Li/Air non-aqueous batteries

• US 8,652,692 B2
• Filed: 11/22/2006
• Issued: 02/18/2014
• Est. Priority Date: 11/23/2005
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Nimon, Yevgeniy S., Katz, Bruce
• Primary Examiner(s): Wang, Eugenia
• Application Number:
  US11/562,883
• Publication Number:
  US 20070117007A1
• Time in Patent Office: 2,645 Days
• Field of Search: 429/403, 429/405, 429/144, 429/326, 429/339, 429/340, 429/341, 429/231.9, 429/231.95, 429/246
• US Class Current: 429/405
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/381 Alkaline or alkaline earth metals elements H01M4/40 takes precedence
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 50/434 Ceramics
• CPC Class Codes: H01M 50/437 Glass
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: H01M 6/16 with organic electrolyte H01M6/18 takes precedence
• CPC Class Codes: H01M 6/164 by the solvent
• CPC Class Codes: H01M 6/185 with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: H01M 6/187 : Solid electrolyte characterised by the form
• CPC Class Codes: H01M 6/22 : Immobilising of electrolyte
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Non-aqueous alkali metal (e.g., Li)/oxygen battery cells constructed with a protected anode that minimizes anode degradation and maximizes cathode performance by enabling the use of cathode performance enhancing solvents in the catholyte have negligible self-discharge and high deliverable capacity. In particular, protected lithium-oxygen batteries with non-aqueous catholytes have this improved performance.

Claims

1. A non-aqueous alkali metal/oxygen battery cell, comprising:

a protected anode, comprising,

an alkali 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 an oxygen electrode, molecular oxygen, and a non-aqueous oxygen electrode-compatible catholyte comprising a first alkali metal anode-incompatible solvent, the first alkali metal anode-incompatible solvent in contact with and enhancing the performance of the oxygen electrode, the first alkali metal anode-incompatible solvent not in contact with the alkali metal anode, the first alkali metal anode-incompatible solvent selected from the group consisting of amides, amines, nitriles, organophosphorous solvents, organosulfur solvents, alcohols, diols and liquid polyols; 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; and

further wherein the cell is configured for electrochemical reduction of the molecular oxygen on the surface or in the bulk of the oxygen electrode to produce lithium peroxide and electrochemical oxidation at the anode without contact between the alkali metal anode and the first alkali metal anode-incompatible solvent.

2. The battery cell of claim 1 wherein the oxygen electrode is exposed to ambient air and the molecular oxygen is accessed from the ambient air.

3. The battery cell of claim 2 wherein the protective membrane architecture comprises at least a first material component in contact with the anode and a second material component in contact with the components of the cathode compartment.

4. The battery cell of claim 3 wherein the second material component is substantially impervious.

5. The battery cell of claim 4 wherein the second material component is about 10 to 1000 microns thick.

6. The battery cell of claim 5 wherein the second material component has conductivity of at least 10⁻

5 S/cm.

7. The battery cell of claim 6 wherein the second material component comprises a material selected from the group consisting of polycrystalline ceramics, glass ceramics and glass.

8. The battery cell of claim 7 wherein the second material component comprises a material selected from the group consisting of phosphorous based glass, oxide based glass, oxide sulfide based glass, selenide glass, gallium based glass, germanium based glass, sodium and lithium beta-alumina, glass ceramic alkali metal ion conductors, and Nasiglass.

9. The battery cell of claim 7 wherein the second material component comprises a polycrystalline ceramic selected from the group consisting of LISICON, NASICON, Li_0.3La_0.7TiO₃, sodium and lithium beta alumina.

10. The battery cell of claim 9 wherein the second component material comprises a LISICON polycrystalline ceramic selected from the group consisting of lithium metal phosphates.

11. The battery cell of claim 10 wherein the lithium metal phosphates have the formula Li_1+x+r(Ti₂₋

yGe_y)<sub>2−

x</sub>(Al<sub>2−

z</sub>Ga_z)_xSi_rP<sub>3−

y</sub>O₁₂ wherein (0.0≦

x≦

0.9) and (0.0≦

y≦

2.0) and (0.0≦

z≦

2.0) and (0.0≦

r≦

1.0).

