Protected active metal electrode and battery cell with ionically conductive protective architecture

• US 8,293,398 B2
• Filed: 09/22/2010
• Issued: 10/23/2012
• Est. Priority Date: 02/06/2004
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Katz, Bruce D., Nimon, Yevgeniy S., De Jonghe, Lutgard C.
• Primary Examiner(s): Dove, Tracy
• Application Number:
  US12/888,154
• Publication Number:
  US 20110014522A1
• Time in Patent Office: 762 Days
• Field of Search: 429/117, 429/126, 429/142, 429/300, 429/303, 429337-339, 429/231.95
• US Class Current: 429/126
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/52 Separators
• CPC Class Codes: H01G 11/58 Liquid electrolytes
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• 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 2300/0002 Aqueous electrolytes
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 50/451 comprising layers of only organic material and layers containing inorganic material
• 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: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• 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

Active metal and active metal intercalation electrode structures and battery cells having ionically conductive protective architecture including an active metal (e.g., lithium) conductive impervious layer separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers. Safety additives and designs that facilitate manufacture are also provided.

Claims

1. An electrochemical cell structure, comprising:

an anode comprising a material selected from the group consisting of an active metal, active metal-ion, active metal alloy, active metal alloying metal and active metal intercalating material; and

an ionically conductive protective architecture on a first surface of the anode, the architecture comprising,

an active metal ion conducting separator layer comprising a semi-permeable polymer membrane comprising a non-aqueous anolyte, the separator layer being chemically compatible with the active metal, and in contact with the anode, and

a substantially impervious ionically conductive layer chemically compatible with the separator layer, and in contact with the separator layer.

2. The structure of claim 1, wherein the anolyte is in the liquid phase.

3. The structure of claim 1, wherein the anolyte is in the gel phase.

4. The structure of claim 1, wherein the substantially impervious ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.

5. The structure of claim 4, wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:

6. The structure of claim 1, wherein the protective architecture has an ionic conductivity of at least 10⁻

4S/cm.

7. The structure of claim 1, wherein the active metal anode is selected from the group consisting of lithium metal, lithium metal alloy and lithium intercalation material.

8. The structure of claim 7, wherein the active metal anode is lithium metal.

9. The structure of claim 1, wherein the anode comprises lithium metal-ions.

10. The structure of claim 1, wherein the anode comprises lithium metal alloying metal.

11. The structure of claim 10, wherein the lithium metal alloying metal is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb.

12. The structure of claim 1, wherein the anode comprises lithium metal intercalating material.

13. The structure of claim 12, wherein the lithium metal intercalating material comprises carbon.

14. A battery cell, comprising:

an electrochemical cell structure in accordance with claim 1; and

a cathode structure.

15. The cell of claim 14, wherein the cathode structure comprises a catholyte selected from the group consisting of aqueous and non-aqueous electrolytes.

16. The cell of claim 15, wherein the cathode structure further comprises electrochemically active material selected from the group consisting of solid, liquid and gaseous oxidizers.

17. The cell of claim 14, wherein the cathode structure comprises seawater.

19. The cell of claim 14, wherein the cathode structure comprises an ionic liquid.

20. The cell of claim 14, wherein the active metal anode is lithium metal.

21. The cell of claim 14, wherein the anode comprises lithium metal-ions.

22. The cell of claim 14, wherein the anode comprises lithium metal alloying metal.

23. The cell of claim 14, wherein the anode comprises lithium metal intercalating material.

24. The cell of claim 22 wherein the lithium metal intercalating material comprises carbon.

25. The cell of claim 14, wherein the anolyte is in the liquid phase.

26. The cell of claim 14, wherein the anolyte is in the gel phase.

27. The cell of claim 14, wherein the substantially impervious ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.

28. The structure of claim 22, wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:

29. The cell of claim 14, wherein the protective architecture has an ionic conductivity of at least 10⁻

4S/cm.

18. The cell of clam 14, wherein the cathode structure comprises an air electrode.