Fast response, high rate, gas diffusion electrode and method of making same

• US 4,615,954 A
• Filed: 09/27/1984
• Issued: 10/07/1986
• Est. Priority Date: 09/27/1984
• Status: Expired due to Fees

• Current Assignee: Eltech Systems Corporation (Industrie De Nora S.p.A)
• Original Assignee: Eltech Systems Corporation (Industrie De Nora S.p.A)
• Inventors: Solomon, Frank, Grun, Charles
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US06/655,129
• Time in Patent Office: 740 Days
• Field of Search: 429/42, 429/41, 429/43, 429/40, 429/45, 429/44, 429/27, 252/182.1, 204/294, 204/292
• US Class Current: 429/405
• CPC Class Codes: H01M 4/9008 Organic or organo-metallic compounds
• CPC Class Codes: H01M 4/96 Carbon-based electrodes
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Disclosed are gas fed, porous electrodes capable of steady, high current density operation for practical periods of service, e.g. as oxygen cathodes in metal-air batteries. The subject electrodes feature at least two bonded composite layers, one of which is a form-stable, conductive wetproofing layer while the other is an unusually thin active layer containing active carbon particles predominantly between about 2 and about 20 micrometers and having a high internal surface area, e.g. a B.E.T. surface area of over 1000 m² /gram. A simple and highly successful method of preparing such electrodes is also disclosed, which avoids the necessity of separately forming and handling the thin active layer.

Claims

1. A fast response, high current density oxygen cathode comprising:

a form-stable, electrically conductive, wetproofing layer composed essentially of an intimate, consolidated and heat sintered mixture of carbon black and particulate hydrophobic polymeric binder derived predominantly from tetrafluoroethylene, having at least one anisometric electroconductive reinforcing material incorporated therein; and

, directly adhered to one surface of said wetproofing layer, a porous active layer having a thickness between about 0.03 and about 0.1 millimeter and composed essentially of a mixture of particles of a polymer of tetrafluoroethylene and cobalt catalyst-containing particles of an active carbon predominantly of a size between about 2 and about 20 micrometers and having a B.E.T. surface area of over about 1000 m² /gram.

2. An oxygen cathode as in claim 1 wherein said reinforcing material comprises at least one coextensive layer of fine mesh or gauze having a thickness of between about 50 and about 200 micrometers.

3. An oxygen cathode as in claim 1 wherein said reinforcing material comprises short, chopped fibers of fine denier.

4. An oxygen cathode as in claim 3 wherein said fibers are between about 1 and about 10 millimeters in length and about 5 to 100 micrometers in diameter.

5. An oxygen cathode as in claim 4 wherein said fibers are carbon or graphite.

6. An oxygen cathode as in claim 1 wherein said carbon black has a particle size between about 50 and about 3000 Angstroms.

7. An oxygen cathode as in claim 6 wherein said carbon black is an acetylene carbon black.

8. An oxygen cathode as in claim 1 wherein said cobalt catalyst-containing particles of active carbon contain between about 5% and about 25% by weight of a cobalt effective in promoting reduction of oxygen.

9. An oxygen cathode as in claim 8 wherein said catalyst is a macrocyclic organic compound of cobalt.

10. An oxygen cathode as in claim 9 wherein said catalyst is cobalt tetramethoxyphenylporphyrin (which is heat treated after being deposited on said active carbon).

11. An oxygen cathode as in claim 1 wherein the thickness of said active layer is between about 50 and about 80 micrometers.

12. An oxygen cathode as in claim 1 wherein polytetrafluoroethylene is the predominant polymeric constituent in both the wetproofing and the active layers.

13. An oxygen cathode as in claim 1 wherein a thin outer layer of submicron sized silver particles is deposited on the exposed face of said active layer.

14. An oxygen cathode as in claim 13 wherein said layer of silver particles is thinner than said active layer.

15. An oxygen cathode as in claim 1 wherein said active carbon particles are predominantly in the range between about 5 and about 10 micrometers.

16. An oxygen cathode as in claim 1 wherein said wetproofing layer is thicker than 0.1 millimeter.

17. An oxygen cathode as in claim 1 wherein said reinforcing material is fibrous and it accounts for between about 3% and about 25% of the combined weight of carbon black and binder and the weight proportion of carbon black to hydrophobic polymeric binder therein is between about 3 to 2 and about 4 to 1, while the weight proportion of catalyzed active carbon to polymer particles in said active layer is between about 7 to 3 and about 9 to 1.

18. An oxygen cathode as in claim 1 wherein said active layer is also heat sintered.

19. A metal-air battery contining an oxygen cathode as defined in claim 1.