EP0126490B1 - 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
EP0126490B1
EP0126490B1 EP84105869A EP84105869A EP0126490B1 EP 0126490 B1 EP0126490 B1 EP 0126490B1 EP 84105869 A EP84105869 A EP 84105869A EP 84105869 A EP84105869 A EP 84105869A EP 0126490 B1 EP0126490 B1 EP 0126490B1
Authority
EP
European Patent Office
Prior art keywords
titanium
nickel
oxide
diaphragm
mass
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
EP84105869A
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German (de)
English (en)
Other versions
EP0126490A1 (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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    • 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.
  • 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 that are usually used. These low temperatures are both thermodynamically and kinetically disadvantageous: This means that an unnecessarily high electrolysis voltage is required, and the entire process appears uneconomical for energy reasons.
  • Potassium silicate was added to the KOH electrolyte to reduce asbestos solubility in KOH (R.L. Vic et al in Hydrogen Energy Progress IV, 4th WHE Conference, June 13-17, 1982, California, pp. 129-140). It is clear that this measure cannot be considered as finally satisfactory.
  • 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 caused 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.
  • the diaphragms obtained using the simplified manufacturing process have since been used repeatedly in a wide variety of electrolysis tests and have proven themselves very well. Their long-term stability in alkaline water electrolysis was checked, the longest test to date lasting over 8000 hours (at 120 ° C.). Even after this time, the diaphragms were still intact. Thermodynamic considerations suggest, however, that these diaphragms can be reduced to metallic nickel after a certain sufficiently long time on the cathodic side either by the cathode itself or by the hydrogen formed. This thermodynamic effect is only opposed by a kinetic inhibition, which has to subside after a previously unknown time. This may be sufficient for the purposes of water electrolysis, but there is still a degree of uncertainty.
  • a diaphragm manufactured according to DE-OS 30 31 064 was exposed to a hydrogen atmosphere at 200 ° C. A gradual reduction of the Ni0 to Ni was observed, which increased suddenly after 1500 hours, so that after 2000 hours the total NiO was completely reduced.
  • Such a reductive attack Hydrogen are subject to ceramic diaphragms made of thermodynamically stable oxide compounds, such as. B. Zr0 2 , SaTi0 3 , K 2 Ti s 0 13 etc. ( see above) not, but the production of such diaphragms is associated with the disadvantages mentioned above, in particular very high production temperatures, and they are in 10 N KOH increased temperature attacked with time.
  • the invention is therefore based on the object of improving the reduction stability of the nickel oxide diaphragms under the conditions of alkaline water electrolysis.
  • the nickel oxide-based diaphragm according to the invention developed for this purpose is characterized by a titanium oxide content in the nickel oxide mass corresponding to 0.5 to 10% by weight of Ti based on the total oxide mass of Ti0 2 and NiO.
  • the titanium oxide content of the porous oxide mass preferably corresponds to 1 to 5% by weight of Ti, in particular 2.5% by weight of Ti, in each case based on the sum of Ti0 2 and NiO, and the diaphragm expediently has a framework-forming lattice made of anoxidized nickel.
  • the reduction stability of the NiO diaphragms was exceptionally increased if the nickel powder in the manufacture of the diaphragm according to the method of claim 5 TiO in amounts of 1 to 20% by weight (based on the sum of metallic nickel and Titanium dioxide) was added (which corresponds to an addition of 0.6 to 13.0% by weight of titanium, based on the sum of titanium and nickel).
  • 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.
  • a ceramic diaphragm based on NiO was produced according to DE-OS 30 31 064 with the addition of Ti0 2 . This manufacture comprises the individual steps indicated in FIG. 3:
  • 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.
  • z. B. a diaphragm made of pure NiO in 2000 hours. 7% of the oxygen and even a diaphragm stabilized with Al 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 is after 2000 hours in 10 N KOH at 120 ° C only 0.3%.
  • a pure NiO diaphragm loses 0.8%, a BaTi0 3 diaphragm 2% and a diaphragm mixed with 5% AI 2 0 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 were 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)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Saccharide Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Magnetic Ceramics (AREA)

