Electroactivated cathode materials

• US 4,940,524 A
• Filed: 06/20/1988
• Issued: 07/10/1990
• Est. Priority Date: 06/19/1987
• Status: Expired due to Term

• Current Assignee: Chloralp (BNP Paribas S.A.)
• Original Assignee: Rhone-Poulenc Chimie
• Inventors: Bachot, Jean, Perineau, Jean-Maurice
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): GORGOS, KATHRYN L
• Application Number:
  US07/208,503
• Time in Patent Office: 750 Days
• Field of Search: 427/94, 427/77, 427/243, 427/247, 427/301, 502/101, 502/159, 428/332, 428/357, 428/367, 428/402, 428/288, 428/290, 204/283, 204/284, 204/282, 204/290 R, 204/279, 204/291, 204/292, 204/293, 204/242, 264/109, 264/238
• US Class Current: 204/242
• CPC Class Codes: C25B 11/00 Electrodes; Manufacture thereof not otherwise provided for
• CPC Class Codes: C25B 11/031 Porous electrodes
• CPC Class Codes: C25B 11/091 consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/2918 including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 442/696 Including strand or fiber material which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous compositions, water solubility, heat shrinkability, etc.]

Abstract

Disclosed are electroactivated shaped articles, well adapted as cathode elements and composites, especially for electrolytic cells for the electrolysis of sodium chloride. The articles include a mass of fibrous material consolidated in a matrix of fluoropolymer binder wherein at least a portion of the fibers are electrically conductive. The shaped articles have a resistivity of less than 0.4 ohm cm, and have at least one electrocatalytically active agent uniformly dispersed therethrough. The electrocatalytically active agent(s) is (are) selected from Raney metals or Raney alloys depleted in fugitive metal values.

Claims

1. An electroactivated shaped article, which comprises a mass of fibrous material consolidated in a matrix of fluoropolymer binder, at least a portion of the fibers comprising said fibrous material being electrically conductive, said shaped article having a resistivity of less than 0.4 ohm cm and having at least one electrocatalytically active agent uniformly distributed therethrough, and said electrocatalytically active agent comprising at least one Raney metal, or Raney alloy depleted in fugitive metal values.

2. The electroactivated shaped article as defined by claim 1, comprising from 30 to 70% by weight of said electrocatalytically active agent, based on the total weight of fibers+binder+electrocatalytically active agent.

3. The electroactivated shaped article as defined by claim 1, wherein the combination fibers+binder+electrocatalytically active agent, the binder constitutes from 5 to 20% by weight and the fibers from 10 to 65% by weight, with the proviso that the proportion by weight of binder in the subcombination fibers+binder ranges from 20 to 50%.

4. The electroactivated shaped article as defined by claim 1, comprising a sheet material having a thickness ranging from 0.5 to 3 mm.

5. The electroactivated shaped article as defined by claim 1, said electrically conductive fibers comprising monodisperse carbon or graphite fibers.

6. The electroactivated shaped article as defined by claim 1, further comprising up to 50% by weight of electrically nonconductive fibers, based on the weight of said electrically conductive fibers.

7. The electroactivated shaped article as defined by claim 1, further comprising up to 30% by weight of electrically nonconductive fibers, based on the weight of said electrically conductive fibers.

8. The electroactivated shaped article as defined by claim 1, said electrocatalytically active agent comprising Raney nickel, or a Raney nickel alloy depleted in fugitive metal values.

9. The electroactivated shaped article as defined by claim 1, said electrocatalytically active agent comprising a Raney alloy containing not more than 20% by weight of residual fugitive metal values.

10. The electroactivated shaped article as defined by claim 1, comprising a porous composite.

11. The electroactivated shaped article as defined by claim 1, comprising a cathode assembly.

12. A composite structure comprising the electroactivated shaped article as defined by claim 1 and an elementary cathode.

13. A laminate comprising the electroactivated shaped article as defined by claim 1, having an elementary cathode on one face surface thereof and a diaphragm on another face surface.

14. The laminate as defined by claim 13, said diaphragm comprising asbestos fibers in a matrix of fluoropolymer binder and having controlled porosity.

15. The laminate as defined by claim 14 said fluoropolymer binder comprising polychlorofluoroethylene.

16. A process for the production of the shaped article as defined by claim 15, comprising:

(a) preparing, in an aqueous medium, a dispersion comprising the fibers, the binder, and the electrocatalytically active agent or precursor thereof;

(b) forming a sheet by filtration, under programmed vacuum, of said suspension through an elementary cathode including a metal surface having mesh openings ranging from 20 μ

m to 5 mm;

(c) removing the liquid medium and drying the sheet thus formed;

(d) sintering the sheet thus obtained;

(e) filtering through the sheet a dispersion, in an aqueous sodium hydroxide solution, comprising asbestos fibers and polychlorotrifluoroethylene; and

(f) sintering the diaphragm thus formed.

17. A process for the production of the shaped article as defined by claim 14, comprising:

(a) preparing, in an aqueous medium, a dispersion comprising the fibers, the binder, and the electrocatalytically active agent or precursor thereof;

(b) forming a sheet by filtration, under programmed vacuum, of said suspension through an elementary cathode including a metal surface having mesh openings ranging from 20 μ

m to 5 mm;

(c) removing the liquid medium and drying the sheet thus formed;

(d) filtering through the sheet an aqueous dispersion comprising asbestos fibers, a fluoropolymer and silica;

(e) removing the liquid medium and drying of the diaphragm thus formed;

(f) consolidating the resulting assembly; and

(g) treating said consolidated assembly with an aqueous sodium hydroxide solution.

18. The electroactivated shaped article as defined by claim 1, further comprising a pore-forming agent.

19. The electroactivated shaped article as defined by claim 1, further comprising up to 10% by weight, based on the weight of said binder, of a hydrophilic material.

20. The electroactivated shaped article as defined by claim 1, said electrocatalytically active agent comprising a Raney alloy depleted in at least one member selected from the group consisting of aluminum, silicon, magnesium and zinc values.

21. In an electrolytic cell, the improvement which comprises, as the cathode element therefor, the electroactivated shaped article as defined by claim 1.

22. A process for the production of the electroactivated shaped article as defined by claim 1 in sheet material form, comprising:

(a) preparing, in an aqueous medium, a dispersion comprising the fibers, the binder, and the electrocatalytically active agent or precursor thereof;

(b) forming a sheet by filtration, under programmed vacuum, of said suspension through a material of high porosity;

(c) optionally sintering said sheet, and then removing the fugitive metal values by leaching the sheet with a solution which does not attack the electroactive fraction of the precursor alloy.