EP0126490A1 - Diaphragme à base d'oxyde de nickel et procédé pour sa fabrication - Google Patents

Diaphragme à base d'oxyde de nickel et procédé pour sa fabrication Download PDF

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Publication number
EP0126490A1
EP0126490A1 EP84105869A EP84105869A EP0126490A1 EP 0126490 A1 EP0126490 A1 EP 0126490A1 EP 84105869 A EP84105869 A EP 84105869A EP 84105869 A EP84105869 A EP 84105869A EP 0126490 A1 EP0126490 A1 EP 0126490A1
Authority
EP
European Patent Office
Prior art keywords
titanium
nickel
oxide
diaphragm
weight
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
EP84105869A
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German (de)
English (en)
Other versions
EP0126490B1 (fr
Inventor
Peter Dr. Malinowski
Jiri Dr. Divisek
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich GmbH
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 Forschungszentrum Juelich GmbH, Kernforschungsanlage Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Priority to AT84105869T priority Critical patent/ATE31432T1/de
Publication of EP0126490A1 publication Critical patent/EP0126490A1/fr
Application granted granted Critical
Publication of EP0126490B1 publication Critical patent/EP0126490B1/fr
Expired 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material

Definitions

  • the invention relates to a diaphragm based on nickel oxide for alkaline water electrolysis and to a method for producing the same.
  • the alkaline water electrolysis generally takes place at relatively low temperatures (below 90 ° C.), which must be chosen in hot KOH because of the low chemical resistance of the asbestos diaphragms usually used. These low temperatures are both thermodynamically and kinetically disadvantageous an unnecessarily high electrolysis voltage is required, and the whole process appears uneconomical for energy reasons.
  • Potassium silicate was added to the KOH electrolyte to reduce asbestos solubility in KOH (RLVic et al in Hydrogen Energy Progress IV, 4th WHE Conference, June 13-17, 1982, California, pp. 129-140). It is clear that this measure is not ultimately satisfactory can be viewed.
  • Porous metallic diaphragms made of sintered nickel have also been proposed (P. Perroud, G. Terrier: "Hydrogen Energy System", Proc. 2nd WHE Conference, Zurich 1978, p. 241). These have a very low electrical resistance and are also mechanically stable and inexpensive.
  • the major disadvantage, however, is that this diaphragm, like the electrodes, is also electron-conductive and there is too great a risk of short-circuiting in a compact design.
  • porous nickel oxide diaphragms have been developed by the applicant (DE-OSes 29 27 566 and 30 31 064), which are produced by oxidation of sintered metal at elevated temperature (DE-OS 29 27 566) or more simply by oxidizing firing a carrier pressed nickel powder layer can be obtained (DE-OS 30 31 064).
  • These NiO diaphragms have excellent properties as separators for alkaline water electrolysis.
  • Such a reductive attack by hydrogen is not subject to ceramic diaphragms made of thermodynamically stable oxide compounds, such as Zr0 2 , BaTiO 3 , K 2 Ti 6 0 13 etc. (see above), but the manufacture of such diaphragms has the disadvantages mentioned above, in particular very high manufacturing temperatures, and they are attacked in 10 N KOH at elevated temperature with time.
