Catholytes for aqueous lithium/air battery cells

• US 8,658,304 B2
• Filed: 10/29/2012
• Issued: 02/25/2014
• 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:
  US13/663,224
• Publication Number:
  US 20130122380A1
• Time in Patent Office: 484 Days
• Field of Search: 429/126, 429/142, 429/304, 429/322, 429/323, 429/108, 429/199, 429/231.95
• 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, an active first salt dissolved therein, such that the catholyte is a saturated salt solution, and;

wherein the protective membrane architecture comprises one or more materials configured to provide a barrier to isolate the lithium anode from components of the cathode compartment while allowing for lithium metal ion transport.

2. The cell of claim 1, wherein the active first salt of the saturated catholyte is selected from the group consisting of halides and nitrates.

3. The cell of claim 1, 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.

4. The cell of claim 1, wherein the active first salt of the saturated catholyte is selected from the group consisting NH₄Br, NH₄Cl, NH₄I, NH₄NO₃, NH₄CNS, and AlCl₃.

5. The cell of claim 1, wherein the catholyte is saturated with the active first salt.

6. The cell of claim 1, wherein the saturated catholyte further comprises a second salt.

7. The cell of claim 6, wherein the second salt is selected from the group consisting of chlorides, bromides, and iodides.

8. The cell of claim 7, wherein the second salt is a lithium salt.

9. The cell of claim 8, wherein the second salt is selected from the group consisting of lithium chloride, lithium bromide, and lithium iodide.

10. The cell of claim 6, wherein the catholyte is saturated with the second salt.

11. The cell of claim 1, 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%.

12. The cell of claim 1, wherein the one or more materials of the protective membrane architecture comprises a solid electrolyte layer that is conductive to lithium ions and substantially impervious to and chemically compatible with the components of the cathode compartment.

13. The cell of claim 12, wherein the lithium ion conductivity of the solid electrolyte layer is at least 10⁻

5 S/cm.

14. 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, and;

wherein the protective membrane architecture comprises one or more materials configured to provide a barrier to isolate the lithium anode from components of the cathode compartment while allowing for lithium metal ion transport.

15. The cell of claim 14, wherein the second salt is a non-active salt.

16. The cell of claim 15, wherein the active first salt and the second salt have a common salt component.

17. The cell of claim 16, wherein the common salt component is halogen.

18. The cell of claim 17, wherein the active first halide salt and the second halide salt do not have a common halogen anion.

19. The cell of claim 17, wherein the halogen concentration in the catholyte is at least 6 Molar.

20. The cell of claim 16, wherein the common salt component is nitrate.

21. The cell of claim 20, wherein the nitrate concentration in the catholyte is at least 6 Molar.

22. The cell of claim 14, wherein the second salt is a lithium salt.

23. The cell of claim 14, wherein the second salt is a lithium halide salt.

24. The cell of claim 14, wherein the one or more materials of the protective membrane architecture comprises a solid electrolyte layer that is conductive to lithium ions and substantially impervious to and chemically compatible with the components of the cathode compartment.

25. The cell of claim 24, wherein the lithium ion conductivity of the solid electrolyte layer is at least 10⁻

5S/cm.