Catholytes for aqueous lithium/air battery cells

• US 8,323,820 B2
• Filed: 06/12/2009
• Issued: 12/04/2012
• Est. Priority Date: 06/16/2008
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., De Jonghe, Lutgard C., Nimon, Yevgeniy S., Petrov, Alexei, Pridatko, Kirill
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): Anthony, Julian
• Application Number:
  US12/484,063
• Publication Number:
  US 20090311596A1
• Time in Patent Office: 1,271 Days
• Field of Search: 429/126, 429/231.95, 429/101, 429/142, 429/304, 429/322, 429/323
• US Class Current: 429/126
• CPC Class Codes: H01M 12/02 Details of electrodes H01M4/00; of non-active parts H01M50/00
• CPC Class Codes: H01M 12/04 composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 6/04 Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/045 characterised by aqueous electrolyte
• CPC Class Codes: H01M 8/08 Fuel cells with aqueous electrolytes
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

Abstract

Li/air battery cells are configurable to achieve very high energy density. The cells include a protected a lithium metal or alloy anode and an aqueous catholyte in a cathode compartment. In addition to the aqueous catholyte, components of the cathode compartment include an air cathode (e.g., oxygen electrode) and a variety of other possible elements.

Claims

1. A battery cell, comprising:

a protected anode, comprising,

a lithium anode having a first surface and a second surface,

a protective membrane architecture on at least the first surface of the anode,

a cathode compartment comprising, prior to initial discharge, a cathode for reducing molecular oxygen and an aqueous catholyte comprising water and an active first salt dissolved therein, wherein the active first salt comprises a component selected from the group consisting of a nitrate, an aluminum halide, a magnesium halide and a titanium halide; and

,

wherein the protective membrane architecture comprises one or more materials configured to provide a first membrane surface chemically compatible with the lithium anode in contact with the anode, and a second membrane surface substantially impervious to and chemically compatible with the aqueous catholyte.

2. The cell of claim 1, wherein the concentration of the active first salt is at least 2 Molar.

3. The cell of claim 1, wherein the active first salt comprises a component selected from the group consisting of an aluminum halide, a magnesium halide and a titanium halide, wherein the halide is selected from the group consisting of bromide, chloride and iodide.

4. The cell of claim 1, wherein the active first salt is a nitrate.

5. The cell of claim 1, wherein the active first salt is NH₄NO₃.

6. The cell of claim 1, wherein the active first salt is selected from the group consisting of an aluminum halide, a magnesium halide and a titanium halide.

7. The cell of claim 1, wherein the active first salt is AlCl₃.

8. The cell of claim 1, wherein the active first substance material dissolves hydrolytically in the water of the catholyte.

9. The cell of claim 1, wherein the catholyte, prior to initial discharge, has an equilibrium relative humidity of a value selected from the group consisting of less than 50%, less than 40%, less than 30%, less than 20%, less than 15%, and less than 10%.

10. The battery cell of claim 1, wherein the water in the catholyte is insufficient for complete discharge of the cell.

11. The battery cell of claim 1, wherein at least one discharge product comprises an anion of the active first salt.

12. The battery cell of claim 11, wherein an anion of the discharge product is selected from the group consisting of halogens and nitrates.

13. The cell of claim 11, wherein the discharge product precipitates out of the catholyte as a solid discharge product, the catholyte being saturated with the discharge product.

14. The cell of claim 13, wherein the solid discharge product further comprises lithium.

15. The cell of claim 14, wherein the catholyte is saturated with the discharge product comprising lithium.

16. The battery cell of claim 15, wherein the catholyte, subsequent to initial discharge, attains an equilibrium relative humidity of a value selected from the group consisting of less than 50%, less than 40%, less than 30%, less than 20%, less than 15%, and less than 10%.

17. The battery cell of claim 1, wherein lithium hydroxide is not formed as a discharge product of the cell.

18. The battery cell of claim 1, wherein the cell is discharged over a first stage wherein dissolved active salt species participate, as a reagent, in the discharge reaction, and the cell is also discharged over a second stage wherein dissolved active salt species do not participate, as a reagent, in the discharge, and water is a reagent that is consumed during second stage discharge.

19. A battery cell, comprising:

a protected anode, comprising,

a lithium anode having a first surface and a second surface,

a protective membrane architecture on at least the first surface of the anode,

a cathode compartment comprising, prior to initial discharge, a cathode for reducing molecular oxygen and an aqueous catholyte comprising water, an active first salt dissolved therein, and a second salt different than the active first salt;

wherein the protective membrane architecture comprises one or more materials configured to provide a first membrane surface chemically compatible with the alkali metal anode in contact with the anode, and a second membrane surface substantially impervious to and chemically compatible with the components of the cathode compartment.

