Electrochemical device component with protected alkali metal electrode

• US 7,858,223 B2
• Filed: 06/28/2007
• Issued: 12/28/2010
• Est. Priority Date: 10/15/2002
• Status: Expired due to Fees

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Katz, Bruce D., Visco, Steven J., Nimon, Yevgeniy S.
• Primary Examiner(s): Cantelmo; Gregg
• Application Number:
  US11/824,579
• Publication Number:
  US 20080057387A1
• Time in Patent Office: 1,279 Days
• Field of Search: 429/137, 429/14, 429/231.95, 429/246, 429/144
• US Class Current: 429/137
• CPC Class Codes: C03C 10/00 Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
• CPC Class Codes: C03C 4/18 for ion-sensitive glass
• 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 10/056 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 10/0583 of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2300/0065 Solid electrolytes
• 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 4/366 as layered products
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/489 Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• 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

Abstract

Disclosed are ionically conductive composites for protection of active metal anodes and methods for their fabrication. The composites may be incorporated in active metal negative electrode (anode) structures and battery cells. In accordance with the invention, the properties of different ionic conductors are combined in a composite material that 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 composite 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 composite is incorporated.

Claims

1. An electrochemical device component, comprising:

an active metal electrode comprising an alkali metal or alkali metal alloy and having a first surface and a second surface;

a protective composite on the first surface of the electrode, the composite comprising,

a first material layer in contact with the electrode, the first material being ionically conductive to ions of the active metal and chemically compatible with the active metal, the first layer comprising a reaction product of the active metal with red phosphorous; and

a substantially impervious second material layer adjacent to and in active metal ion communication with the first layer, the second layer ionically conductive to ions of the active metal;

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

7</sup> S/cm.

2. The component of claim 1, wherein the first material layer is in contact and chemically compatible with the second material layer.

3. The component of claim 1, wherein the second material layer is reactive to the active metal electrode.

4. The component of claim 1, wherein the second material layer is polymer-free.

5. The component of claim 1, wherein the second material layer consists essentially of an inorganic solid electrolyte inherently ionically conductive to ions of the active metal.

6. The component of claim 5, wherein the inorganic solid electrolyte of said second layer has an active alkali metal ion conductivity of at least 10⁻

5 S/cm.

7. The component of claim 6, wherein the active metal is Li.

8. The component of claim 7, wherein the second material layer is an inorganic solid electrolyte.

9. The component of claim 1, wherein the thickness of the first material layer is about 0.2 to 1 micron.

10. The component of claim 1, wherein the inorganic solid electrolyte of the second material layer is a ceramic.

11. The component of claim 10, wherein the inorganic solid electrolyte of the second material layer is selected from the group consisting of lithium beta alumina, LiSICON, sodium beta alumina and NaSICON.

12. The component of claim 10, wherein the inorganic solid electrolyte of the second material layer is a glass-ceramic.

13. The component of claim 7, wherein the inorganic solid electrolyte of the second material layer comprises an ion conductive glass-ceramic having the following composition:

14. The component of claim 10, wherein the inorganic solid electrolyte is a glassy or amorphous compound selected from the group consisting of phosphorous based glass, oxide based glass, sulfur based glass, oxide sulfur based glass, selenide based glass, gallium based glass, germanium based glass.

15. The component of claim 1, wherein the thickness of the second material layer thickness is about 0.1 to 1000 micron.

16. The component of claim 1, wherein the thickness of the second material layer thickness is about 0.25 to 1 micron.

17. The component of claim 1, wherein the ionic conductivity of the second material layer is between about 10⁻

3 to 10<sup>−

6</sup> S/cm.

18. The component of claim 1, wherein the alkali metal comprises lithium.

19. The component of claim 18, wherein the first layer material comprises Li₃P.