Thin Film Encapsulation for Thin Film Batteries and Other Devices

• US 20090181303A1
• Filed: 01/09/2009
• Published: 07/16/2009
• Est. Priority Date: 01/11/2008
• Status: Active Grant

• Current Assignee: Sapurast Research LLC
• Original Assignee: Feenex Inc. (Apple Inc.)
• Inventors: Snyder, Shawn W., NEUDECKER, Bernd J.
• Granted Patent: US 8,518,581 B2
• Time in Patent Office: Days
• US Class Current: 429/209
• 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 2300/0068 inorganic
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/664 Ceramic materials
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 50/117 Inorganic material
• CPC Class Codes: H01M 50/119 Metals
• CPC Class Codes: H01M 50/124 having a layered structure
• CPC Class Codes: H01M 50/128 with two or more layers of only inorganic material
• CPC Class Codes: H01M 50/133 Thickness
• CPC Class Codes: H01M 50/24 adapted for protecting batteries from their environment, e.g. from corrosion thermal insulation H01M10/658
• CPC Class Codes: H01M 50/545 : formed by the casing of the cells cup shaped terminals adapted for cells having curved cross-section H01M50/56
• CPC Class Codes: H01M 6/185 : with oxides, hydroxides or oxysalts as solid 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

An electrochemical device is claimed and disclosed, including a method of manufacturing the same, comprising an environmentally sensitive material, such as, for example, a lithium anode; and a plurality of alternating thin metallic and ceramic, blocking sub-layers. The multiple metallic and ceramic, blocking sub-layers encapsulate the environmentally sensitive material. The device may include a stress modulating layer, such as for example, a Lipon layer between the environmentally sensitive material and the encapsulation layer.

Claims

1. An electrochemical device comprising:

an environmentally sensitive layer; and

a thin encapsulation layer deposited over said sensitive layer, comprising a plurality of alternating metallic sub-layers and ceramic sub-layers.

2. The electrochemical device of claim 1 wherein said metallic sub-layers comprise at least one element selected from the group comprising:

scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminum, carbon, silicon, germanium, beryllium, magnesium, calcium, strontium, barium, lithium, sodium, potassium, rubidium, and caesium.

3. The electrochemical device of claim 1 wherein said ceramic sub-layers comprise nitrides of at least one element selected from the group comprising:

scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminum, carbon, silicon, germanium, beryllium, magnesium, calcium, strontium, barium, lithium, sodium, potassium, rubidium, and caesium.

4. The electrochemical device of claim 1 wherein said ceramic sub-layers comprise oxides of at least one element selected from the group comprising:

scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminum, carbon, silicon, germanium, beryllium, magnesium, calcium, strontium, barium, lithium, sodium, potassium, rubidium, and caesium.

5. The electrochemical device of claim 1 wherein said ceramic sub-layers comprise carbides of at least one element selected from the group comprising:

scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminum, silicon, germanium, beryllium, magnesium, calcium, strontium, barium, lithium, sodium, potassium, rubidium, and caesium.

6. The electrochemical device of claim 1 wherein said ceramic sub-layers comprise silicides of at least one element selected from the group comprising:

scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, aluminum, carbon, germanium, beryllium, magnesium, calcium, strontium, barium, lithium, sodium, potassium, rubidium, and caesium.

7. The electrochemical device of claim 1 wherein said ceramic sub-layers comprise borides of at least one element selected from the group comprising:

scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, aluminum, carbon, silicon, germanium, beryllium, magnesium, calcium, strontium, barium, lithium, sodium, potassium, rubidium, and caesium.

8. The electrochemical device of claim 1 wherein said environmentally sensitive layer comprises at least one material selected from the group consisting of:

lithium alloy, lithium solid solution, metallic lithium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, silver, hafnium, tantalum, tungsten, iridium, platinum, gold, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, indium, carbon, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, and bismuth.

9. The electrochemical device of claim 1 further comprising a stress modulation layer disposed between said environmentally sensitive layer and said encapsulation layer.

10. The electrochemical device of claim 9 wherein said stress modulation layer is not reactive with either said environmentally sensitive layer or said thin encapsulation layer.

