Separators for alkaline electrochemical cells

• US 7,645,540 B2
• Filed: 08/09/2004
• Issued: 01/12/2010
• Est. Priority Date: 08/08/2003
• Status: Active Grant

• Current Assignee: Energizer Brands, LLC (Energizer Holdings, Inc.)
• Original Assignee: Rovcal Inc. (Spectrum Brands Corp.)
• Inventors: Jin, Zhihong, Boone, David, Luecke, Jon, Cheeseman, Paul, Bushong, William C., Ndzebet, Ernest, Destephen, Mario, Vu, Viet H., Mortensen, Erik, Davidson, Gregory J., Ramaswami, Karthik, Sazhin, Sergey
• Primary Examiner(s): Kalafut; Stephen J.
• Application Number:
  US10/914,934
• Publication Number:
  US 20050074674A1
• Time in Patent Office: 1,982 Days
• Field of Search: 429/144, 429/145, 429/220, 429/248, 429/250
• US Class Current: 429/145
• 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 polyvinyl alcohol separator film between the anode and the cathode; 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 polyvinyl alcohol separator film, and further wherein the continuous polyvinyl alcohol separator film has an Exclusion Value of at least 50%.

2. The electrochemical cell of claim 1, wherein the cell is a cylindrical cell.

3. The electrochemical cell of claim 1, wherein the cell is a flat cell.

4. The electrochemical cell of claim 1, wherein the cathode active material is an oxide of a metal.

5. The electrochemical cell of claim 4, wherein the metal is selected from the group consisting of at least one of manganese, copper, nickel, iron and silver.

6. The electrochemical cell of claim 4, wherein the cathode active material is selected from the group consisting of manganese dioxide, copper oxide, and mixtures thereof.

7. The electrochemical cell of claim 1, wherein the cathode active material comprises a sulfide of a metal.

8. The electrochemical cell of claim 7, wherein the metal is selected from the group consisting of at least one of manganese, copper, nickel, iron and silver.

9. The electrochemical cell of claim 1, wherein the cathode active material is selected from the group consisting of manganese dioxide, copper sulfide, copper oxide, copper hydroxide, nickel oxyhydroxide, silver oxides, copper iodate, nickel iodate, copper fluoride, copper chloride, copper bromide, copper iodide, copper silver oxides, copper manganese oxides and mixtures of any of the foregoing.

10. The electrochemical cell of claim 1, wherein the cathode comprises a soluble species at least partially excluded by the separator from the anode.

11. The electrochemical cell of claim 10, wherein the soluble species is a metal species.

12. The electrochemical cell of claim 11, wherein the metal species is an oxide of a metal.

13. The electrochemical cell of claim 11, wherein the metal species is a sulfide of a metal.

14. The electrochemical cell of claim 1, wherein the cathode comprises a soluble species selected from the group consisting of a copper species, a sulfur species, a nickel species, an iron species and a silver species.

15. The electrochemical cell of claim 1, wherein the continuous polyvinyl alcohol separator film has an alkaline aqueous electrolyte retained therein.

16. The electrochemical cell of claim 15, wherein the retained electrolyte has a pH value lower than that of the bulk electrolyte.

17. The electrochemical cell of claim 15, wherein water retained in the continuous polyvinyl alcohol separator film melts at a temperature lower than 0°

C. in a differential scanning calorimetric test.

18. The electrochemical cell of claim 17, wherein at least about 50% of the water retained in the separator material is coupled to the continuous polyvinyl alcohol separator film.

19. The electrochemical cell of claim 17, wherein the continuous polyvinyl alcohol separator film has a dry cross-sectional thickness of between about 10 and about 250 microns.

20. The electrochemical cell of claim 15, wherein the continuous polyvinyl alcohol separator film is a non-woven fabric.

21. The electrochemical cell of claim 20, wherein the fabric is laminated to the continuous polyvinyl alcohol separator film.

22. The electrochemical cell of claim 20, wherein the fabric is tacked to the continuous polyvinyl alcohol separator film.

23. The electrochemical cell of claim 20, wherein the continuous polyvinyl alcohol separator film is formed on at least a portion of the fabric.

24. The electrochemical cell of claim 15, wherein the continuous polyvinyl alcohol separator film comprises no more than about 15% by weight of plasticizers.

25. The electrochemical cell of claim 15, wherein the continuous polyvinyl alcohol separator film comprises no more than about 10% by weight of plasticizers.

26. The electrochemical cell of claim 15, wherein the continuous polyvinyl alcohol separator film comprises no more than about 5% by weight of plasticizers.

