Air battery and electrochemical method

• US 4,172,924 A
• Filed: 02/21/1978
• Issued: 10/30/1979
• Est. Priority Date: 07/19/1974
• Status: Expired due to Term

• Current Assignee: Societe Generale de Constructions Electriques et Mecaniques "Alsthom et CIE"
• Original Assignee: Societe Generale de Constructions Electriques et Mecaniques "Alsthom et CIE"
• Inventors: Warszawski, Bernard
• Primary Examiner(s): Walton, Donald L.
• Application Number:
  US05/879,228
• Time in Patent Office: 616 Days
• Field of Search: 429/12, 429/13, 429/15, 429/27, 429/67, 429/68, 429/101, 429/127
• US Class Current: 429/404
• CPC Class Codes: H01M 8/225 Fuel cells in which the fuel is based on materials comprising particulate active material in the form of a suspension, a dispersion, a fluidised bed or a paste
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Method and apparatus for electrochemically producing electricity. Ion contivity is established between an oxygen-reducing electrode, and adjacent ion pervious insulating membrane, a paste which has flow characteristics comprising particles of an oxidizable metal and a liquid electrolyte, and an inert electrode in physical contact with said paste. In said paste, the metal particles are in an amount constituting from 60% up to the critical pigment volume composition. The metal paste is moved from a first reservoir through the electrochemical battery wherein it is oxidized to the corresponding metal oxide paste and passed to a second reservoir. The battery may be recharged by reversing the movement and electrolyzing, or by reducing the metal oxide paste in an external circuit.

Claims

1. A method for producing electricity by oxidizing a metal and reducing oxygen, comprising

electrolytically connecting an oxygen-reducing electrode with an inert anode which is in contact with a pumpable paste consisting essentially of particles of an oxidizable metal and a liquid electrolyte and being free from gelling agents, said paste being physically separated from said oxygen-reducing electrode by an ion-pervious insulating membrane abutting said oxygen-reducing electrode and providing said electrolytic connection between said oxygen-reducing electrode and said inert anode,

said oxidizable metal being a metal that forms a solid metal oxide and said liquid electrolyte being a liquid which does not dissolve said solid metal oxide,

said paste of said metal and said electrolyte comprising very fine metal particles in metal-to-metal contact with each other, and electrolyte filling the interstices between the metal particles and having a concentration of metal particles between (i) the amount constituting the critical pigment volume composition (CPVC) and (ii) an amount at least 60% by volume of said CPVC

contacting said oxygen-reducing electrode with an oxygen-containing gas;

connecting said electrodes through an external electric circuit, whereby electricity flow through said circuit; and

moving said paste relative to said inert anode while said electrodes are externally connected, whereby the metal particles in said paste are progressively transformed into metal oxide particles.

2. The method of claim 1 where the metal particles'"'"' size is between about 0.1 and 60 microns.

3. The method of claim 1 wherein said paste of metal and electrolyte contacts said ion-pervious insulating membrane.

4. The method of claim 3 wherein said metal is selected from the group consisting of zinc, iron, cadmium and lead.

5. The method of claim 4 wherein said metal is zinc and said electrolyte is alkaline having a concentration between 7 and 13.5 N.

6. The method of claim 5 wherein said electrolyte is selected from the group consisting of sodium hydroxide and potassium hyroxide.

7. The method of claim 6 wherein said concentration of metal particles is between the CPVC value and 90% by volume of the CPVC value.

8. The method of claim 7 wherein said paste contains a powdered polytetrafluoroethylene or powdered graphite as a solid lubricant.

9. The method of claim 7 wherein said oxygen-containing gas is atmospheric air.

10. The method of claim 3 wherein said paste consists essentially of 27% by volume of zinc powder, 3% of polytetrafluorethylene, and 70% of 10 N potassium hydroxide.

11. The method of claim 4 wherein said electrolyte is sodium hydroxide or potassium hydroxide having a pH between 0.1 N and 13.5 N, and where said metal is zinc.

12. The method of claim 6 wherein said oxygen-containing gas is atmospheric air.

13. A paste useful in the method of claim 1 consisting essentially of zinc particles in surface to surface contact and alkaline electrolyte in the interstices between particles, said zinc particles being in an amount between the critical pigment volume composition and 60% by volume of said composition, and said particles having a size of between about 0.1 and 60 microns.

14. The paste of claim 13 consisting essentially of 27% by volume of zinc, 3% of polytetrafluorethylene or graphite, and 70% of 10 N potassium hydroxide.

15. The paste of claim 13 containing zinc particles in an amount between the critical pigment volume composition and 90% by volume of said composition.

16. A paste useful in the method of claim 1 consisting essentially of zinc oxide particles in surface to surface contact and alkaline electrolyte in the interstices between particles, said zinc oxide particles being in an amount between the critical pigment volume composition and 60% by volume of said composition, and said particles having a size of between about 0.1 and 60 microns.

17. The paste of claim 16 consisting essentially of 37% by volume of zinc oxide, 3% of polytetrafluorethylene or graphite, and 60% of 10 N potassium hydroxide.

18. The paste of claim 16 containing zinc particles in an amount between the critical pigment volume composition and 90% by volume of said composition.

19. The method of claim 1 wherein said concentration of metal particles is between the critical pigment volume composition and 90% by volume of said composition.

20. Apparatus for carrying out the method of claim 1 comprising

a first paste reservoir,

a second paste reservoir,

a conduit connecting said first and second paste reservoirs, said conduit containing an electrochemical battery,

said electrochemical battery comprising at least one, inert oxygen-reducing electrode, an ion-pervious insulating diaphragm in electrolytic contact with and abutting said oxygen-reducing electrode, an inernal inert anode, said anode being spaced apart from said diaphragm by an internal space,

said electrochemical battery being at least a portion of said conduit, and said space separating said internal inert anode and said diaphragm, said space communicating with both of said reservoirs,

and means for moving said paste from said first reservoir to said second reservoir through said conduit and electrochemical battery.

21. The apparatus of claim 20 wherein said diaphragm is a simple diaphragm.

22. The apparatus of claim 20 wherein said diaphragm is a composite diaphragm.

23. The apparatus of claim 20 wherein said anode comprises at least a portion of said moving means.

24. The apparatus of claim 23 wherein said anode and moving means comprise a screw-type conveyor in said conduit.