Layered arrangements of lithium electrodes

• US 6,413,285 B1
• Filed: 08/16/2000
• Issued: 07/02/2002
• Est. Priority Date: 11/01/1999
• Status: Expired due to Term

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., DeJonghe, Lutgard C., Chu, May-Ying
• Primary Examiner(s): Brouillette, Gabrielle
• Assistant Examiner(s): Ruthkosky, Mark
• Application Number:
  US09/640,467
• Time in Patent Office: 685 Days
• Field of Search: 429/218.1, 429/232, 296/234, 296/231
• US Class Current: 29/623.4
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0407 by coating on an electrolyte layer
• CPC Class Codes: H01M 4/0411 by extrusion
• CPC Class Codes: H01M 4/0421 involving vapour deposition
• CPC Class Codes: H01M 4/0426 Sputtering
• CPC Class Codes: H01M 4/0428 Chemical vapour deposition
• CPC Class Codes: H01M 4/043 involving compressing or compaction
• CPC Class Codes: H01M 4/0495 Chemical alloying
• 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 4/66 Selection of materials
• 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: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/49114 including adhesively bonding

Abstract

A method employing a bonding layer is used to form active metal electrodes having barrier layers. Active metals such as lithium are highly reactive in ambient conditions. The method involves fabricating a lithium electrode or other active metal electrode without depositing the barrier layer on a layer of metal. Rather a smooth barrier layer is formed on a smooth substrate such as a web carrier or polymeric electrolyte. A bonding or alloying layer is formed on top of the barrier layer. Lithium or other active material is then attached to the bonding layer to form the active metal electrode. A current collector may also be attached to the lithium or active metal during the process.

Claims

1. A method of fabricating an active metal electrode, the method comprising:

(a) providing a barrier layer laminate comprising (i) a barrier layer disposed on a substrate, the barrier layer forming a substantially impervious layer which is conductive to ions of the active metal, and (ii) a foil bonding layer disposed on the barrier layer, the foil bonding layer capable of forming a bond with the active metal; and

(b) bonding active metal to the foil bonding layer.

2. The method of claim 1, wherein the substrate on which the barrier layer is disposed is a releasable web carrier.

3. The method of claim 2, wherein the releasable web carrier includes a release layer of copper, tin, zinc, aluminum, iron, a polymeric material, or combination thereof on which the barrier layer is disposed.

4. The method of claim 1, wherein the substrate on which the barrier layer is disposed is a solid-state or gel-state electrolyte separator.

5. The method of claim 1, wherein the substrate on which the barrier layer is disposed is a polymeric electrolyte separator.

6. The method of claim 1, further comprising forming the barrier layer on the substrate by a physical deposition process or a chemical vapor deposition process.

7. The method of claim 1, wherein the barrier layer is a glass layer that includes at least one of a lithium silicate, a lithium borate, a lithium aluminate, a lithium phosphate, a lithium phosphorus oxynitride, a lithium silicosulfide, a lithium borosulfide, a lithium aluminosulfide, and a lithium phosphosulfide.

8. The method of claim 1, wherein the barrier layer comprises an organic polymeric material.

9. The method of claim 8, wherein the organic polymeric material includes at least one of nitrogen atoms or phosphorus atoms.

10. The method of claim 1, wherein the barrier layer is a glass layer having a thickness of between about 50 angstroms and 5 micrometers.

11. The method of claim 1, wherein the barrier layer has an ionic conductivity of between about 10⁻

8 and about 10<sup>−

2</sup> (ohm-cm)<sup>−

1</sup>.

12. The method of claim 1, wherein the foil bonding layer is not substantially reactive with moisture and air.

13. The method of claim 1, wherein the foil bonding layer is comprised of at least one of aluminum, an aluminum alloy, silicon, zinc, manganese, silver, antimony, magnesium, lead, tin, iron, titanium and alloys of such metals.

14. The method of claim 1, wherein the foil bonding layer is comprised of aluminum or an aluminum alloy.

15. The method of claim 1, wherein the foil bonding layer is an aluminum layer or aluminum alloy layer having a thickness between about 0.1 micrometers and 100 micrometers.

16. The method of claim 1, further comprising attaching a current collector on the active metal.

17. The method of claim 1, wherein the active metal is lithium or an alloy of lithium.

18. The method of claim 1, wherein the active metal is lithium or an alloy of lithium and has a thickness of at least about 0.2 micrometers.

19. The method of claim 1, wherein bonding active metal to the foil bonding layer comprises bonding a free standing lithium layer to the foil bonding layer.

20. The method of claim 1, wherein bonding the active metal to the foil bonding layer comprises bonding a laminate of an active metal layer and a current collector layer to the foil bonding layer.

21. The method of claim 1, wherein bonding the active metal to the foil bonding layer comprises pressing an active metal layer to the barrier layer laminate.

22. The method of claim 21, wherein pressing the active metal layer to the barrier layer laminate is done in a hot press.

23. The method of claim 1, wherein bonding the active metal to the foil bonding layer comprises evaporating or sputtering the active metal on to the barrier layer laminate.

