MultiLayer Solid Electrolyte for Lithium Thin Film Batteries

• US 20100285372A1
• Filed: 06/11/2007
• Published: 11/11/2010
• Est. Priority Date: 06/11/2007
• Status: Active Grant

• Current Assignee: Alliance For Sustainable Energy LLC
• Original Assignee: Alliance For Sustainable Energy LLC
• Inventors: Tracy, Edwin C., Lee, Se-Hee, Liu, Ping, Pitts, John Roland
• Granted Patent: US 9,093,707 B2
• Time in Patent Office: Days
• US Class Current: 429/320
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• 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 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• 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 6/20 working at high temperature deferred-action thermal cells H01M6/36
• CPC Class Codes: H01M 6/24 Cells comprising two different electrolytes
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• 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

Abstract

A lithium metal thin-film battery composite structure is provided that includes a combination of a thin, stable, solid electrolyte layer [18] such as Lipon, designed in use to be in contact with a lithium metal anode layer; and a rapid-deposit solid electrolyte layer [16] such as LiAlF₄ in contact with the thin, stable, solid electrolyte layer [18]. Batteries made up of or containing these structures are more efficient to produce than other lithium metal batteries that use only a single solid electrolyte. They are also more resistant to stress and strain than batteries made using layers of only the stable, solid electrolyte materials. Furthermore, lithium anode batteries as disclosed herein are useful as rechargeable batteries.

Claims

1. A lithium metal thin-film battery composite structure comprising:

a. a thin, stable, solid electrolyte layer designed, in use, to be in contact with a lithium metal anode layer; and

b. a rapid-deposit solid electrolyte layer in contact with said thin, stable, solid electrolyte layer.

2. A secondary battery composite structure of claim 1.

3. The battery composite structure of claim 1 also comprising at least one additional rapid-deposit solid electrolyte layer in contact with said rapid-deposit solid electrolyte layer.

4. The battery composite structure of claim 1 wherein said thin, stable solid electrolyte layer has a thickness between about 10 nm and about 100 nm.

5. The battery composite structure of claim 4 wherein said thin, stable solid electrolyte layer has a thickness between about 50 nm and about 100 nm.

6. The battery composite structure of claim 1 wherein said rapid-deposit solid electrolyte layer has a thickness between about 650 nm and about 1000 nm.

7. The battery composite structure of claim 6 wherein said rapid-deposit solid electrolyte layer has a thickness between about 900 nm and about 1000 nm.

8. The battery composite structure of claim 1 wherein the combined thickness of the solid electrolyte layers including said rapid-deposit solid electrolyte layer and said additional rapid-deposit solid electrolyte layer(s) is no more than about 20 μ

m.

9. The battery composite structure of claim 1 also comprising a lithium metal anode layer.

10. The battery composite structure of claim 1 also comprising an anode current collector, a cathode layer, and a cathode collector layer.

11. The battery composite structure of claim 1 wherein said thin, stable, solid electrolyte layer is made of a material selected from the group consisting of lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorus oxynitrides, lithium silicosulfides, lithium borosulfides, lithium aluminosulfides, and lithium phosphosulfides.

12. The battery composite structure of claim 1 wherein said rapid-deposit solid electrolyte layer(s) are independently made of solid inorganic materials selected from the group consisting of sodium beta alumina, Nasicon or Lisicon glass or ceramic, Li₃N, LiF₃, LiAlF₄ and Li_1-xAl_xTi_2-x(PO₄)₃, where x is determined by the concentration of Al in the compound;

and solid polymeric lithium-ion-conducting electrolyte materials selected from the group consisting of polyethers, polyimines, polythioethers, polyphosphazenes, polyalkylene oxides, and polymer blends, mixtures, and copolymers thereof to which an appropriate electrolyte salt has optionally been added containing less than about 20% liquid.

13. A process for producing a lithium metal, thin-film battery composite structure, the process comprising the steps of:

a. depositing a cathode layer on an exposed, conductive cathode current collector layer;

b. depositing a rapid-deposit solid electrolyte layer on said cathode layer;

c. depositing a thin, stable solid electrolyte layer on said rapid-deposit solid electrolyte layer; and

d. depositing a lithium anode layer on said thin, stable solid electrolyte layer.

14. The process of claim 13 in which the step of depositing said thin, stable solid electrolyte layer on said rapid-deposit solid electrolyte layer is conducted at a deposition rate between about 5 and about 15 nm/min using CVD or PVD.

15. The process of claim 13 in which the step of depositing said rapid-deposit solid electrolyte layer on said cathode layer is conducted at a deposition rate between about 100 and about 1000 nm/min using CVD or PVD.

16. The process of claim 13 wherein, in step b. at least one additional rapid-deposit solid electrolyte layer is deposited on said rapid-deposit solid electrolyte layer.

17. The process of claim 13 in which an anode current collector layer is deposited on said lithium anode layer.

18. A lithium metal, thin-film battery composite structure made by the process of claim 13.

19. A process for producing a lithium metal, thin-film battery composite structure, the process comprising the steps of:

a. depositing a thin, stable solid electrolyte layer on a conductive face of a lithium-containing anode current collector layer;

b. depositing a rapid-deposit solid electrolyte layer on said thin, stable solid electrolyte layer;

c. depositing a cathode layer on said rapid-deposit solid electrolyte layer;

d. depositing a cathode current collector layer on said cathode layer; and

e. electrolytically forming a lithium anode between said anode current collector layer and said thin, stable solid electrolyte layer.

20. The process of claim 19 wherein the step of depositing said thin, stable solid electrolyte layer on said conductive face of the lithium-containing anode current collector layer is conducted at a rate of about 5-15 nm/min using reactive sputtering deposition method.

21. The process of claim 19 wherein the step of depositing said rapid-deposit solid electrolyte layer on said thin, stable solid electrolyte layer is conducted at a rate of about 100 to about 1000 nm/min using CVD or PVD.

22. The process of claim 19 wherein said electrolytic forming step is performed by flowing an electric current between the conductive face of said anode current collector layer and said cathode current collector layer.

23. The process of claim 19 wherein said lithium-containing anode current collector layer is formed by lithiating a transition metal oxide anode current collector layer until it contains a supra-stoichiometric amount of lithium.

24. The process of claim 19 wherein, in step b. at least one additional rapid-deposit solid electrolyte layer is deposited on said rapid-deposit solid electrolyte layer.

25. A lithium metal, thin-film battery composite structure made by the process of claim 19.

26. A method of providing an electric current to a device comprising placing in electrical connection with said device, a lithium metal, thin-film battery composite structure comprising:

a. a lithium metal anode layer; and

b. a plurality of solid electrolyte layers, including;

i. a thin, stable solid electrolyte layer adjacent to said lithium metal anode layer;

ii. a rapid-deposit solid electrolyte layer adjacent to said thin, stable solid electrolyte layer; and

iii. optionally, one or more additional rapid deposit solid electrolyte layer(s), wherein one such layer is adjacent said layer of paragraph ii;

c. aggregating said battery composite structure with components required to form a complete, functioning battery;

d. placing said functioning battery in operational connection with said device and activating said device.

27. The method of claim 26 further comprising recharging and reusing said battery.