Claims (5)

1. Diaphragme à base d'oxyde de nickel pour l'électrolyse alcaline de l'eau, caractérisé par une teneur en oxyde de titane dans la composition à base d'oxyde de nickel correspondant à 0,5 à 10 % en poids de Ti rapportée à la masse totale d'oxyde de Ti02 et de NiO.
2. Diaphragme suivant la revendication 1, caractérisé par une teneur en oxyde de titane de la composition à base de l'oxyde de nickel correspondant à 1 à 5 % en poids de Ti rapportée à la masse totale d'oxyde de Ti02 et de NiO.
3. Diaphragme suivant la revendication 2, caractérisé par une teneur en oxyde de titane de la composition à base d'oxyde de nickel correspondant à 2,5 % en poids de Ti rapportée à la masse totale d'oxyde de Ti02 et de NiO.
4. Diaphragme suivant l'une des revendications précédentes, caractérisé par une grille support en nickel ayant subi un commencement d'oxydation.
5. Procédé de fabrication d'un diaphragme suivant l'une des revendications précédentes, dans lequel on soumet une couche de poudre de nickel densifiée par pression et se trouvant sur un support, notamment sur une grille en nickel, à un traitement oxydant de frittage, à une température élevée, jusqu'à transformation de la poudre de nickel en une composition poreuse à base d'oxyde de nickel, caractérisé en ce que l'on ajoute à la masse de poudre de nickel à fritter de 0,6 à 13 % en poids de titane (rapporté à la somme du titane et du nickel), sous la forme de titane métallique, d'oxyde de titane ou d'un composé du titane, en le répartissant d'une manière aussi uniforme que possible, ou on imprègne le diaphragme à base d'oxyde de nickel obtenu après le traitement oxydant de frittage d'une quantité d'un composé de titane correspondant à la teneur en titane souhaitée et on le soumet à un traitement final de calcination pour transformer le titane en Ti02, de manière à obtenir un diaphragme ayant une teneur en titane de 0,5 à 10 % en poids de Ti rapportée à la composition totale d'oxyde de Ti02 et de NiO.
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 EP0126490A1 (fr) 1984-11-28
EP0126490B1 true 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)

Families Citing this family (9)

* 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
DE3813743A1 (de) * 1988-04-23 1989-11-02 Metallgesellschaft Ag Verfahren und vorrichtung zur herstellung von diaphragmen
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
DE102019123858A1 (de) 2019-09-05 2021-03-11 Thyssenkrupp Uhde Chlorine Engineers Gmbh Kreuzflusswasserelektrolyse

Family Cites Families (8)

* 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
GB1503915A (en) * 1974-05-24 1978-03-15 Ici Ltd Electrolytic process
IT1115372B (it) * 1977-07-15 1986-02-03 Oronzio De Nora Impianti Membrane ceramiche a due fasi per celle elettrolitiche
DE2927566C2 (de) * 1979-07-07 1986-08-21 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma für alkalische Elektrolyse, Verfahren zur Herstellung desselben und dessen Verwendung
US4394224A (en) * 1980-04-24 1983-07-19 British Aerospace Public Limited Company Treatment of titanium prior to bonding
DE3031064C2 (de) * 1980-08-16 1986-09-04 Kernforschungsanlage Jülich GmbH, 5170 Jülich Poröses Oxiddiaphragma für alkalische Elektrolysen und dessen Verwendung
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

Also Published As

Publication number Publication date
US4559124A (en) 1985-12-17
DE3468129D1 (en) 1988-01-28
JPS59229489A (ja) 1984-12-22
NO161628B (no) 1989-05-29
NO842048L (no) 1984-11-26
EP0126490A1 (fr) 1984-11-28
ZA843921B (en) 1986-01-29
CA1254857A (fr) 1989-05-30
BR8402480A (pt) 1985-04-02
ATE31432T1 (de) 1988-01-15
DE3318758C2 (de) 1985-06-13
NO161628C (no) 1989-09-06
DE3318758A1 (de) 1984-11-29

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