Battery cells with lithium ion conducting tape-cast ceramic, glass and glass-ceramic membranes

• US 9,601,779 B2
• Filed: 06/03/2016
• Issued: 03/21/2017
• Est. Priority Date: 10/14/2003
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Nimon, Yevgeniy S.
• Primary Examiner(s): Le, Emily
• Assistant Examiner(s): WILLS, MONIQUE M
• Application Number:
  US15/173,303
• Publication Number:
  US 20160351911A1
• Time in Patent Office: 291 Days
• 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 10/0562 Solid materials
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 10/24 Alkaline accumulators
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 10/38 Construction or manufacture
• 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 16/00 Structural combinations of different types of electrochemical generators
• CPC Class Codes: H01M 16/003 of fuel cells with other electrochemical devices, e.g. capacitors, electrolysers
• CPC Class Codes: H01M 2300/0071 Oxides
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/628 Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: H01M 50/414 Synthetic resins, e.g. thermoplastics or thermosetting resins
• CPC Class Codes: H01M 50/431 Inorganic material
• CPC Class Codes: H01M 50/434 Ceramics
• CPC Class Codes: H01M 50/437 Glass
• CPC Class Codes: H01M 50/451 : comprising layers of only organic material and layers containing inorganic material
• CPC Class Codes: H01M 6/04 : Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/34 : Immersion cells, e.g. sea-water cells
• CPC Class Codes: H01M 8/1016 : characterised by the electrolyte material H01M8/12 takes precedence
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells
• 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 29/4911 : including sealing
• CPC Class Codes: Y10T 29/49115 : including coating or impregnating

Abstract

Alkali (or other active) metal battery and other electrochemical cells incorporating active metal anodes together with aqueous cathode/electrolyte systems. The battery cells have a highly ionically conductive protective membrane adjacent to the alkali metal anode that effectively isolates (de-couples) the alkali metal electrode from solvent, electrolyte processing and/or cathode environments, and at the same time allows ion transport in and out of these environments. Isolation of the anode from other components of a battery cell or other electrochemical cell in this way allows the use of virtually any solvent, electrolyte and/or cathode material in conjunction with the anode. Also, optimization of electrolytes or cathode-side solvent systems may be done without impacting anode stability or performance. In particular, Li/water, Li/air and Li/metal hydride cells, components, configurations and fabrication techniques are provided.

Claims

1. A method of making an electrochemical cell structure, the method comprising:

tape-casting an inherently lithium ion conductive separator membrane selected from the group consisting of a glass, a ceramic and a glass-ceramic, the membrane having a first surface and a second surface; and

assembling the tape-cast inherently lithium ion conductive separator membrane with a lithium-containing anode adjacent to the first surface;

wherein the membrane effectively isolates the lithium-containing anode from an environment at the second surface of the membrane, while allowing transport of lithium ions across the membrane, the membrane having a lithium ion conductivity of at least 10<sup>−

5</sup>S/cm.

2. The method of claim 1, wherein following tape-casting, the inherently lithium ion conductive separator membrane is fired to full density.

3. The method of claim 2, wherein the tape-cast inherently lithium ion conductive separator membrane is selected from the group consisting of a ceramic and a glass-ceramic.

4. The method of claim 3, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Ga, Ge, Ti, Nb and Zr.

5. The method of claim 4, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Ge and Ti.

6. The method of claim 4, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Nb and Zr.

7. The method of claim 1, wherein the tape-cast inherently lithium ion conductive separator membrane the membrane has a lithium ion conductivity of at least 10⁻

4S/cm.

8. An electrochemical cell structure, comprising:

a tape-cast inherently lithium ion conductive separator membrane selected from the group consisting of a glass, a ceramic and a glass-ceramic, the membrane having a first surface and a second surface; and

a lithium-containing anode on the first surface of the membrane;

wherein the membrane effectively isolates the lithium-containing anode from an environment at the second surface of the membrane, while allowing transport of lithium ions across the membrane, the membrane having a lithium ion conductivity of at least 10<sup>−

5</sup>S/cm.

9. The electrochemical cell structure of claim 8, wherein the tape-cast inherently lithium ion conductive separator membrane is a dense ceramic or a glass-ceramic comprising an element selected from the group consisting of Ga, Ge, Ti, Nb and Zr.

10. The electrochemical cell structure of claim 9, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Ge and Ti.

11. The electrochemical cell structure of claim 9, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Nb and Zr.

12. The electrochemical cell structure of claim 8, wherein the tape-cast inherently lithium ion conductive separator membrane the membrane has a lithium ion conductivity of at least 10⁻

4S/cm.

20. The battery cell of claim 8, wherein the tape-cast inherently lithium ion conductive separator membrane the membrane has a lithium ion conductivity of at least 10⁻

4S/cm.

13. A battery cell comprising:

a tape-cast inherently lithium ion conductive separator membrane selected from the group consisting of a glass, a ceramic and a glass-ceramic, the membrane having a first surface and a second surface;

a lithium-containing anode on the first surface of the membrane; and

a cathode environment comprising a cathode adjacent the second surface of the membrane;

wherein the membrane effectively isolates the lithium-containing anode from the cathode environment, while allowing transport of lithium ions across the membrane, the membrane having a lithium ion conductivity of at least 10<sup>−

5</sup>S/cm.

14. The battery cell of claim 13, wherein the tape-cast inherently lithium ion conductive separator membrane comprises a dense ceramic or glass-ceramic comprising an element selected from the group consisting of Ga, Ge, Ti, Nb and Zr.

15. The battery cell of claim 14, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Ge and Ti.

16. The battery cell of claim 14, wherein the tape-cast inherently lithium ion conductive separator membrane comprises an element selected from the group consisting of Nb and Zr.

17. The battery cell of claim 13, wherein the cathode comprises a transition metal oxide.

18. The battery cell of claim 13, wherein the cathode comprises on ionic liquid.

19. The battery cell of claim 13, further comprising a porous polyolefin separator disposed between the cathode and the second surface of the membrane.