20. The cell of claim 19, wherein the second salt is a non-active salt.

21. The cell of claim 20, wherein the active first salt and the second salt have a common salt component.

22. The cell of claim 21, wherein the common salt component is halogen.

23. The cell of claim 21, wherein the common salt component is nitrate.

24. The cell of claim 23, wherein the nitrate concentration in the catholyte is at least 6 Molar.

25. The cell of claim 24, wherein the active first halide salt and the second halide salt do not have a common halogen anion.

26. The cell of claim 22, wherein the halogen concentration in the catholyte is at least 6 Molar.

27. The cell of claim 19, wherein the second salt is a lithium salt.

28. The cell of claim 27, wherein the concentration of the active first salt is greater than the concentration of the lithium salt.

29. The cell of claim 27, wherein the concentration of the active first salt is sufficient to suppress the solubility of the lithium salt, and wherein the catholyte is saturated with at least one of the active first salt and the lithium salt.

30. The cell of claim 19, wherein the second salt is a lithium halide salt.

31. The cell of claim 19, wherein the second salt is selected from the group consisting of LiC, LiBr, and LiI.

32. The cell of claim 19, wherein the active first salt and the second salt are halide salts.

33. The cell of claim 32, wherein the active first halide salt and the second halide salt have a common halogen anion.

34. The cell of claim 19, wherein the second salt is a lithium halide and the active first salt is an ammonium halide.

35. The cell of claim 19, wherein the second salt is lithium chloride and the active first salt is ammonium chloride.

36. The cell of claim 19, wherein the second salt is lithium bromide, and the catholyte further comprises lithium chloride.

37. The cell of claim 19, wherein the second salt is lithium nitrate and the active first salt is ammonium nitrate.

38. The cell of claim 19, wherein the catholyte, prior to initial discharge, has a halogen concentration of at least 6 Molar and a Li concentration of at least 2 Molar.

40. The battery cell of claim 19, wherein the active first salt comprises an ammonium component.

41. The battery cell of claim 40, wherein the active first salt is an ammonium salt.

42. The battery cell of claim 41, wherein the ammonium active first salt is selected from the group consisting of NH₄Br, NH₄Cl, NH₄I, NH₄NO₃, and NH₄CNS.

43. The battery cell of claim 41, wherein the concentration of the ammonium active first salt is at least 2M.

44. The battery cell of claim 41, wherein the concentration of the ammonium active first salt is at about 4M.

39. The cell of 19, wherein the catholyte, prior to initial discharge, has a nitrate concentration of at least 6 Molar and a Li concentration of at least 2 Molar.

45. A battery cell, comprising:

a protected anode, comprising,

a lithium anode having a first surface and a second surface,

a protective membrane architecture on at least the first surface of the anode,

a cathode compartment comprising, prior to initial discharge, a cathode for reducing molecular oxygen and an aqueous catholyte comprising water, an active first salt dissolved therein, and wherein the catholyte is a saturated salt solution,

wherein the protective membrane architecture comprises one or more materials configured to provide a first membrane surface chemically compatible with the lithium anode in contact with the anode, and a second membrane surface substantially impervious to and chemically compatible with the aqueous catholyte.

46. The cell of claim 45, wherein the active first salt of the saturated catholyte is selected from the group consisting of halides and nitrates.

47. The cell of claim 45, wherein the active first salt of the saturated catholyte is selected from the group consisting of ammonium halides, ammonium nitrates, and metal halides wherein the metal of the halide is not lithium.

48. The cell of claim 45, wherein the active first salt of the saturated catholyte is selected from the group consisting NH₄Br, NH₄Cl, NH₄I, NH₄NO₃, NH₄CNS, and AlCl₃.

49. The cell of claim 45, wherein the catholyte is saturated with the active first salt.

50. The cell of claim 45, wherein the saturated catholyte further comprises a second salt.

51. The cell of claim 50, wherein the second salt is selected from the group consisting of chlorides, bromides, and iodides.

52. The cell of claim 51, wherein the second salt is a lithium salt.

53. The cell of claim 52, wherein the second salt is selected from the group consisting of lithium chloride, lithium bromide, and lithium iodide.

54. The cell of claim 50, wherein the catholyte is saturated with the second salt.

55. The cell of claim 45, wherein the saturated catholyte, prior to initial discharge, has an equilibrium relative humidity of value selected from the group consisting of less than 50%, less than 40%, less than 30%, less than 20%, less than 15%, and less than 10%.