Advanced lithium ion batteries based on solid state protected lithium electrodes

• US 9,362,538 B2
• Filed: 05/30/2014
• Issued: 06/07/2016
• Est. Priority Date: 10/15/2002
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Nimon, Yevgeniy S., Katz, Bruce D.
• Primary Examiner(s): Cantelmo, Gregg
• Application Number:
  US14/292,699
• Publication Number:
  US 20140272524A1
• Time in Patent Office: 739 Days
• Field of Search: None
• US Class Current: 1/1
• 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 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• 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 2300/0065 Solid electrolytes
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/008 Halides
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• 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 6/18 with solid electrolyte
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: H01M 6/182 with halogenide as solid electrolyte
• 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 6/188 Processes of manufacture
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• 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
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

Disclosed are ionically conductive membranes for protection of active metal anodes and methods for their fabrication. The membranes may be incorporated in active metal negative electrode (anode) structures and battery cells. In accordance with the invention, the membrane has the desired properties of high overall ionic conductivity and chemical stability towards the anode, the cathode and ambient conditions encountered in battery manufacturing. The membrane is capable of protecting an active metal anode from deleterious reaction with other battery components or ambient conditions while providing a high level of ionic conductivity to facilitate manufacture and/or enhance performance of a battery cell in which the membrane is incorporated.

Claims

1. A battery cell, comprising:

an anode and a lithium ion cathode comprising a lithium ion intercalation compound;

wherein the anode is an electrochemical device component comprising;

an active metal lithium electrode having a first surface and a second surface; and

a composite protective membrane on the first surface of the electrode, the composite protective membrane being ionically conductive and chemically compatible with the active metal lithium on a side in contact with the active metal electrode, and substantially impervious, ionically conductive and chemically compatible with active metal lithium corrosive environments on the other side, the membrane comprising a substantially impervious sintered ceramic or glass-ceramic layer having a thickness between 10 and 1000 microns;

wherein the ionic conductivity of the membrane is at least 10-7 S/cm;

a current collector on the second surface of the active metal electrode; and

wherein the device component can be handled or stored in normal ambient atmospheric conditions without degradation prior to incorporation into an electrochemical device.

2. The battery cell of claim 1, wherein the active metal electrode is lithium metal.

3. The battery cell of claim 1, wherein the active metal electrode comprises a lithium alloy.

4. The battery cell of claim 1, wherein ceramic is a sintered ceramic.

5. The battery cell of claim 1, wherein ceramic is a glass-ceramic.

6. The battery cell of claim 1, further comprising a liquid electrolyte disposed between and in contact with the cathode and the protective membrane.

7. The battery cell of claim 1, wherein the composite protective membrane further comprises a lithium ion conductive material interlayer in direct contact with the active lithium metal electrode and the substantially impervious layer, the interlayer chemically compatible with the impervious layer and the active lithium metal electrode.

8. The battery cell of claim 7, wherein the interlayer thickness is in the range of 0.1 to 5 microns.

9. The battery cell of claim 7, wherein the interlayer thickness is in the range of 0.2 to 1 micron.

10. The battery cell of claim 7, wherein the interlayer is a lithium ion conducting glass.

11. The battery cell of claim 7, wherein the interlayer comprises LiPON.

12. The battery cell of claim 7, wherein the interlayer is a layer of LiPON.

13. The battery cell of claim 7, wherein the interlayer comprises a material selected from the group consisting of lithium nitride, lithium phosphide, and lithium iodide.

14. The battery cell of claim 7, wherein the interlayer comprises a material selected from the group consisting of Li₃N, LI, and Li₃P.

15. The battery cell of claim 7, wherein the interlayer comprises the reaction product of a precursor material layer with lithium metal.

16. The battery cell of claim 15, wherein the precursor material is selected from the group consisting of copper nitride, tin nitride, zinc nitride, iron nitride, cobalt nitride, aluminum nitride and silicon nitride.

17. The battery cell of claim 15, wherein the precursor material comprises red phosphorous.

18. The battery cell of claim 15, wherein the precursor material comprises I₂.

19. The battery cell of claim 1, wherein the lithium ion intercalation cathode is a 4V cathode.

20. The battery cell of claim 1, wherein the lithium ion intercalation cathode is a 5V cathode.

21. The battery cell of claim 1, wherein the lithium ion intercalation compound is a metal oxide or a metal sulfide.

22. The battery cell of claim 1, wherein the lithium ion intercalation compound is a metal oxide.

23. The battery cell of claim 1, wherein the intercalation compound comprises a transition metal selected from the group consisting of Co, Ni, Mn, Fe, V, Mo, Cu, Ti and Cr.

24. The battery cell of claim 1 wherein the intercalation compound comprises a transition metal selected from the group consisting Co, Ni, Mn and Fe.

25. The battery cell of claim 1 wherein the intercalation compound is selected from the group consisting of LixCoO₂, LixNiO₂, LixMn₂O₄ and LiFePO₄.

26. The battery cell of claim 1 wherein the intercalation compound is unlithiated.

27. The battery cell of claim 1, further comprising a liquid electrolyte disposed between and in contact with the cathode and the protective membrane, and not in contact with the active lithium metal electrode.

28. The battery cell of claim 27, wherein the liquid electrolyte comprises a solvent selected from the group consisting of organic carbonate, ether, and ester.

29. The battery cell of claim 27, wherein the liquid electrolyte comprises at least one solvent or salt that is chemically incompatible with the active lithium metal electrode.

30. The battery cell of claim 29, wherein the liquid electrolyte comprises a the salt that is an ionic liquid.

31. The battery cell of claim 30, wherein the ionic liquid is selected from the group consisting of imidazolium, pyridinium, phosphonium and tetralkylammonium compounds.

32. The battery cell of claim 1, further comprising a gel electrolyte disposed between and in contact with the cathode and the protective membrane, and not in contact with the active lithium metal electrode.

33. The battery cell of claim 1, wherein the cathode lithium ion intercalation compound is a lithium metal oxide.

34. The battery cell of claim 1, wherein the cathode lithium ion intercalation compound is selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide and lithium iron phosphate.

35. The battery cell of claim 1, wherein the cathode lithium ion intercalation compound is unlithiated.

36. The battery cell of claim 35, wherein the cathode lithium ion intercalation compound is a metal oxide or a metal sulfide.