12. The battery cell of claim 10 wherein the second component is LiTi₂(PO₄)₃.

13. The battery cell of claim 7 wherein the glass ceramic is

14. The battery cell of claim 3 wherein the first material component is a separator layer comprising a semi-permeable membrane impregnated with anolyte.

15. The battery cell of claim 14 wherein the semi-permeable membrane is a microporous polymer.

16. The battery cell of claim 15 wherein the anolyte is in a liquid phase.

17. The battery cell of claim 16 wherein the anolyte is in a gel phase.

18. The battery cell of claim 16 wherein the first material component comprises LiPON.

19. The battery cell of claim 3 wherein the first material component comprises a material selected from the group consisting of a composite reaction product of alkali metal with Cu₃N, alkali metal nitrides, alkali metal phosphides, alkali metal halides, alkali metal phosphorus sulfide glass and alkali metal phosphorous oxynitride glass.

20. The battery cell of claim 19 wherein the first material component comprises a material selected from the group consisting of a composite reaction product of alkali metal with Cu₃N, L₃N, Li₃P, LiI, LiF, LiBr, LiCl and LiPON.

21. The battery cell of claim 20 wherein the alkali metal anode comprises lithium and the first material component comprises the composite reaction product of Li with Cu₃N.

22. The battery cell of claim 2 wherein the battery cell self discharge rate after battery activation is less than 0.01 mA/cm².

23. The battery cell of claim 2 wherein a moisture content of the non-aqueous catholyte is greater than 100 ppm.

27. The battery cell of claim 1 wherein the first alkali metal anode-incompatible solvent is a non-aqueous protic solvent.

28. The battery cell of claim 27 wherein the non-aqueous protic solvent is present in the catholyte to at least 20% by solvent volume of the catholyte.

29. The battery cell of claim 27 wherein the non-aqueous protic solvent is selected from the group consisting of alcohols, diols and liquid polyols.

30. The battery cell of claim 29 wherein the non-aqueous protic solvent is a diol.

31. The battery cell of claim 30 wherein the diol is ethylene glycol.

32. The battery cell of claim 1 wherein the non-aqueous catholyte comprises a non-aqueous donor solvent and a non-aqueous acceptor solvent.

33. The battery cell of claim 32 wherein the non-aqueous donor solvent is present in the catholyte to at least 20% by solvent volume of the catholyte.

34. The battery cell of claim 33 wherein the donor solvent is N,N-dimethylformamide (DMF).

35. The battery cell of claim 32 wherein the non-aqueous acceptor solvent is present in the catholyte to at least 20% by solvent volume of the catholyte.

36. The battery cell of claim 35 wherein the acceptor solvent is ethylene glycol.

37. The battery cell of claim 32 wherein the ratio of donor to acceptor solvent ratio is in the range of about 1 to 10 to about 10 to 1.

38. The battery cell of claim 37 wherein the donor solvent and the acceptor solvent are both present in the catholyte to about 50% by solvent volume of the catholyte.

39. The battery cell of claim 37 wherein the donor solvent is present in the catholyte to about 35% and the acceptor solvent is present in the catholyte to about 65% by solvent volume of the catholyte.

40. The battery cell of claim 39 wherein the acceptor solvent is ethylene glycol.

41. The battery cell of claim 40 wherein the donor solvent is N,N-dimethylformamide (DMF).

42. The battery cell of claim 1, wherein the non-aqueous catholyte further comprises a non-aqueous solvent that is compatible with the alkali metal anode.

43. The battery cell of claim 42 wherein the non-aqueous solvent that is compatible with the alkali metal anode is selected from the group consisting of ethers, glymes, carbonates, and g-butyrolactone (GBL).

44. The battery cell of claim 1 wherein the cathode compartment further comprises a porous reservoir layer disposed between the second surface of the protective membrane architecture and the oxygen electrode, in contact with the oxygen electrode.

