EP0170051A2 - Diaphragme pour électrolyses alcalines et son procédé de fabrication - Google Patents

Diaphragme pour électrolyses alcalines et son procédé de fabrication Download PDF

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Publication number
EP0170051A2
EP0170051A2 EP85107908A EP85107908A EP0170051A2 EP 0170051 A2 EP0170051 A2 EP 0170051A2 EP 85107908 A EP85107908 A EP 85107908A EP 85107908 A EP85107908 A EP 85107908A EP 0170051 A2 EP0170051 A2 EP 0170051A2
Authority
EP
European Patent Office
Prior art keywords
diaphragm
layer
fine
grains
coarser
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.)
Withdrawn
Application number
EP85107908A
Other languages
German (de)
English (en)
Other versions
EP0170051A3 (fr
Inventor
Jiri Dr. Divisek
Peter Dr. Malinowski
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
Publication of EP0170051A2 publication Critical patent/EP0170051A2/fr
Publication of EP0170051A3 publication Critical patent/EP0170051A3/fr
Withdrawn legal-status Critical Current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
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • 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
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • 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
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/24997—Of metal-containing material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y10T442/102—Woven scrim
    • Y10T442/109—Metal or metal-coated fiber-containing scrim
    • Y10T442/11—Including an additional free metal or alloy constituent
    • Y10T442/112—Particulate free metal or alloy constituent

