Substantially impervious lithium super ion conducting membranes

• US 8,334,075 B2
• Filed: 04/23/2012
• Issued: 12/18/2012
• Est. Priority Date: 12/19/2005
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., De Jonghe, Lutgard C., Nimon, Yevgeniy S.
• Primary Examiner(s): Ryan, Patrick
• Assistant Examiner(s): Lewis, Ben
• Application Number:
  US13/453,964
• Publication Number:
  US 20120270112A1
• Time in Patent Office: 239 Days
• Field of Search: 429/104, 429/126, 429/145, 429/300, 429/304, 429/306, 429321-323, 429/218.1, 429/231.95, 429/231.9, 429/236, 429/251, 429/249, 429/465, 429/475, 429/476, 429/477, 429/479, 429/489, 429/492, 429/529, 429/530, 429/532
• US Class Current: 429/231.95
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/0561 the electrolyte being constituted of inorganic materials only
• CPC Class Codes: H01M 10/0566 Liquid materials
• 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 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2300/0005 Acid electrolytes
• CPC Class Codes: H01M 2300/0017 Non-aqueous electrolytes
• CPC Class Codes: H01M 2300/0065 Solid electrolytes
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 2300/0091 in the form of mixtures
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0416 involving impregnation with a solution, dispersion, paste or dry powder H01M4/0438 takes precedence
• CPC Class Codes: H01M 4/08 Processes of manufacture
• 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 4/131 : Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 : Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/139 : Processes of manufacture
• CPC Class Codes: H01M 4/242 : Hydrogen storage electrodes
• CPC Class Codes: H01M 4/32 : Nickel oxide or hydroxide electrodes
• CPC Class Codes: H01M 4/38 : of elements or alloys
• CPC Class Codes: H01M 4/383 : Hydrogen absorbing alloys
• CPC Class Codes: H01M 4/385 : of the type LaNi5
• CPC Class Codes: H01M 4/387 : Tin or alloys based on tin
• CPC Class Codes: H01M 4/62 : Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/86 : Inert electrodes with catalytic activity, e.g. for fuel cells
• 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 6/16 : with organic electrolyte H01M6/18 takes precedence
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: H01M 6/185 : with oxides, hydroxides or oxysalts as solid electrolytes
• CPC Class Codes: H01M 6/188 : Processes of manufacture
• CPC Class Codes: H01M 6/24 : Cells comprising two different electrolytes
• CPC Class Codes: H01M 6/34 : Immersion cells, e.g. sea-water cells
• CPC Class Codes: H01M 8/08 : Fuel cells with aqueous electrolytes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells

Abstract

A composite solid electrolyte includes a monolithic solid electrolyte base component that is a continuous matrix of an inorganic active metal ion conductor and a filler component used to eliminate through porosity in the solid electrolyte. In this way a solid electrolyte produced by any process that yields residual through porosity can be modified by the incorporation of a filler to form a substantially impervious composite solid electrolyte and eliminate through porosity in the base component. Such composites may be made by disclosed techniques. The composites are generally useful in electrochemical cell structures such as battery cells and in particular protected active metal anodes, particularly lithium anodes, that are protected with a protective membrane architecture incorporating the composite solid electrolyte.

Claims

1. A substantially impervious metal ion conductive composite solid electrolyte layer comprising:

a monolithic metal ion conductive continuous inorganic solid electrolyte membrane base component of a material selected from the group consisting of ceramic and glass-ceramic, the membrane base component having fluid permeable through pores that extend from one major surface of the base component membrane to an opposing major surface;

a filler component, the filler component not conductive to metal ions, the filler component contained in the membrane through pores, and therein providing a fluid barrier;

wherein the composite layer has a metal ion conductivity of at least 10<sup>−

6</sup> S/cm.

2. The solid electrolyte layer of claim 1, wherein the membrane base component is a ceramic.

3. The solid electrolyte layer of claim 2, wherein the ceramic is a sintered ceramic.

4. The solid electrolyte layer of claim 3, wherein the ceramic membrane base component comprises an inorganic solid electrolyte material selected from the group consisting of lithium metal phosphate.

5. The solid electrolyte layer of claim 2, wherein the ceramic membrane base component comprises an inorganic solid electrolyte material selected from the group consisting of lithium titanium phosphate, lithium germanium phosphate, and lithium hafnium phosphate.

6. The solid electrolyte layer of claim 2, wherein the base component is sodium beta alumina.

7. The solid electrolyte layer of claim 2, wherein the filler component comprises a ceramic.

8. The solid electrolyte layer of claim 2, wherein the filler component comprises a glass.

9. The solid electrolyte layer of claim 2, wherein the filler component comprises a glass-ceramic.

10. The solid electrolyte layer of claim 1, wherein the membrane base component is a glass-ceramic.

11. The solid electrolyte layer of claim 10, wherein the glass-ceramic is a sintered glass-ceramic.

12. The solid electrolyte layer of claim 11, wherein the glass-ceramic membrane base component comprises an inorganic solid electrolyte material selected from the group consisting of lithium metal phosphate.

13. The solid electrolyte layer of claim 10, wherein the glass-ceramic membrane base component comprises an inorganic solid electrolyte material selected from the group consisting of lithium titanium phosphate, lithium germanium phosphate, and lithium hafnium phosphate.

14. The solid electrolyte layer of claim 10, wherein the filler component comprises a ceramic.

15. The solid electrolyte layer of claim 10, wherein the filler component comprises a glass.

16. The solid electrolyte layer of claim 10, wherein the filler component comprises a glass-ceramic.

17. The solid electrolyte layer of claim 10, wherein said metal ion is lithium.

18. The solid electrolyte layer of claim 10, wherein said metal ion is sodium.

19. A protected anode, comprising:

an active metal anode having a first and second surface;

a protective membrane architecture on at least the first surface of the anode, the architecture having ionic conductivity of the active metal of at least 10<sup>−

6</sup> S/cm; and

,

wherein the protective membrane architecture comprises a substantially impervious metal ion conductive composite solid electrolyte layer according to claim 1.

20. The protected anode of claim 19, wherein said metal ion is lithium.

21. The protected anode of claim 19, wherein said metal ion is sodium.

22. A battery cell, comprising:

an anode;

a cathode; and

,

a substantially impervious metal ion conductive composite solid electrolyte layer according to claim 1, the solid electrolyte layer disposed between the anode and cathode.

23. The battery cell of claim 22, wherein said metal ion is lithium.

24. The battery cell of claim 22, wherein said metal ion is sodium.