WO1983003105A1 - Method for manufacturing a large surface current collector for an electrochemical cell in the form of a porous titanium plate or sheet - Google Patents

Method for manufacturing a large surface current collector for an electrochemical cell in the form of a porous titanium plate or sheet Download PDF

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Publication number
WO1983003105A1
WO1983003105A1 PCT/CH1983/000021 CH8300021W WO8303105A1 WO 1983003105 A1 WO1983003105 A1 WO 1983003105A1 CH 8300021 W CH8300021 W CH 8300021W WO 8303105 A1 WO8303105 A1 WO 8303105A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
titanium
powder
graphite
paste
Prior art date
Application number
PCT/CH1983/000021
Other languages
German (de)
English (en)
French (fr)
Inventor
Boveri & Cie Bbc Aktiengesellschaft Brown
Original Assignee
Devantay, Hubert
Stucki, Samuel
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 Devantay, Hubert, Stucki, Samuel filed Critical Devantay, Hubert
Publication of WO1983003105A1 publication Critical patent/WO1983003105A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/006Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Definitions

  • the invention is based on a method for producing a large-area current collector according to the preamble of claim 1.
  • Titanium foils of limited dimensions for experimental purposes are Titanium foils of limited dimensions for experimental purposes
  • the invention is based on the object of specifying an economical method for producing a current collector in the form of a porous plate or foil made of titanium, the area of which is not limited and the thickness and porosity of which are uniform over the entire area, the density or Porosity can be selectively reproduced within narrow limits with narrow tolerances.
  • Fig. 3 is a Flie 'ssdiagramm the method.
  • the diagram 1 shows the temperature profile as a function of time for the heat treatment of the titanium powder. posed.
  • the diagram is self-explanatory. In deviation from the diagram, heating to 500 ° C. can also be carried out in the period from 30 to 90 minutes.
  • the sintering temperature can be 900 to 1200 c.
  • 1 is the support in the form of a flat plate (non-porous, non-sticky graphite).
  • 2 represents the viscous, homogeneous paste consisting of titanium powder and terpineol (C .H Collector0).
  • 3 is the coherent, uniform layer of this paste.
  • a movable coating device 4 to be displaced in the direction of the arrow in the form of a container tapering downward can be used as a means for applying the paste.
  • 2 and 3 represent the dry, free-flowing titanium powder or the upper layer thus produced on the carrier 1.
  • Terpineol evaporated in air by heating to approx. 200 ° C.
  • Layer 3 was then dried together with carrier substance 1 in a vacuum drying cabinet at approx. 200 ° C.
  • the titanium powder was already compacted. Furthermore, the material was subjected to a multi-stage heat treatment. To this end, the layer
  • the material was heated to a temperature of 500 C over a period of about 90 min and during
  • the cold-rolled foil was then placed on a graphite powder-coated support 1 and subjected to a further heat treatment according to FIG. 1.
  • the measured porosity was still 58%.
  • a layer consisting of platinum was applied to the porous titanium foil in an electrochemical manner.
  • the case was a mixture of ruthenium oxide
  • the process steps of cold rolling and sintering can be carried out several times in succession until the desired targeted density or porosity of the film or plate has been reached.
  • paste 2 can also be produced with the aid of a suitable liquid other than C.
  • the application of the paste is also not bound to the coating device 4 for thin-layer plates, but can be carried out with the aid of any other suitable device.
  • the condition is that a viscous, homogeneous paste is first produced and then applied as uniformly as possible to a non-adhesive substrate (carrier 1).
  • a current collector * for an electrochemical ozone cell in the form of a porous titanium foil 1.45 mm thick was produced as follows: On one with graphite powder (KS 75 from Lonza) coated support 1 made of fine-grained graphite (ground plate, quality Ringsdorff EK 72) was dry, free-flowing titanium powder 2 (Sumitomo, Osaka) in the form of a uniform layer using a movable coating device 4 (Camag thin-layer apparatus for chromatography) 3 applied. The layer thickness was approximately 1.9 mm; the area was a square with a side length of 200 mm. The whole was then subjected to a multi-stage heat treatment in a vacuum oven in order to sinter the titanium powder.
  • KS 75 from Lonza coated support 1 made of fine-grained graphite (ground plate, quality Ringsdorff EK 72) was dry, free-flowing titanium powder 2 (Sumitomo, Osaka) in the form of a uniform layer using a movable coating
  • the mixture was first heated from room temperature to 500 ° C. over a period of about 90 minutes and this temperature was kept constant for a further 30 minutes. The mixture was then heated to 1000 ° C. for 30 minutes and this temperature was maintained for 3 hours. After cooling to room temperature, the pre-sintered in this way
  • Titanium foil can be easily detached from the carrier 1, since the graphite powder had formed a protective layer.
  • the thickness of the film after presintering was approx. 1.8 mm, the porosity 70%.
  • the film was cold rolled in several passes in a roll stand with rolls of 130 mm in diameter.
  • the decrease in height per stitch was approx. 0.1 mm, so that after 3 stitches a film thickness of approx. 1.5 was now achieved.
  • the rolling speed was 1.2 m / min. Care must be taken that the total cross-sectional reduction before the next heat treatment does not exceed 30%, since otherwise the material could tear.
  • the decrease in height per stitch should not exceed 15%.
  • the rolling speed can advantageously be set to 1 to 30 m / min.
  • the porosity had dropped to about 62% after cold rolling.
  • the cold-rolled titanium foil was then subjected to a further sintering process in accordance with the heat treatment described above. * The thickness of the film was still after sintering approx.1.45 mm, the porosity approx. 59%.
  • the porous titanium foil was now coated with platinum according to Example I. An additional layer consisting of PbO p in
  • any desired film thickness and any porosity between 0 and that approximately corresponds to the loosely poured titanium powder can be achieved, which is primarily used for sintering heat treatment can be carried out under vacuum or protective gas.
  • the porous titanium foil is provided with a thin layer of platinum, on which another layer made of at least one platinum metal or one
  • Platinum metal oxide or PbO existing electrocatalyst layer is applied.
  • the process according to the invention enables the economical production of current collectors in the form of porous titanium foils and titanium plates of 0.1 to approximately 5 mm constant thickness with uniform, targeted porosity and practically any surface area, such as that required for the construction of large industrial ones electrochemical devices, in particular electrolysis apparatus (individual parts and entire batteries constructed according to the filter press principle) are required.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Inert Electrodes (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Catalysts (AREA)
  • Powder Metallurgy (AREA)
PCT/CH1983/000021 1982-03-05 1983-02-28 Method for manufacturing a large surface current collector for an electrochemical cell in the form of a porous titanium plate or sheet WO1983003105A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1343/82-0820305 1982-03-05
CH1343/82A CH653581A5 (de) 1982-03-05 1982-03-05 Verfahren zur herstellung einer grossflaechigen platte oder folie aus poroesem titan.