Definitions

  • the invention relates to a diaphragm for alkaline electrolysis, in particular for alkaline water electrolysis, with a fine-pored, in particular ceramic layer, and to a method for producing the same.
  • the following description therefore largely refers to these special diaphragms.
  • Alkaline water electrolysis is generally carried out at temperatures below 90 ° C. These relatively low temperatures are necessary because of the low chemical resistance of the commercially used asbestos diaphragms in hot KOH. For reasons of stability, the diaphragms must also be chosen much thicker than would be required for the actual electrolysis. This in turn causes an undesirable high electrolysis voltage and makes the entire process, from an energy perspective, appear uneconomical.
  • the "sandwich construction" also has a disadvantage that does not occur with the usual energetically disadvantageous constructions: the diaphragm only remains functional if no deposits form on the electrodes, which can then propagate further into the diaphragm located in the immediate vicinity (zero distance). Of course, this presupposes that the entire cell system including its periphery must be so corrosion-resistant that practically no corrosion takes place. Corrosion products would, as a result of the electrode reactions, either deposit or deposit cathodically as metals or anodically as hydrated oxides and pass from the electrodes into the diaphragm and clog it or even lead to short circuits. In practice, however, it is very difficult or at least very expensive to maintain a corrosion-free state.
  • the energy-saving and thus economical reduction of the electrode spacing on the one hand is associated with the need for expensive systems, while the structurally cheaper solution working with a noticeable distance between the diaphragm electrodes is energetically disadvantageous.
  • a diaphragm of the type mentioned at the outset which is characterized by coarser grains which protrude from the surface and are distributed over the surface and which protrude from the surface on one or both sides of the diaphragm.
  • the diaphragm preferably comprises a framework for the fine-porous layer, which is formed in particular by an oxidized metal net, which also allows the handling of large, thin diaphragms.
  • the diaphragm according to the invention specifically comprises a fine-porous layer which is formed by oxidation of sintered metal or pressed metal powder based on nickel until a sufficiently electrically insulating layer is obtained, in particular on or on an oxidized metal mesh support, the coarser grains of oxidized metal protruding from the layer. or metal oxide.
  • the coarser grains protruding from the surface make it somewhat minimal Distance between the actual fine-pored diaphragm and an immediately applied electrolyte- and gas-permeable electrode made of perforated plate or the like. maintained so that the function of the diaphragm is maintained even over longer times even under conditions of the electrolysis cell that are not absolutely corrosion-free, although the distance between the electrode (adjustable via the grain size and the protruding part of the grains) from the fine-pored diaphragm layer is so small, that there are no significant energy losses.
  • the coarser grains preferably have a diameter of about 10 to 250 ⁇ m, in particular one of 50 to 150 ⁇ m, and they preferably protrude from the surface by about 50 to 70%. They are relatively thin (and usually indiscriminately) distributed over the surface, since the stability and thickness of the electrode generally prevent "sagging" between the contact points, which can therefore be relatively far apart.
  • the average distance between the coarser grains is expediently chosen to be up to 100 times the grain diameter, grain spacings in the range from 10 to 50 times the grain diameter being preferred.
  • the coarser grains integrated in the fine-porous diaphragm layer consist made of oxidized metal and are "baked" into the layer during the manufacture of the diaphragm. It is therefore expedient to use coarse-grained powders made of iron, cobalt, nickel or mixtures thereof for the production.
  • the diaphragm is expediently produced by oxidatively sintering a further metal or oxide powder with a coarser grain along the surface onto the fine-pore layer of the actually writable diaphragm.
  • a fine-grained metal powder (grain size approx. 1 to 5 ⁇ m) is compacted on a mesh as a carrier, in particular on a nickel mesh carrier, by means of a pressing or rolling process, and a metal powder with a coarser grain size is again applied to this fine-pored metal powder layer 10 to 250 ⁇ m) thinly distributed and then. (with little pressure application) pressed or rolled.
  • the coarser metal powder is temporarily embedded and fixed in the fine-pored layer. In this way, small "knobs" protrude beyond the surface of the fine-pored layer.
  • This arrangement is fired oxidatively in a further step, so that the metal structure is largely converted into an oxidic diaphragm.
  • FIG. 1 schematically shows the structure of the diaphragm 1 with a fine-porous layer 2 on a mesh-like carrier 3.
  • Coarser grains 4 which have been oxidized on are coagulated into the fine-porous layer 2 with a space 5 between them.
  • Gas and electrolyte-permeable electrodes 6 for example perforated sheet metal or porous, galvanically produced thin electrodes
  • nickel powder and a nickel carrier are used for the manufacture of the diaphragm and coarse-grain powder of metals for the "knobs", which is produced on the basis of comparable heat development should be oxidizable during the oxidation process together with the press and sintered layer and should be able to be integrated into the fine-porous layer.
  • the pressure for the manufacture of the diaphragm depends on the desired porosity and the embedding depth of the coarser grains, whereby an unburnt layer should be created in all cases.
  • Preferred dimensions are given on the left-hand edge of FIG. 1 and it can be seen that the distance of the electrode from the actual diaphragm can be kept variable up to in particular 200 ⁇ m, depending on the grain size and injection pressure when the coarser grains are applied.
  • the fine-porous diaphragm structure is removed from the direct range of the electrode only as far as is necessary to avoid the harmful side effects of the electrodes on the diaphragm during electrolysis operation, the advantageous small electrode spacing being retained.
  • microspacers or "knobs” formed in the manner described have no hydrophobic properties and are therefore particularly advantageous for gas-developing electrochemical processes since there are no harmful side effects due to the so-called bubble curtain effect on the cell voltage may occur.
  • the layer thickness was 40 mg / cm 2 .
  • a nickel mesh with a mesh size of 0.20 mm and a wire thickness of 0.125 mm was placed over it and the whole was cold-compressed with a pressure of approx. 200 N / cm 2 . That way
  • a (unfired) preform in the form of a nickel mesh support with a powder layer on one side.
  • Iron powder with a grain size of 10D to 150 ⁇ m was then uniformly distributed over a metal plate in a surface density of 10 mg / cm 2 .
  • the diaphragm preform was placed on this layer and pressed in under slight pressure (approx. 10 N / cm 2 ).
  • the second page was treated analogously.
  • This preform was then oxidatively sintered in air in a furnace at 1000 ° C. for 15 minutes, whereby a diaphragm with “microspacers” suitable for installation in an electrolysis cell with adjacent electrodes was obtained.

