Separators for alkaline electrochemical cells

• US 7,931,981 B2
• Filed: 10/20/2009
• Issued: 04/26/2011
• Est. Priority Date: 08/08/2003
• Status: Expired due to Term

• Current Assignee: Energizer Brands, LLC (Energizer Holdings, Inc.)
• Original Assignee: Rovcal Inc. (Spectrum Brands Corp.)
• Inventors: Boone, David, Luecke, Jon, Cheeseman, Paul, Bushong, William C., Ndzebet, Ernest, Destephen, Mario, Jin, Zhihong, Vu, Viet H., Mortensen, Erik, Davidson, Gregory J., Sazhin, Sergiy V., Ramaswami, Karthik
• Primary Examiner(s): Kalafut; Stephen J.
• Application Number:
  US12/582,022
• Publication Number:
  US 20100112431A1
• Time in Patent Office: 553 Days
• Field of Search: 429/144, 429/145, 429/220, 429/248, 429/250
• US Class Current: 429/144
• CPC Class Codes: H01M 10/24 Alkaline accumulators
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/48 of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present invention relates to a high capacity electrochemical cell having a cathode containing an oxide of copper as an active material, as well as an anode, an electrolyte, and separators for use with the cathodes of the invention in an alkaline electrochemical cell.

Claims

1. An electrochemical cell comprising:

an anode;

a cathode comprising a cathode active material;

at least one layer of a continuous polymer separator film between the anode and the cathode, the continuous polymer separator film comprising a polymer backbone, electrolyte-retaining side groups coupled to the backbone, and alkaline aqueous electrolyte retained therein; and

,

an alkaline aqueous bulk electrolyte in fluid communication with the anode and the cathode, wherein substantially all of the fluid communication is through the continuous polymer separator film, and further wherein the continuous polymer has an Exclusion Value of at least 50%.

2. The electrochemical cell of claim 1, wherein the electrolyte-retaining side group modulates the pH value of the retained electrolyte relative to that of the bulk electrolyte.

3. The electrochemical cell of claim 1, wherein the electrolyte-retaining side group is selected from an alcohol moiety, a linear side chain, a cyclic side chain, and a branched side chain, wherein the side chain comprises at least one alcohol moiety.

4. The electrochemical cell of claim 1, wherein the polymer backbone is selected from a straight chain polymer backbone and a branched polymer backbone.

5. The electrochemical cell of claim 1, wherein the continuous polymer separator film comprises a polymer selected from the group consisting of a polyvinyl alcohol, a polyethylvinyl alcohol and a cellophane.

6. The electrochemical cell of claim 1, wherein water retained in the continuous polymer separator film melts at a temperature lower than 0°

C. in a differential scanning calorimetric test.

7. The electrochemical cell of claim 1, wherein the continuous polymer separator film has a dry cross-sectional thickness of between about 10 and 250 microns.

8. The electrochemical cell of claim 1, wherein the continuous polymer separator film is coupled to a non-woven fabric.

9. The electrochemical cell of claim 8, wherein (i) the fabric is laminated to the continuous polymer separator film, (ii) the fabric is tacked to the continuous polymer separator film, or (iii) the continuous polymer separator film is formed on at least a portion of the fabric.

10. The electrochemical cell of claim 1, wherein the continuous polymer separator film comprises no more than about 5% by weight of plasticizers.

11. The electrochemical cell of claim 1, wherein the continuous polymer separator film comprises no more than about 3% by weight of plasticizers.

12. The electrochemical cell of claim 1, wherein the continuous polymer separator film comprises no more than about 1% by weight of plasticizers.

13. The electrochemical cell of claim 1, wherein the continuous polymer separator film comprises retained electrolyte and the retained electrolyte has a pH value lower than that of the bulk electrolyte.

14. The electrochemical cell of claim 1, wherein the bulk electrolyte and the retained electrolyte comprise potassium hydroxide.

15. The electrochemical cell of claim 1, wherein the retained electrolyte has a pH value between 0.5 and 3 pH units lower than that of the bulk electrolyte.

16. The electrochemical cell of claim 1, wherein the continuous polymer separator film has an Exclusion Value of at least 75%.

17. The electrochemical cell of claim 1, wherein the continuous polymer separator film has an Exclusion Value of at least 80%.

18. The electrochemical cell of claim 1, wherein the continuous polymer separator film has an Exclusion Value of at least 90%.

19. The electrochemical cell of claim 1, wherein the continuous polymer separator film has an Exclusion Value of at least 95%.

20. The electrochemical cell of claim 1, wherein the continuous polymer separator film has an Exclusion Value of at least 97%.