27. The electrochemical cell of claim 15, wherein the continuous polyvinyl alcohol separator film comprises no more than about 3% by weight of plasticizers.

28. The electrochemical cell of claim 15, wherein the continuous polyvinyl alcohol separator film comprises no more than about 1% by weight of plasticizers.

29. The electrochemical cell of claim 15, wherein the bulk electrolyte and the retained electrolyte comprise potassium hydroxide.

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

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

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

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

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

35. The electrochemical cell of claim 1, wherein the continuous polyvinyl alcohol separator has an Exclusion Value of at least 97%.

36. The electrochemical cell of claim 1, wherein the continuous polyvinyl alcohol separator has an Exclusion Value of at least 99%.

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

38. The electrochemical cell of claim 37, wherein at least a portion of the continuous polyvinyl alcohol separator seal is a heat or a weld seal.

39. The electrochemical cell of claim 37, wherein at least a portion of the continuous polyvinyl alcohol separator seal is an adhesive seal.

40. The electrochemical cell of claim 1, wherein the continuous polyvinyl alcohol separator film actively transports water and hydroxide ions.

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

42. 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.

43. The electrochemical cell as recited in claim 42, wherein the additive is selected from the group consisting of elemental sulfur, selenium, tellurium, and compounds thereof.

44. The electrochemical cell of claim 43, wherein the additive comprises a sulfide of copper.

45. The electrochemical cell as recited in claim 1, wherein the cathode further comprises an oxide of copper.

46. The electrochemical cell of claim 1, wherein the continuous polyvinyl alcohol separator film is selected from the group consisting of a cast polyvinyl alcohol separator film, an extruded polyvinyl alcohol separator film, and a meltblown polyvinyl alcohol separator film.

47. The electrochemical cell of claim 1, wherein the continuous polyvinyl alcohol separator film has a Curley Air Permeability of 500 Gurley seconds or higher.

48. An electrochemical cell comprising:

an anode comprising anode active material;

a cathode comprising cathode active material selected from the group consisting of an oxide of copper, and iodate, Ag₂Cu₂O₄, and Ag₂Cu₂O₃ and at least one anode-fouling soluble species;

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.

49. The electrochemical cell of claim 48, 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.

50. The electrochemical cell of claim 48, wherein the continuous polyvinyl alcohol separator film comprises no more than about 15% percent by weight of plasticizers.

51. The electrochemical cell of claim 48, wherein the continuous polyvinyl alcohol separator film comprises no more than about 10% percent by weight of plasticizers.

52. The electrochemical cell of claim 48, wherein the continuous polyvinyl alcohol separator film comprises no more than about 5% percent by weight of plasticizers.

53. The electrochemical cell of claim 48, wherein the continuous polyvinyl alcohol separator film comprises no more than about 3% percent by weight of plasticizers.

54. The electrochemical cell of claim 48, further comprising a weld or heat seal on the continuous polyvinyl alcohol separator film.

55. The electrochemical cell of claim 48, wherein the continuous polyvinyl alcohol separator film comprises a seal.

56. The electrochemical cell of claim 55, wherein at least a portion of the seal is a heat or a weld seal.

57. The electrochemical cell of claim 55, wherein at least a portion of the seal is an adhesive seal.

58. The electrochemical cell of claim 48 wherein the continuous polyvinyl alcohol separator film has opposing sides and, the ability to effectively limit the migration of soluble copper species from one side of the polymer film to the other side of the polymer film.

59. The electrochemical cell of claim 48 wherein the continuous polyvinyl alcohol separator film has opposing sides and, the ability to effectively limit the migration of soluble sulfur species from one side of the polymer film to the other side of the polymer film.

60. The electrochemical cell of claim 48 wherein the continuous polyvinyl alcohol separator film has opposing sides and, the ability to effectively limit the migration of soluble copper species, soluble silver species and soluble sulfur species from one side of the polymer film to the other side of the polymer film.

61. The electrochemical cell of claim 48, wherein the continuous polyvinyl alcohol separator film comprises no more than about 1% percent by weight of plasticizers.

62. An electrochemical cell comprising:

a zinc anode;

a cathode comprising an oxide of copper and CuS;

a separator situated between the anode and the cathode; and

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

the separator (i) comprising a polyvinyl alcohol film and (ii) being configured to effectively limit soluble copper species and soluble sulfur species from migrating to the anode.

63. The electrochemical cell of claim 62, wherein the electrolyte situated within the separator has a pH value lower than that of the electrolyte situated in the anode and the cathode.

64. The electrochemical cell of claim 62, wherein substantially all of the fluid communication is through the separator.