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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)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP85107908A 1984-06-30 1985-06-26 Diaphragme pour électrolyses alcalines et son procédé de fabrication Withdrawn EP0170051A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843424203 DE3424203A1 (de) 1984-06-30 1984-06-30 Diaphragma fuer alkalische elektrolysen und verfahren zur herstellung desselben
DE3424203 1984-06-30

Publications (2)

Publication Number Publication Date
EP0170051A2 true EP0170051A2 (fr) 1986-02-05
EP0170051A3 EP0170051A3 (fr) 1986-06-25

Family

ID=6239568

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85107908A Withdrawn EP0170051A3 (fr) 1984-06-30 1985-06-26 Diaphragme pour électrolyses alcalines et son procédé de fabrication

Country Status (6)

Country Link
US (1) US4636291A (fr)
EP (1) EP0170051A3 (fr)
JP (1) JPS6144191A (fr)
DE (1) DE3424203A1 (fr)
NO (1) NO852601L (fr)
ZA (1) ZA854894B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206032A1 (fr) * 1985-06-12 1986-12-30 Forschungszentrum Jülich Gmbh Electrolyseur présentant un assemblage diaphragme-électrode sous forme sandwich et dispositif de montage approprié

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5332483A (en) * 1990-07-06 1994-07-26 Igr Enterprises, Inc. Gas separation system
WO1992000934A2 (fr) * 1990-07-06 1992-01-23 Igr Enterprises, Inc. Composites ceramiques ductiles
US6592965B1 (en) 1990-07-06 2003-07-15 Igr Enterprises, Inc. Ductile ceramic composite electrolyte
US6071635A (en) * 1998-04-03 2000-06-06 Plug Power, L.L.C. Easily-formable fuel cell assembly fluid flow plate having conductivity and increased non-conductive material
US6007933A (en) * 1998-04-27 1999-12-28 Plug Power, L.L.C. Fuel cell assembly unit for promoting fluid service and electrical conductivity
US9222178B2 (en) 2013-01-22 2015-12-29 GTA, Inc. Electrolyzer
US8808512B2 (en) 2013-01-22 2014-08-19 GTA, Inc. Electrolyzer apparatus and method of making it
US11248303B2 (en) 2018-06-06 2022-02-15 Molecule Works Inc. Electrochemical device comprising thin porous metal sheet
WO2022167880A1 (fr) * 2021-02-04 2022-08-11 CTS H2 S.r.l. Ensemble particulièrement compact et efficace avec séparateur et électrodes pour utilisation dans l'électrolyse d'eau pour la production d'hydrogène à haute pression

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1082286A (en) * 1912-10-02 1913-12-23 Niagara Alkali Company Diaphragm for electrolytic apparatus.
US4073999A (en) * 1975-05-09 1978-02-14 Minnesota Mining And Manufacturing Company Porous ceramic or metallic coatings and articles
US4032427A (en) * 1975-11-03 1977-06-28 Olin Corporation Porous anode separator
DE2927566C2 (de) * 1979-07-07 1986-08-21 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma für alkalische Elektrolyse, Verfahren zur Herstellung desselben und dessen Verwendung
JPS5693883A (en) * 1979-12-27 1981-07-29 Permelec Electrode Ltd Electrolytic apparatus using solid polymer electrolyte diaphragm and preparation thereof
DE3031064C2 (de) * 1980-08-16 1986-09-04 Kernforschungsanlage Jülich GmbH, 5170 Jülich Poröses Oxiddiaphragma für alkalische Elektrolysen und dessen Verwendung
JPS57174482A (en) * 1981-03-24 1982-10-27 Asahi Glass Co Ltd Cation exchange membrane for electrolysis
US4476002A (en) * 1982-06-29 1984-10-09 Union Carbide Corporation Metal current carrier for electrochemical cell electrodes
US4457832A (en) * 1983-01-19 1984-07-03 Chevron Research Company Combination catalytic reforming-isomerization process for upgrading naphtha
DE3318758C2 (de) * 1983-05-24 1985-06-13 Kernforschungsanlage Jülich GmbH, 5170 Jülich Diaphragma auf Nickeloxidbasis und Verfahren zur Herstellung desselben

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206032A1 (fr) * 1985-06-12 1986-12-30 Forschungszentrum Jülich Gmbh Electrolyseur présentant un assemblage diaphragme-électrode sous forme sandwich et dispositif de montage approprié

Also Published As

Publication number Publication date
NO852601L (no) 1986-01-02
EP0170051A3 (fr) 1986-06-25
ZA854894B (en) 1986-03-26
DE3424203A1 (de) 1986-01-16
US4636291A (en) 1987-01-13
JPS6144191A (ja) 1986-03-03

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Inventor name: DIVISEK, JIRI, DR.