  • the "in situ" NiO diaphragm according to DE-OS 30 31 064 is alkali-resistant and its manufacture not only starts from a cheap starting material, but also offers the decisive technological advantage that the exothermic reaction 2 Ni + 0 2 ⁇ 2 Ni0 only expires when the diaphragm is manufactured. This results in a considerable temperature increase locally and the external manufacturing temperature can only be 1000 ° C., which is advantageous. Due to the manufacturing process (oxidizing sintering), there is also no need to maintain an inert atmosphere, which is also a significant relief.
  • the invention is therefore based on the object, the reduction stability of the nickel oxide diaphragms to improve under the conditions of alkaline water electrolysis.
  • the nickel oxide-based diaphragm according to the invention developed for this purpose is characterized by a content of 0.5 to 10% by weight of titanium (in oxidized form; based on the oxide mass).
  • NiO 2 was added to the nickel powder in the preparation of the diaphragm in amounts of 1 to 20% by weight (based on the sum of metallic nickel and titanium dioxide) .
  • the grain size of the admixed powder should be approximately comparable or smaller than that of the nickel powder in order to ensure a uniform distribution of the titanium over the oxide mass.
  • titanium powder can also be admixed to the nickel powder mass in the manufacture of the diaphragm, or else as a compound, which transform into titanium oxide during the oxidizing sintering treatment. If necessary, a nickel oxide diaphragm which has already been produced can also be impregnated with a titanium compound which is converted into oxidized form by afterburning.
  • the assembly was sintered in air at 1050 ° C for about 20 minutes.
  • the chemical stability was, however, greatly improved, as can be seen from FIGS. 1 and 2:
  • the decrease in oxygen in a pure hydrogen atmosphere at 140 to 170 ° C. can no longer be measured during the first 2000 h, which indicates an enormously increased reduction stability.
  • a diaphragm made of pure NiO loses 7% of the oxygen in 2000 hours and even a diaphragm stabilized with A1 2 0 3 additive still loses about 1.5% of the oxygen content in the same time.
  • the already excellent chemical stability in hot KOH is further increased: As FIG. 2 shows, the total weight loss after 2000 hours in 10 N KOH at 120 ° C. is only 0.3%.
  • a pure NiO diaphragm loses 0.8%, a BaTi0 3 diaphragm 2% and a diaphragm mixed with 5% Al 2 O 3 8% of the total weight, which is attributable to A1 2 0 3 .
  • Example 1 Before the slurrying step, 8% by weight of metallic Ti (based on the powder mixture) of approximately the same grain size as Ni was added to the Ni powder. The subsequent production steps were the same as in Example 1. After the oxidizing sintering, both nickel and titanium were present in oxidic form. This diaphragm had the same properties as that of Example 1 with respect to the reducibility in H 2 atmosphere.
  • Example 1 50% TiO 2 was added to the Ni powder before slurrying. Otherwise, the preparation corresponded to that of Example 1.
  • the diaphragm produced in this way showed a weight loss of 10% after only 500 hours in 10 N KOH at 120 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Saccharide Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Magnetic Ceramics (AREA)
EP84105869A 1983-05-24 1984-05-23 Diaphragme à base d'oxyde de nickel et procédé pour sa fabrication Expired EP0126490B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84105869T ATE31432T1 (de) 1983-05-24 1984-05-23 Diaphragma auf nickeloxidbasis und verfahren zur herstellung desselben.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3318758 1983-05-24
DE3318758A DE3318758C2 (de) 1983-05-24 1983-05-24 Diaphragma auf Nickeloxidbasis und Verfahren zur Herstellung desselben

