nickel powder at 300-500 ° C, which is alloyed with 1-15 wt .-%, preferably about 2 wt .-% titanium and the surface layer is generated from a nickel-titanium mixed oxide by oxidation of the electrode surface.
  • a NiTi x (OH) 2 layer can be applied chemically, preferably electrochemically, to the surface of the electrode and the nickel-titanium mixed oxide layer can be produced from it by thermal decomposition at temperatures above 150 ° C .
  • Another method for producing the electrode is characterized in that before or after the hot pressing or sintering, titanium is applied to the nickel surface in the form of an aqueous titanyl sulfate solution (TiO (SO 4 ) solution), which is then dried, the solution being used for the solution such an amount and / or concentration is selected that after hot pressing or sintering the highly porous electrode at 300-500 ° C or after annealing the hot-pressed or sintered highly porous electrode at 150-500 ° C in air or in a 0 2 atmosphere Titanium content in the surface surface nickel-titanium mixed oxide layer is about 2-3 wt .-%.
  • the solution can be mixed with the nickel powder before pressing.
  • the electrode pre-pressed from nickel powder at room temperature is impregnated with the solution and then hot pressed or sintered.
  • the electrode, hot-pressed or sintered from nickel powder can be soaked and tempered with the solution.
  • the nickel-titanium mixed oxide layer covering the inner and outer surface of the electrode can be achieved by tempering the nickel electrodes in air or in a 0 2 atmosphere.
  • the temperature should be at least 150 ° C and at most 500 ° C.
  • the amount of 0 2 required for the oxidation can also be provided by using nickel powder for the production of the electrode which has an air and / or oxygen loading sufficient for the nickel-titanium mixed oxide layer when the electrode is hot pressed or sintered to train, which are carried out at temperatures between 300 and 500 ° C.
  • the catalytically and stabilizing mixed oxide layer is already achieved by hot pressing or sintering in air, thus saving a subsequent work step.
  • the annealing time should be a minimum of 0.5 h.
  • the tempering time can be extended up to 20 h.
  • the catalytically and stabilizing nickel-titanium mixed oxide layer must have a minimum thickness in the range of 0.002 5-0.1 wm, which in any case ensures a tight, closed covering of the nickel supporting structure of the electrode.
  • the electrode according to the invention resists the strongest known oxidant even in long-term operation. namely oxygen in statu nascendi and is therefore superior to platinum, which cannot be used for electrodes for water electrolysis for economic reasons.
  • electrodes according to the invention are particularly well suited for use in newer electrolyzers. They can be used both as anodes and as cathodes.
  • the impregnated carbonyl nickel powder After the impregnated carbonyl nickel powder has dried, it is mixed with 4 g of salt filler (Na 2 C0 3 ; grain size 50-75 ⁇ m) to achieve the necessary macro- or volume porosity, smoothly coated into a die of 40 mm inside diameter, with 0.32 to / cm 2 cold pressed and after heating in air at 400 ° C with 0.8 to / cm 2 hot pressed to a disc-shaped electrode. After the pressing process, the added salt filler is dissolved out in hot distilled water.
  • salt filler Na 2 C0 3 ; grain size 50-75 ⁇ m
  • carbonyl nickel powder carbonyl nickel T 255; grain fraction ⁇ 50 ⁇ m
  • 4 g salt filler Na 2 C0 3 ; grain fraction 50-75 ⁇ m
  • the added salt filler is dissolved out in hot water and the electrode is dried.
  • the porous Ni electrode is mixed with an aqueous titanyl sulfate solution containing 0.24 g of Ti, dried and annealed at 200 ° C. for 4 hours to form the Ni-Ti mixed oxides.
  • An electrode to be used as an anode is produced as in the first exemplary embodiment, but the hot pressing is carried out in a gas-tight steel mold without any appreciable air access. After the salt filler has been removed, the electrode is dried and heated in air at 200 ° C. for 10 hours. By hot-pressing the electrode in the absence of air, a stronger welding of the Ni grains is achieved.

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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)
  • Powder Metallurgy (AREA)
  • Inert Electrodes (AREA)

Claims (7)