Publications (1)

Publication Number Publication Date
WO1983003105A1 true WO1983003105A1 (en) 1983-09-15

Family

ID=4208261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH1983/000021 WO1983003105A1 (en) 1982-03-05 1983-02-28 Method for manufacturing a large surface current collector for an electrochemical cell in the form of a porous titanium plate or sheet

Country Status (4)

Country Link
EP (1) EP0102966A1 (it)
CH (1) CH653581A5 (it)
IT (1) IT1160493B (it)
WO (1) WO1983003105A1 (it)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2591529A1 (fr) * 1985-11-20 1987-06-19 Permelec Electrode Ltd Materiau composite a base de titane ou d'un alliage de titane et son procede de preparation
EP0339717A1 (de) * 1988-04-23 1989-11-02 Metallgesellschaft Ag Verfahren zur Herstellung von Werkstoffverbunden als Blechtafeln, Blechbänder und Folien mit oberflächiger Skelettstruktur und Verwendung der Werkstoffverbunde
CN115821332A (zh) * 2022-11-28 2023-03-21 西北有色金属研究院 一种质子交换膜电解水制氢装置用钛集电器及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4838710A (en) * 1986-09-14 1989-06-13 Canon Kabushiki Kaisha Static pressure gas bearing assembly

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB863989A (en) * 1958-01-15 1961-03-29 Ici Ltd Improvements in the rolling of strip from powder
GB922599A (en) * 1960-03-11 1963-04-03 Ici Ltd Methods of manufacturing electrodes
US3489555A (en) * 1967-05-18 1970-01-13 Clevite Corp Method of slip casting titanium structures
DE1483690A1 (de) * 1965-05-05 1970-01-22 Deutsche Edelstahlwerke Ag Verfahren zum Erhoehen der Durchflussleistung von poroesgesinterten Metallfiltern
US3877962A (en) * 1972-12-18 1975-04-15 Owens Illinois Inc Substrate coating composition and process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB863989A (en) * 1958-01-15 1961-03-29 Ici Ltd Improvements in the rolling of strip from powder
GB922599A (en) * 1960-03-11 1963-04-03 Ici Ltd Methods of manufacturing electrodes
DE1483690A1 (de) * 1965-05-05 1970-01-22 Deutsche Edelstahlwerke Ag Verfahren zum Erhoehen der Durchflussleistung von poroesgesinterten Metallfiltern
US3489555A (en) * 1967-05-18 1970-01-13 Clevite Corp Method of slip casting titanium structures
US3877962A (en) * 1972-12-18 1975-04-15 Owens Illinois Inc Substrate coating composition and process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2591529A1 (fr) * 1985-11-20 1987-06-19 Permelec Electrode Ltd Materiau composite a base de titane ou d'un alliage de titane et son procede de preparation
EP0339717A1 (de) * 1988-04-23 1989-11-02 Metallgesellschaft Ag Verfahren zur Herstellung von Werkstoffverbunden als Blechtafeln, Blechbänder und Folien mit oberflächiger Skelettstruktur und Verwendung der Werkstoffverbunde
CN115821332A (zh) * 2022-11-28 2023-03-21 西北有色金属研究院 一种质子交换膜电解水制氢装置用钛集电器及其制备方法

Also Published As

Publication number Publication date
IT1160493B (it) 1987-03-11
CH653581A5 (de) 1986-01-15
EP0102966A1 (de) 1984-03-21
IT8319907A1 (it) 1984-09-04
IT8319907A0 (it) 1983-03-04

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