ELECTROCHEMICAL DEVICE HAVING A SOLID ALKALINE ION-CONDUCTING ELECTROLYTE AND AN AQUEOUS ELECTROLYTE

• US 20120183868A1
• Filed: 10/21/2010
• Published: 07/19/2012
• Est. Priority Date: 10/27/2009
• Status: Active Grant

• Current Assignee: Electricitã© De France
• Original Assignee: Electricitã© De France
• Inventors: Stevens, Philippe, Toussaint, Gwenaelle
• Granted Patent: US 9,178,221 B2
• Time in Patent Office: Days
• US Class Current: 429/403
• CPC Class Codes: H01M 10/26 Selection of materials as electrolytes
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0094 in the form of layered products, e.g. coatings
• 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: H01M 6/24 Cells comprising two different electrolytes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present invention relates to an alkaline cation-conducting ceramic membrane covered, over at least a portion of the surface thereof, with a cation-conducting organic polyelectrolyte layer that is insoluble and chemically stable in pH-basic water. The invention also relates to an electrochemical device including such a membrane as a solid electrolyte in contact with a liquid electrolyte formed of an alkali metal hydroxide aqueous solution.

Claims

1. (canceled)

2. (canceled)

3. (canceled)

4. (canceled)

5. (canceled)

6. (canceled)

7. (canceled)

8. (canceled)

9. (canceled)

10. (canceled)

11. (canceled)

12. (canceled)

13. A ceramic membrane, the ceramic membrane comprising:

at least part of the surface of the membrane being covered with an organic polymer layer comprising an organic cation-conductive polyelectrolyte, said organic polymer layer being insoluble and chemically stable in water at basic pH.

14. The ceramic membrane as claimed in claim 13, wherein it is a ceramic membrane with the chemical formula:

Li_1+x(M,Ga,Al)_x(Ge_1-yTi_y)_2-x(PO₄)₃,

where M is one or more metals chosen from Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, and where 0<

x≦

0.8 and 0≦

y≦

1.0, or it is a ceramic membrane with the chemical formula;

Na_1+xZr₂Si_xP_3-xO₁₂,

where 0≦

x≦

3.

15. The ceramic membrane as claimed in claim 13, wherein the ceramic membrane is from 30 μ

m to 500 μ

m in thickness.

16. The ceramic membrane as claimed in claim 13, wherein the organic polymer in the organic polymer layer is a halopolymer.

17. The ceramic membrane as claimed in claim 16, wherein the organic polymer in the organic polymer layer is a copolymer of tetrafluoroethylene and a comonomer bearing an acid group, preferably an —

SO₃⁻

M⁺ group.

18. The ceramic membrane as claimed in claim 13, wherein the organic polymer layer is from 1 to 50 μ

m in thickness, preferably from 2 to 10 μ

m in thickness.

19. The ceramic membrane as claimed in claim 13, wherein the other surface of the ceramic membrane is covered with a protective coating comprising Li₃N, Li₃P, LiI, LiBr, LiF or lithium phosphorus oxynitride (LiPON.

25. The ceramic membrane as claimed in claim 13, wherein the ceramic membrane is from 50 μ

m to 160 μ

m in thickness.

26. The ceramic membrane as claimed in claim 13, wherein the organic polymer is a fluoropolymer, bearing acid groups.

27. The ceramic membrane as claimed in claim 13, wherein the other surface of the ceramic membrane is covered with a protective coating comprising sodium phosphorus oxynitride (NaPON).

28. The ceramic membrane as claimed in claim 13, wherein the other surface of the ceramic membrane is covered with LiPON protective coating.

20. An electrochemical device containing:

as a solid electrolyte, a ceramic membrane, the membrane being covered with an organic cation-conductive polymer that is insoluble and chemically stable in water at basic pH; and

as a liquid electrolyte, an aqueous solution of alkali-metal hydroxide making contact with said organic polymer.

21. The electrochemical device as claimed in claim 20, wherein it is a metal-air battery.

22. The electrochemical device as claimed in claim 20, wherein it the electrochemical device is a metal-water battery.

23. The electrochemical device as claimed in claim 20, wherein the electrochemical device is an electrolysis cell.

24. The electrochemical device as claimed in claim 20, wherein the electrochemical device is a lithium pump.

29. The electrochemical device as claimed in claim 20, wherein the electrochemical device is a lithium-air battery.

30. The electrochemical device as claimed in claim 20, wherein the electrochemical device is a lithium-water battery.

31. The electrochemical device as claimed in claim 20, wherein the electrochemical device is a sodium pump.