1. Electrode très poreuse formée par compression à chaud de poudre de nickel, pour électrolyseurs d'eau alcalins, qui est couverte sur ses surfaces intérieure et extérieure d'une couche d'oxyde de 0,002 5 à 0,1 µm d'épaisseur, caractérisée par le fait que cette couche superficielle est formée d'un oxyde mixte nickel-titane.
2. Procédé de fabrication d'une électrode selon la revendication 1, caractérisé par le fait que l'on comprime à chaud ou que l'on fritte l'électrode, à 300 à 500 °C, en partant d'une poudre de nickel qui est alliée de 1 à 15% en poids, de préférence d'environ 2% en poids de titane et que l'on forme la couche superficielle en oxyde mixte nickel-titane par oxydation de la surface de l'électrode.
3. Procédé de fabrication d'une électrode selon la revendication 2, caractérisé par le fait que pour engendrer la couche d'oxyde mixte nickel-titane, on applique chimiquement, de préférence électrochimiquement une couche de NiT!x(OH)2 sur la surface de l'électrode et qu'en partant de cette couche, par décomposition thermique à des températures supérieures à 150 °C, on engendre la couche d'oxyde mixte nickel-titane.
4. Procédé de fabrication d'une électrode selon la revendication 1, caractérisé par le fait qu'avant ou après la compression à chaud ou le frittage, on applique du titane sur la surface de nickel sous la forme d'une solution aqueuse de sulfate de titanyle (solution de TiO(S04)) que l'on sèche ensuite, en choisissant pour la solution une quantité et/ou une concentration telles qu'après la compression à chaud ou le frittage de l'électrode très poreuse à 300 à 500 °C, ou après recuit de l'électrode très poreuse comprimée à chaud ou frittée, à 150 à 500 °C à l'air ou dans une atmosphère de O2, la proportion de titane dans la couche superficielle d'oxyde mixte nickel-titane formée soit d'environ 2 à 3 % en poids.
5. Procédé selon la revendication 4, caractérisé par le fait que l'on mélange la solution à la poudre de nickel avant la compression à chaud ou le frittage.
6. Procédé selon la revendication 4, caractérisé par le fait que l'on imprègne de la solution l'électrode précomprimée à la température et qu'alors on la comprime à chaud ou on la fritte.
7. Procédé selon la revendication 4, caractérisé par le fait que l'on imprègne de la solution l'électrode comprimée à chaud ou frittée en partant de poudre de nickel et qu'on la recuit.
EP82101509A 1981-03-11 1982-02-27 Electrode en poudre de nickel à haute porosité pressée à chaud destinée aux cellules pour l'électrolyse alcaline de l'eau Expired EP0059902B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82101509T ATE14323T1 (de) 1981-03-11 1982-02-27 Aus nickelpulver heissgepresste hochporoese elektrode fuer alkalische wasserelektrolyseure.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3109183A DE3109183C2 (de) 1981-03-11 1981-03-11 Aus Nickelpulver heißgepreßte hochporöse Elektrode für alkalische Wasserelektrolyseure
DE3109183 1981-03-11

Publications (2)

Publication Number Publication Date
EP0059902A1 EP0059902A1 (fr) 1982-09-15
EP0059902B1 true EP0059902B1 (fr) 1985-07-17

Family

ID=6126884

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82101509A Expired EP0059902B1 (fr) 1981-03-11 1982-02-27 Electrode en poudre de nickel à haute porosité pressée à chaud destinée aux cellules pour l'électrolyse alcaline de l'eau

Country Status (13)

Country Link
US (1) US4447302A (fr)
EP (1) EP0059902B1 (fr)
JP (1) JPS57161078A (fr)
AR (1) AR228643A1 (fr)
AT (1) ATE14323T1 (fr)
AU (1) AU547889B2 (fr)
BR (1) BR8201247A (fr)
CA (1) CA1191815A (fr)
CS (1) CS241504B2 (fr)
DD (1) DD201701A5 (fr)
DE (1) DE3109183C2 (fr)
ES (1) ES8303547A1 (fr)
HU (1) HU188056B (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3318758C2 (de) * 1983-05-24 1985-06-13 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma auf Nickeloxidbasis und Verfahren zur Herstellung desselben
US4648945A (en) * 1985-03-21 1987-03-10 Westinghouse Electric Corp. Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell
JPS6286187A (ja) * 1985-10-09 1987-04-20 Asahi Chem Ind Co Ltd 水素発生用の電極
EP1240680A2 (fr) * 1999-11-18 2002-09-18 Proton Energy Systems, Inc. Cellule electrochimique a pression differentielle elevee
DE10007480A1 (de) * 2000-02-18 2001-08-23 Provera Ges Fuer Projektierung Bipolare Elektrode mit Halbleiterbeschichtung und damit verbundenes Verfahren zur elektrolytischen Wasserspaltung
US20050250003A1 (en) * 2002-08-09 2005-11-10 Proton Energy Systems, Inc. Electrochemical cell support structure
KR100930790B1 (ko) * 2009-02-18 2009-12-09 황부성 수소산소 발생용 전극판 및 그를 제조하기 위한 제조방법
US20150287980A1 (en) * 2012-10-12 2015-10-08 Zhongwei Chen Method of producing porous electrodes for batteries and fuel cells

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE290407C (fr) *
DE1269213B (de) * 1963-09-27 1968-05-30 Asea Ab Verfahren zur Herstellung von poroesen Brennstoffelektroden fuer Brennstoffelemente
US3505118A (en) * 1966-12-05 1970-04-07 Du Pont Fuel cell and process for producing electric current using titanium dioxide catalyst
US3959014A (en) * 1971-12-14 1976-05-25 Varta Batterie Aktiengesellschaft Method to produce a protective oxide on the surface of positive nickel electrodes for galvanic cells
FR2362945A1 (fr) * 1976-08-24 1978-03-24 Comp Generale Electricite Electrolyseur pour solutions basiques
DE2903407C2 (de) * 1979-01-30 1983-12-15 BOMIN Bochumer Mineralöl GmbH & Co, 4630 Bochum Verwendung einer aus Nickelpulver heißgepreßten oder gesinterten porösen Elektrode
US4289650A (en) * 1979-03-29 1981-09-15 Olin Corporation Cathode for chlor-alkali cells

Also Published As

Publication number Publication date
JPS57161078A (en) 1982-10-04
DD201701A5 (de) 1983-08-03
ES510290A0 (es) 1983-02-01
EP0059902A1 (fr) 1982-09-15
ES8303547A1 (es) 1983-02-01
US4447302A (en) 1984-05-08
AU547889B2 (en) 1985-11-07
DE3109183C2 (de) 1983-05-11
ATE14323T1 (de) 1985-08-15
CA1191815A (fr) 1985-08-13
AR228643A1 (es) 1983-03-30
AU8079882A (en) 1982-09-16
DE3109183A1 (de) 1982-09-23
BR8201247A (pt) 1983-01-18
HU188056B (en) 1986-03-28
CS159882A2 (en) 1985-08-15
CS241504B2 (en) 1986-03-13

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