11. The electrochemical device of claim 9 where said stress modulation layer comprises Lipon.

12. The electrochemical device of claim 1 where said environmentally sensitive layer is soft.

13. The electrochemical device of claim 12 wherein said soft, environmentally sensitive layer comprises of at least one material selected from the group consisting of:

lithium alloy, lithium solid solution, and metallic lithium.

14. The electrochemical device of claim 1 wherein at least one sub-layer of said encapsulation layer is deposited using sputtering from a metallic target.

15. The electrochemical device of claim 1 wherein at least one sub-layer of said encapsulation layer is deposited using a dual sputter cathode deposition method.

16. The electrochemical device of claim 1 wherein said environmentally sensitive material comprises an anode.

17. The electrochemical device of claim 1 wherein said device maintains thermal stability under solder reflow conditions of up to 265°

C.

18. The electrochemical device of claim 1 wherein said encapsulating layer is selectively conductive.

19. The electrochemical device of claim 18 wherein said selectively conductive thin encapsulation serves as one electrical terminal of said device.

20. The electrochemical device of claim 1 wherein said encapsulation layer is flexible.

21. The electrochemical device of claim 1 further comprising:

a cathode;

an electrolyte deposited on said cathode;

an anode deposited on said electrolyte;

a stress modulating layer deposited between said anode and said encapsulation layer.

22. The electrochemical device of claim 21 wherein said cathode comprises LiCoO₂.

23. The electrochemical device of claim 21 wherein said electrolyte comprises Lipon.

24. The electrochemical device of claim 21 wherein said anode comprises at least one material selected from the group consisting of:

lithium alloy, lithium solid solution, and metallic lithium.

25. The electrochemical device of claim 21 wherein said stress modulating material comprises Lipon.

26. The electrochemical device of claim 21 wherein said cathode thickness is between about 0.5 μ

m and 200 μ

m.

27. The electrochemical device of claim 21 wherein said electrolyte thickness is less than about 5 μ

m.

28. The electrochemical device of claim 21 wherein said anode thickness is between about 0.1 μ

m and 30 μ

m.

29. The electrochemical device of claim 21 wherein the thickness of said alternating metallic layers and ceramic layers are each at least about 500 angstroms.

30. The electrochemical device of claim 1 wherein said alternating metallic and blocking layers comprise at least two metallic sub-layers and at least two ceramic sub-layers, respectively.

31. The electrochemical device of claim 30 wherein the total thickness of every metallic layer and every ceramic layer is less than about 5 μ

m.

32. An electrochemical device comprising:

a cathode;

an electrolyte deposited on said cathode;

a soft, environmentally sensitive anode deposited on said electrolyte;

a stress modulating layer deposited on said anode;

an encapsulation layer, comprising a plurality of alternating metallic and ceramic sub-layers, deposited on said modulating layer.

33. An electrochemical device comprising:

a LiCoO₂ layer;

a first Lipon layer deposited on said LiCoO₂ layer;

a lithium layer deposited on said first Lipon layer;

a second Lipon layer deposited on said lithium layer; and

an encapsulation layer, comprising a plurality of alternating metallic and ceramic sub-layers, deposited on said second Lipon layer.

34. An electrochemical device comprising:

a cathode greater than about 0.5 μ

m and less than about 200 μ

m thick;

an electrolyte less than about 5 μ

m thick;

an anode greater than about 0.1 μ

m and less than about 30 μ

m thick;

a modulating layer; and

a plurality of alternating metallic and ceramic sub-layers, wherein each sub-layer is less than about 5 μ

m thick.

35. A method of manufacturing an electrochemical device comprising:

depositing an environmentally sensitive layer; and

depositing a plurality of alternating metallic sub-layers and ceramic sub-layers.

36. The method of claim 35 wherein said environmentally sensitive layer comprises at least one material selected from the group consisting of:

lithium alloy, lithium solid solution, and metallic lithium.

37. The method of claim 35 further comprising a stress modulator layer deposed over said sensitive layer.

38. The method of claim 35 where said environmentally sensitive layer is soft.

39. The method of claim 38 wherein said soft, environmentally sensitive layer comprises at least one material selected from the group consisting of:

lithium alloy, lithium solid solution, and metallic lithium.