45. The battery cell of claim 44 wherein the porous reservoir layer is fully oxidized.

46. The battery cell of claim 45 wherein the fully oxidized porous reservoir layer is a metal oxide.

47. The battery cell of claim 46 wherein the reservoir layer is porous ZrO₂.

48. The battery cell of claim 1 wherein the deliverable capacity is greater than 10 mAh/cm².

49. The battery cell of claim 1 wherein the alkali metal anode is solid-state and non-flowing.

50. The battery cell of claim 1 wherein the alkali metal anode is selected from the group consisting of an alkali metal, an alkali metal intercalation material and an alkali metal alloy.

51. The battery cell of claim 1 wherein the alkali metal anode is a carbon alkali metal intercalation material.

52. The battery cell of claim 1 wherein the alkali metal anode is lithium metal.

53. The battery cell of claim 52 wherein a thickness of the lithium metal is greater than 100 um.

54. The battery cell of claim 52 wherein the alkali metal anode is lithium metal foil.

55. The battery cell of claim 54 wherein the lithium foil has a thickness greater than 100 um.

56. The battery cell of claim 1 wherein the first alkali metal anode-incompatible solvent is present in the catholyte to at least 5% by solvent volume.

57. The battery cell of claim 1 wherein the first alkali metal anode-incompatible solvent is present in the catholyte to at least 10% by solvent volume.

58. The battery cell of claim 1 wherein the first alkali metal anode-incompatible solvent is present in the catholyte to at least 20% by solvent volume.

59. The battery cell of claim 1 wherein the first alkali metal anode-incompatible solvent is an amide.

60. The battery cell of claim 59 wherein the first alkali metal anode-incompatible solvent is dimethylformamide.

61. The battery cell of claim 1 wherein the non-aqueous catholyte further comprises a second alkali metal anode incompatible, cathode performance enhancing, electrolyte solvent that is different from the first alkali metal anode-incompatible solvent, the second solvent selected from the group consisting of amides, amines, nitriles, organophosphorous solvents, organosulfur solvents, alcohols, diols and liquid polyols;

and

wherein the electrochemical reduction of molecular oxygen occurs on the surface or in the bulk of the oxygen electrode in contact with the non-aqueous catholyte and the electrochemical oxidation takes place at the anode without contact between the alkali metal anode and the second solvent.

62. The battery cell of claim 61 wherein the second solvent is a diol or liquid polyol.

63. The battery cell of claim 61 wherein the second solvent is ethylene glycol.

64. The battery cell of claim 61 wherein the second solvent is a nitrile.

65. The battery cell of claim 61 wherein the second solvent is acetonitrile.

66. The battery cell of claim 61 wherein the second solvent is an alcohol.

67. The battery cell of claim 61 wherein the second solvent is an amine.

68. The battery cell of claim 61 wherein the second solvent is an organophosphrous solvent or an organosulfur solvent.

69. The battery cell of claim 1 wherein the first alkali metal anode-incompatible solvent is characterizable as adversely reacting with and degrading the surface of the alkali metal anode material in contact with said anode material.

70. The battery cell of claim 69 wherein the first alkali metal anode-incompatible solvent is further characterizable as aggressively corroding the alkali metal anode material in contact with the anode material.

71. The battery cell of claim 69 wherein a concentration of HF in the catholyte is less than 10 ppm.

72. The battery cell of claim 1 wherein the catholyte further comprises an alkali metal cation salt.

73. The battery cell of claim 1 wherein the alkali metal cation salt does not react with moisture to form HF.

24. The battery cell of 1 wherein the first alkali metal anode-incompatible solvent is present in the catholyte to at least 20% by solvent volume.

25. The battery cell of claim 24 wherein the first alkali metal anode-incompatible solvent is selected from the group consisting of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), hexamethylphosphoramide (HMPA), and acetonitrile (AN).

26. The battery cell of claim 25 wherein the first alkali metal anode-incompatible solvent is N,N-dimethylformamide (DMF).