EP0059902A1 - 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
EP0059902A1
EP0059902A1 EP82101509A EP82101509A EP0059902A1 EP 0059902 A1 EP0059902 A1 EP 0059902A1 EP 82101509 A EP82101509 A EP 82101509A EP 82101509 A EP82101509 A EP 82101509A EP 0059902 A1 EP0059902 A1 EP 0059902A1
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EP
European Patent Office
Prior art keywords
electrode
nickel powder
pressed
hot
titanium
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.)
Granted
Application number
EP82101509A
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German (de)
English (en)
Other versions
EP0059902B1 (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
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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 (10-100 molecular layer) layer with NiO.
  • the object of the invention is to provide an electrode of the type mentioned at the outset which has an improved ("doctorate”) 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 is to 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 NiO.
  • the surface layer consists of a Ni-Ti mixed oxide.
  • a nickel powder which is alloyed with 1-15% by weight of titanium can be used to produce such an electrode.
  • the total amount of titanium in the electrode should be about 2% by weight. If the surface of this electrode is oxidized, Ni-Ti mixed oxides are formed on the surface. The oxidation processes are described below.
  • Another method for producing the surface layer from a Ni-Ti mixed oxide provides that pure Ni powder is used as the starting material and the Ti catalyst additive is applied to the Ni surface in such an amount and / or concentration by means of a titanium salt solution that the The total proportion of titanium in the Ni-Ti mixed oxide layer is about 2 to 3% by weight. It is particularly expedient to apply the Ti catalyst additive in the form of an aqueous titanyl sulfate solution (TiO (SO 4 ) solution).
  • TiO (SO 4 ) solution aqueous titanyl sulfate solution
  • Such a solution can be used to impregnate the amount of Ni powder required to produce the Ni support structure.
  • the electrode is then cold-pressed from the impregnated and dried Ni powder, and the Ni-Ti mixed oxide layer is then formed during hot pressing or sintering.
  • Another possibility is to impregnate the electrode, which has been cold-pressed from pure Ni powder, with the titanyl sulfate solution.
  • the impregnated electrode is hot pressed and / or sintered after drying.
  • titanyl sulfate solution can also be added to the hot-pressed or sintered electrode by soaking. The electrode is then annealed or sintered again.
  • the Ti catalyst additive can also be applied with solutions of other titanium salts, the solvent need not be water.
  • the inner and outer surface of the Ni-Ti mixed oxide layer covering the electrode can be achieved by tempering the porous Ti-containing Ni 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 O 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 Ni-Ti mixed oxide layer when the electrode is hot pressed or sintered training that 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.
  • Ni-Ti mixed oxide layer can also be produced by other processes, for example by thermal decomposition at temperatures above 150 ° C. of a surface chemically or electrochemically applied Ni Ti x (OH) 2 layer.
  • the catalytically effective stabilizing and Ni-Ti mixed oxide layer should have a minimum ceiling 0.0025 to 0.1 microns (10 to 100 molecular layers) in order a density in any case, e- g to ensure closed coverage of the Ni supporting structure of the electrode.
  • the electrode according to the invention resists the strongest known oxidant, namely oxygen in statu nascendi, even in long-term operation, 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 electrolysers, such as the ELOFLUX water electrolysis cell. They can be used both as anodes and as cathodes.
  • the task of reducing the polarizations occurring in the H 2 and O 2 deposition and complicating the further oxidation of the nickel is achieved without the use of rare or expensive noble metals, such as platinum.
  • 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 with an inner diameter of 40 mm, 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
  • 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. The electrode is hot-pressed with the exclusion of air, which results in a stronger welding of the Ni grains.
  • NiO x For the nickel oxide, which is normally given as NiO, the formula NiO x is used in the foregoing, since nickel oxide occurs in variable compositions. Nickel oxide is a non-stoichiometric compound. For x, i.e. the number of oxygen atoms that combine with a nickel atom, values between 1 and 1.5 have been demonstrated. The existence of connections with x to 2 is assumed.

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)
  • Powder Metallurgy (AREA)
  • Inert Electrodes (AREA)
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 true EP0059902A1 (fr) 1982-09-15
EP0059902B1 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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10007480A1 (de) * 2000-02-18 2001-08-23 Provera Ges Fuer Projektierung Bipolare Elektrode mit Halbleiterbeschichtung und damit verbundenes Verfahren zur elektrolytischen Wasserspaltung

Families Citing this family (7)

* 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
JP2003515237A (ja) * 1999-11-18 2003-04-22 プロトン エネルギー システムズ，インク． 高差圧電気化学電池
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
WO2014056114A1 (fr) * 2012-10-12 2014-04-17 Zhongwei Chen Procédé de production d'électrodes poreuses pour batteries et piles à combustible

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505118A (en) * 1966-12-05 1970-04-07 Du Pont Fuel cell and process for producing electric current using titanium dioxide catalyst
DE2737041A1 (de) * 1976-08-24 1978-03-09 Comp Generale Electricite Elektrolysiergeraet fuer basische loesungen und verfahren zu seiner herstellung
DE2903407A1 (de) * 1979-01-30 1980-08-14 Justi Eduard W Prof Dr Phil Heissgepresste poroese elektrode und verfahren zu ihrer herstellung

Family Cites Families (4)

* 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
FR2163638A1 (fr) * 1971-12-14 1973-07-27 Siemens Ag
US4289650A (en) * 1979-03-29 1981-09-15 Olin Corporation Cathode for chlor-alkali cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505118A (en) * 1966-12-05 1970-04-07 Du Pont Fuel cell and process for producing electric current using titanium dioxide catalyst
DE2737041A1 (de) * 1976-08-24 1978-03-09 Comp Generale Electricite Elektrolysiergeraet fuer basische loesungen und verfahren zu seiner herstellung
DE2903407A1 (de) * 1979-01-30 1980-08-14 Justi Eduard W Prof Dr Phil Heissgepresste poroese elektrode und verfahren zu ihrer herstellung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10007480A1 (de) * 2000-02-18 2001-08-23 Provera Ges Fuer Projektierung Bipolare Elektrode mit Halbleiterbeschichtung und damit verbundenes Verfahren zur elektrolytischen Wasserspaltung

Also Published As

Publication number Publication date
ES510290A0 (es) 1983-02-01
HU188056B (en) 1986-03-28
ATE14323T1 (de) 1985-08-15
DD201701A5 (de) 1983-08-03
CS159882A2 (en) 1985-08-15
DE3109183C2 (de) 1983-05-11
JPS57161078A (en) 1982-10-04
AU8079882A (en) 1982-09-16
ES8303547A1 (es) 1983-02-01
BR8201247A (pt) 1983-01-18
DE3109183A1 (de) 1982-09-23
CS241504B2 (en) 1986-03-13
EP0059902B1 (fr) 1985-07-17
AU547889B2 (en) 1985-11-07
US4447302A (en) 1984-05-08
CA1191815A (fr) 1985-08-13
AR228643A1 (es) 1983-03-30

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