Protective composite battery separator and electrochemical device component with red phosphorus

• US 7,838,144 B2
• Filed: 05/29/2009
• Issued: 11/23/2010
• Est. Priority Date: 10/15/2002
• Status: Expired due to Fees

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Katz, Bruce D., Nimon, Yevgeniy S.
• Primary Examiner(s): Cantelmo; Gregg
• Application Number:
  US12/475,403
• Publication Number:
  US 20090297935A1
• Time in Patent Office: 543 Days
• Field of Search: 429/137, 429/144, 429/231.95, 429/246
• US Class Current: 429/137
• 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 protective composite battery separator, consisting essentially of:

an ionically conductive first material layer precursor comprising red phosphorus; and

a second material layer in contact with the first layer, the second material selected from the group consisting of ceramic metal ion conductors and glass ceramic active metal ion conductors;

wherein the ionic conductivity of the composite separator is at least 10<sup>−

4</sup> S/cm.

2. The separator of claim 1, wherein the second material layer is a sintered material having a thickness of about 10 to 1000 microns.

3. The separator of claim 1, wherein the ionic conductivity of the second material layer is about 10⁻

3 S/cm.

4. The separator of claim 1, wherein the thickness of the first material layer precursor is about 0.1 to 5 microns.

5. The separator of claim 1, wherein the thickness of the second material layer is about 0.1 to 1000 microns.

6. The separator of claim 1, wherein the ionic conductivity of the second material layer is between 10⁻

4 and 10<sup>−

3</sup> S/cm and the thickness of the second material layer is about 10 to 500 microns.

7. The separator of claim 6, wherein the thickness of the second material layer is 10 to 100 microns.

8. The separator of claims 1, wherein the second layer comprises a material selected from the group consisting of glass-ceramic active metal ion conductors, lithium beta-alumina, LISICON, sodium beta-alumina and NASICON.

9. The separator of claim 1, wherein the second layer is an ion conductive glass-ceramic having the following composition:

10. An electrochemical device component, comprising:

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

a protective composite separator as claimed in claim 1 on the first surface of the electrode and having a smooth gap-free interface therewith.

11. The component of claim 10, wherein the active metal of the electrode is an alkali metal.

12. The component of claim 10, wherein the active metal of the electrode is lithium or a lithium alloy.

13. The component of claim 10, wherein the second layer is an ion conductive glass-ceramic having the following composition:

14. The component of claim 13, further comprising a positive electrode chosen from a sulfur-based positive electrode, a metal oxide based positive electrode, and a metal sulfide based positive electrode in contact with said second layer material.

15. The component of claim 10, wherein a first layer comprises a composite in situ reaction product of the first material layer precursor and active metal of the negative electrode.

16. The component of claim 15, wherein the active metal of the negative electrode is lithium or a lithium alloy.