21. The electrochemical cell of claim 1, wherein the continuous polymer separator film has an Exclusion Value of at least 99%.

22. The electrochemical cell of claim 1, further comprising a continuous polymer separator film seal that prevents fluid communication of the bulk electrolyte between the cathode and the anode except through the separator.

23. The electrochemical cell of claim 22, wherein at least a portion of the continuous polymer separator film seal is a heat, weld or adhesive seal.

24. The electrochemical cell of claim 1, wherein the continuous polymer separator film actively transports water and hydroxide ions.

25. The electrochemical cell of claim 24, wherein the continuous polymer separator film preferentially transports water over hydroxide ions.

26. The electrochemical cell of claim 1, wherein the continuous polymer separator film preferentially permits diffusion of water and hydroxide ions relative to soluble electrode species.

27. The electrochemical cell of claim 1, wherein the cathode active material has a voltage, the cathode further comprising an additive, the additive having a voltage less than the voltage of the active material and wherein a combination of the active material and the additive has a voltage greater than the voltage of either the active material or the additive alone.

28. The electrochemical cell of claim 27, wherein the additive is selected from the group consisting of elemental sulfur, selenium, tellurium, and compounds thereof.

29. The electrochemical cell of claim 28, wherein the additive comprises a sulfide of copper.

30. The electrochemical cell of claim 1, wherein the cathode further comprises an oxide of copper.

31. An electrochemical cell comprising:

an anode comprising anode active material;

a cathode comprising a cathode active material and at least one anode-fouling soluble species, wherein the cathode active material comprises a compound selected from the group consisting of an oxide of copper, an iodate, copper sulfide, manganese dioxide, copper hydroxide, copper fluoride, copper chloride, copper bromide, copper iodide, a compound comprising Ni, Co, Ag or Pb, and combinations thereof;

at least one layer of a continuous polyvinyl alcohol separator film between the cathode and the anode;

an alkaline aqueous bulk electrolyte in fluid communication with the anode and the cathode;

wherein substantially all of the fluid communication is through the continuous polyvinyl alcohol separator film, and further wherein the continuous polyvinyl alcohol separator film is adapted to effectively limit migration of the at least one anode-fouling soluble species through the continuous polyvinyl alcohol separator film from the cathode to the anode.

32. The electrochemical cell of claim 31, wherein the continuous polyvinyl alcohol separator film comprises retained alkaline aqueous electrolyte therein, the retained alkaline aqueous electrolyte having a pH value lower than that of the bulk electrolyte.

33. The electrochemical cell of claim 31, wherein the continuous polyvinyl alcohol separator film comprises no more than about 5% by weight of plasticizers.

34. The electrochemical cell of claim 31, wherein the continuous polyvinyl alcohol separator film comprises no more than about 3% by weight of plasticizers.

35. The electrochemical cell of claim 31, wherein the continuous polyvinyl alcohol separator film comprises no more than about 1% by weight of plasticizers.

36. The electrochemical cell of claim 31, wherein the cathode active material comprises an oxide of copper.

37. The electrochemical cell of claim 36, wherein the oxide of copper is a silver copper oxide or a copper manganese oxide.

38. The electrochemical cell of claim 31, wherein the continuous polyvinyl alcohol separator film comprises a seal.

39. The electrochemical cell of claim 38, wherein at least a portion of the seal is a heat, weld or adhesive seal.

40. The electrochemical cell of claim 31, wherein the cathode active material comprises an iodate selected from the group consisting of copper iodate, nickel iodate, and combinations thereof.

41. The electrochemical cell of claim 31, wherein the cathode active material comprises MnO₂, NiO, NiOOH, Cu(OH)₂, cobalt oxide, copper oxide, PbO₂, AgO, Ag₂O, and combinations thereof.

42. The electrochemical cell of claim 31, wherein the cathode active material comprises a compound having a formula M_xCu_yO_z, wherein M is selected from the group consisting of Mn, Ni, Co, Fe, Sn, V, Mo, Pb, Ag and combinations thereof;

x is from 1 to 5;

y is from 1 to 5; and

z is from 1 to 20.

43. The electrochemical cell of claim 31, wherein the cathode active material comprises a compound having a formula AM_xCu_yO_z, wherein A is selected from the group consisting of Li, Na, K, Rb, Cs, Ca, Mg, Sr and Ba;

M is selected from the group consisting of Mn, Ni, Co, Fe, Sn, V, Mo, Pb, Ag and combinations thereof;

x is from 1 to 5;

y is from 1 to 5; and

z is from 1 to 20.

44. The electrochemical cell of claim 31, wherein the continuous polyvinyl alcohol separator film has a Gurley Air Permeability of 500 Gurley seconds or higher.