High energy density aqueous lithium/air-battery cells

• US 8,673,477 B2
• Filed: 06/12/2009
• Issued: 03/18/2014
• Est. Priority Date: 06/16/2008
• Status: Expired due to Fees

• 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, Katz, Bruce
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): Anthony, Julian
• Application Number:
  US12/484,065
• Publication Number:
  US 20090311603A1
• Time in Patent Office: 1,740 Days
• Field of Search: 429/126, 429/231.95, 429/101, 429/199, 429/201
• 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, prior to initial discharge, comprising;

a cathode for reducing molecular oxygen;

an aqueous catholyte comprising a dissolved portion of an active substance material; and

an un-dissolved solid phase portion of the active substance material, in contact with the aqueous catholyte;

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.

2. The cell of claim 1, wherein the un-dissolved solid phase portion of the active substance material is a solid phase active salt.

3. The cell of claim 2, wherein said solid phase active salt in contact with the catholyte operably dissolves therein.

4. The cell of claim 2, wherein the operable dissolution of the solid phase active salt in the catholyte generates dissolved active solute species that participate, as a reagent, in the cell reaction.

5. The cell of claim 2 wherein the solid phase active salt is hygroscopic.

6. The cell of claim 2 wherein the solid phase active salt is deliquescent.

7. The cell of claim 2, wherein the solid phase active salt comprises a halogen.

8. The cell of claim 2, wherein the solid phase active salt comprises nitrate.

9. The cell of claim 2, wherein the solid phase active salt comprises ammonium.

10. The cell of claim 2, wherein the solid phase active salt comprises a metal that is not lithium, and the solid substance operably dissolves hydrolytically in the water of the catholyte.

11. The cell of claim 10, wherein the solid phase active salt is a halide.

12. The cell of claim 11, wherein the halide is ammonium halide.

13. The cell of claim 10, wherein the solid phase active salt is a nitrate salt.

14. The cell of claim 10, wherein the solid phase active salt is a metal halide, wherein the metal of the halide is not lithium.

15. The cell of claim 10, wherein the solid phase active salt is selected from the group consisting of NH₄Cl, NH₄Br, AlCl₃, NH₄NO₃, NH₄CNS, MgCl₂.

16. The cell of claim 2, wherein the catholyte is saturated with the salt.

17. The cell of claim 2, wherein the salt is an active salt.

18. The battery cell of claim 17 wherein, prior to cell activation, the mole ratio of the solid phase active substance to active salt dissolved in the catholyte has a value selected from the group consisting of greater than 1, greater than 2, and greater than 10.

19. The battery cell of claim 17 wherein the mole ratio has a value within a range selected from the group consisting of from 2 to 3;

from 3 to 4;

from 4 to 5;

from 5 to 6;

from 6 to 7;

from 7 to 8;

from 8 to 9; and

from 9 to 10.

20. The cell of claim 2, further comprising a non-active salt.

21. The cell of claim 20, wherein the non-active salt is a lithium salt.

22. The cell of claim 1, wherein the cathode compartment further comprises a reservoir disposed between the cathode and the protected anode.

23. The cell of claim 22, wherein the reservoir comprises a porous solid structure chemically compatible with the catholyte and chemically and electrochemically compatible with the cathode.

24. The cell of claim 23, wherein at least a portion of the surface or the pore structure of the porous solid structure is substantially covered or contains and/or in contact with the solid phase active substance.

25. The cell of claim 24, wherein the solid phase active substance is present or contained in at least a portion of the pore structure of the porous solid structure, the solid phase active substance in contact with the porous solid structure.

26. The cell of claim 22, wherein the cell is figured such that prior to initial activation of the cell the reservoir comprises solid phase active substance and substantially no catholyte, and the catholyte is formed in-situ upon activation.

27. The cell of claim 22, wherein the reservoir is substantially empty and the cell is figured such that the solid phase active substance is introduced into the reservoir after cell assembly or after cell assembly but prior to initial cell discharge.

28. The cell of claim 1, wherein the aqueous catholyte is substantially formed in-situ after exposure of the cathode compartment to ambient, whereby moisture from the ambient air enters the cathode compartment and dissolves the solid phase active substance to form aqueous catholyte.

29. The cell of claim 1 wherein, prior to exposing the cathode compartment to ambient air, the compartment further comprises a solid lithium supporting electrolyte salt.

30. The cell of claim 29, wherein the aqueous catholyte is substantially formed in-situ after exposure of the cathode compartment to ambient, whereby moisture from the ambient air enters the cathode compartment and dissolves the solid lithium supporting salt to form aqueous catholyte.

31. The cell of claim 1, wherein the solid phase active substance is in the form of a compact.

32. The cell of claim 31, wherein the solid phase active substance compact further comprises a second component material.

33. The cell of claim 32, wherein the second component material is an inorganic powder.

34. The cell of claim 33, wherein the inorganic powder is selected from the group consisting of silica, alumina and titania.

35. The cell of claim 31, wherein the compact is porous.

36. The cell of claim 35, wherein the pores of the compact contain catholyte.

37. The cell of claim 1, wherein the cathode compartment is open to air.

38. The cell of claim 1, wherein the solid phase active substance contacts the air cathode.

39. The cell of claim 1, wherein, prior cell activation, the compartment is substantially devoid of liquid water.

40. The cell of claim 39, wherein the active solid substance is microencapsulated.

41. The cell of claim 1, wherein the cathode compartment further comprises a hydrogel.

42. The cell of claim 1, wherein the cathode comprises a porous solid structure.

43. The battery cell of claim 1, wherein the solid phase active substance is incorporated in the cathode compartment during cell manufacture;

and

further wherein, subsequent to the start of initial discharge, at least a portion of the solid phase active substance remains in the cathode compartment as un-dissolved solid.

44. The battery cell of claim 43, further wherein an amount of the solid phase active substance remains in the cathode compartment as an un-dissolved solid subsequent to the cell delivering a percentage of its rated discharge capacity, said percentage selected from the group consisting of 25% or 50% or 75% or 90% of its rated discharge capacity.

45. The cell of claim 1, wherein the catholyte, prior to initial discharge, has an equilibrium relative humidity of less than 50%.

46. The cell of claim 1, wherein the catholyte, prior to initial discharge, has an equilibrium relative humidity of less than 30%.

47. The cell of claim 1, wherein the catholyte, prior to initial discharge, has an equilibrium relative humidity of less than 15%.

48. The cell of claim 1, wherein the protective membrane architecture comprises one or more lithium ion conducting oxide having a garnet like structure.

49. A method of making a battery cell comprising:

providing,

a protected anode, comprising,

a lithium metal 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,

an aqueous catholyte, the catholyte comprising a dissolved portion of an active substance material, and

an un-dissolved solid phase portion of the active substance material in contact with the aqueous catholyte; and

,

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.