Publications (2)

Publication Number Publication Date
EP0126490A1 true EP0126490A1 (fr) 1984-11-28
EP0126490B1 EP0126490B1 (fr) 1987-12-16

Family

ID=6199718

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84105869A Expired EP0126490B1 (fr) 1983-05-24 1984-05-23 Diaphragme à base d'oxyde de nickel et procédé pour sa fabrication

Country Status (9)

Country Link
US (1) US4559124A (fr)
EP (1) EP0126490B1 (fr)
JP (1) JPS59229489A (fr)
AT (1) ATE31432T1 (fr)
BR (1) BR8402480A (fr)
CA (1) CA1254857A (fr)
DE (2) DE3318758C2 (fr)
NO (1) NO161628C (fr)
ZA (1) ZA843921B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339728A1 (fr) * 1988-04-23 1989-11-02 Metallgesellschaft Ag Procédé et dispositif de fabrication de diaphragmes
WO2021043578A1 (fr) 2019-09-05 2021-03-11 Thyssenkrupp Uhde Chlorine Engineers Gmbh Électrolyse de l'eau à flux croisé

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3424203A1 (de) * 1984-06-30 1986-01-16 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma fuer alkalische elektrolysen und verfahren zur herstellung desselben
DE8517106U1 (de) * 1985-06-12 1985-08-01 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma für alkalische Elektrolysen
US7329332B2 (en) * 2004-08-25 2008-02-12 Ppg Industries Ohio, Inc. Diaphragm for electrolytic cell
US7618527B2 (en) * 2005-08-31 2009-11-17 Ppg Industries Ohio, Inc. Method of operating a diaphragm electrolytic cell
US8460536B2 (en) * 2006-01-19 2013-06-11 Eagle Controlled 2 Ohio Spinco, Inc. Diaphragm for electrolytic cell
CN102400139A (zh) * 2010-09-15 2012-04-04 鸿富锦精密工业（深圳）有限公司 镀膜件及其制作方法
ITMI20131804A1 (it) * 2013-10-30 2015-05-01 Intecna S R L Processo e apparato per la produzione in continuo di ferrati alcalini, in particolare di ferrato di sodio

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT343146B (de) * 1974-05-24 1978-05-10 Ici Ltd Elektrochemische diaphragmazelle und verfahren zu ihrer herstellung
DE2927566A1 (de) * 1979-07-07 1981-01-08 Kernforschungsanlage Juelich Diaphragma fuer alkalische wasserelektrolysen und verfahren zur herstellung desselben sowie dessen verwendung
DE3031064A1 (de) * 1980-08-16 1982-03-04 Kernforschungsanlage Jülich GmbH, 5170 Jülich Poroeses oxiddiaphragma fuer alkalische elektrolysen, dessen herstellung und verwendung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1002909B (it) * 1973-02-17 1976-05-20 Deutsche Automobilgesellsch Membrana per la separazione di idro geno da miscele di gas contenenti idrogeno
IT1115372B (it) * 1977-07-15 1986-02-03 Oronzio De Nora Impianti Membrane ceramiche a due fasi per celle elettrolitiche
US4394224A (en) * 1980-04-24 1983-07-19 British Aerospace Public Limited Company Treatment of titanium prior to bonding
DE3108255C2 (de) * 1981-03-05 1986-05-07 Kernforschungsanlage Jülich GmbH, 5170 Jülich Baueinheit für Elektrolysezellen für die alkalische Wasserelektrolyse und Verfahren zur Herstellung derselben
DE3109183C2 (de) * 1981-03-11 1983-05-11 BOMIN Bochumer Mineralöl GmbH & Co, 4630 Bochum Aus Nickelpulver heißgepreßte hochporöse Elektrode für alkalische Wasserelektrolyseure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT343146B (de) * 1974-05-24 1978-05-10 Ici Ltd Elektrochemische diaphragmazelle und verfahren zu ihrer herstellung
DE2927566A1 (de) * 1979-07-07 1981-01-08 Kernforschungsanlage Juelich Diaphragma fuer alkalische wasserelektrolysen und verfahren zur herstellung desselben sowie dessen verwendung
DE3031064A1 (de) * 1980-08-16 1982-03-04 Kernforschungsanlage Jülich GmbH, 5170 Jülich Poroeses oxiddiaphragma fuer alkalische elektrolysen, dessen herstellung und verwendung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339728A1 (fr) * 1988-04-23 1989-11-02 Metallgesellschaft Ag Procédé et dispositif de fabrication de diaphragmes
DE3813743A1 (de) * 1988-04-23 1989-11-02 Metallgesellschaft Ag Verfahren und vorrichtung zur herstellung von diaphragmen
WO2021043578A1 (fr) 2019-09-05 2021-03-11 Thyssenkrupp Uhde Chlorine Engineers Gmbh Électrolyse de l'eau à flux croisé

Also Published As

Publication number Publication date
US4559124A (en) 1985-12-17
DE3318758A1 (de) 1984-11-29
EP0126490B1 (fr) 1987-12-16
ZA843921B (en) 1986-01-29
ATE31432T1 (de) 1988-01-15
NO842048L (no) 1984-11-26
NO161628B (no) 1989-05-29
DE3318758C2 (de) 1985-06-13
NO161628C (no) 1989-09-06
DE3468129D1 (en) 1988-01-28
CA1254857A (fr) 1989-05-30
BR8402480A (pt) 1985-04-02
JPS59229489A (ja) 1984-12-22

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