24. An active metal electrode formed by the method of claim 1, wherein the bonding layer is a metal.

25. A battery comprising the active metal electrode of claim 24.

26. The battery of claim 25, wherein the battery is a lithium-sulfur battery.

27. The method of claim 1,

wherein the barrier layer laminate further comprises an active metal layer that is disposed on a side of the foil bonding layer that is opposite the barrier layer, and

wherein bonding the active metal to the foil bonding layer comprises bonding the active metal to the active metal layer of the barrier layer laminate.

28. A method of fabricating an active metal electrode, the method comprising:

(a) providing a barrier layer laminate comprising a barrier layer disposed on a substrate, the barrier layer forming a substantially impervious layer which is conductive to ions of active metal;

(b) attaching a foil bonding layer to the barrier layer of the barrier layer laminate, wherein the foil bonding layer comprises a material capable of forming a bond with active metal; and

(c) bonding active metal to the foil bonding layer.

29. A barrier layer laminate for use in fabricating an active metal electrode, the barrier layer laminate comprising:

(i) a substantially smooth and flat substrate;

(ii) a barrier layer disposed on the substrate, the barrier layer forming a substantially impervious layer which is conductive to ions of the active metal, and

(iii) a foil bonding layer disposed on the barrier layer, wherein the foil bonding layer comprises a material capable of forming a bond with the active metal.

30. The barrier layer laminate of claim 29, wherein the substrate on which the barrier layer is disposed is a releasable web carrier.

31. The barrier layer laminate of claim 29, wherein the substrate on which the barrier layer is disposed is a polymeric electrolyte separator.

32. The barrier layer laminate of claim 31, wherein the polymeric electrolyte separator comprises a material selected from the group consisting of polyethers, polyimines, polythioethers, polyphosphazenes, and polymer blends, mixtures, and copolymers thereof.

33. The barrier layer laminate of claim 31, wherein the polymeric electrolyte separator comprises a polyalkylene oxide.

34. The barrier layer laminate of claim 29, wherein the barrier layer includes at least one of a lithium silicate, a lithium borate, a lithium aluminate, a lithium phosphate, a lithium phosphorus oxynitride, a lithium silicosulfide, a lithium borosulfide, a lithium aluminosulfide, and a lithium phosphosulfide.

35. The barrier layer laminate of claim 29, wherein the barrier layer is a glass layer having a thickness of between about 50 angstroms and 5 micrometers.

36. The barrier layer laminate of claim 29, wherein the barrier layer is a glass and has a thickness of between about 500 angstroms and 2000 angstroms.

37. The barrier layer laminate of claim 29, wherein the foil bonding layer is not substantially reactive with moisture and air.

38. The barrier layer laminate of claim 29, wherein the foil bonding layer is comprised of at least one of aluminum, an aluminum alloy, silicon, zinc, manganese, silver, antimony, magnesium, lead, tin, iron, titanium and alloys of such metals.

39. The barrier layer laminate of claim 29, wherein the foil bonding layer is comprised of aluminum or an aluminum alloy.

40. The barrier layer laminate of claim 29, wherein the foil bonding layer is an aluminum or aluminum alloy layer having a thickness between about 0.1 micrometers and 100 micrometers.

41. The barrier layer laminate of claim 29, wherein the active metal is lithium or an alloy of lithium.

42. An active metal electrode comprising an active metal layer bonded to the foil bonding layer of the barrier layer laminate of claim 29.

43. A battery comprising the active metal electrode of claim 42.

44. The battery of claim 43, wherein the battery is a lithium-sulfur battery.

45. An active metal electrode capable of serving as a negative electrode in a battery, the active metal electrode comprising:

(i) a barrier layer forming a substantially impervious layer which is conductive to ions of the active metal;

(ii) a first active metal layer having a first side disposed on to the barrier layer;

(iii) a bonding layer disposed on a second side, opposite the first side, of the active metal layer, the bonding layer material being capable of forming a bond with the active metal; and

(iv) a second active metal layer disposed on the bonding layer, wherein the bonding layer is sandwiched between the first and second active metal layers.

46. The active metal electrode of claim 45, further comprising a substantially smooth and flat substrate disposed on a first side of the barrier layer, wherein the active metal layer is disposed on a second side, opposite the first side, of the barrier layer.

47. The active metal electrode of claim 45, wherein the bonding layer is a foil bonding layer.

48. A method of fabricating an active metal electrode, the method comprising:

(a) providing a barrier layer laminate comprising a barrier layer disposed on a substrate, the barrier layer forming a substantially impervious layer which is conductive to ions of the active metal;

(b) providing an active metal laminate comprising at least one active metal layer and a bonding layer affixed to one another, wherein the bonding layer is capable of forming a bond with the active metal; and

(c) bonding at least the active metal laminate and the barrier layer laminate to form an electrode structure in which (i) the bonding layer is sandwiched between two separate active metal layers, at least one of which was provided in the active metal laminate, and (ii) one of the two separate active metal layers is affixed to the barrier layer provided in the barrier layer laminate.

49. The method of claim 48, wherein the bonding layer is a foil.

50. The method of claim 48,

wherein the active metal laminate consists essentially of the bonding layer and a single active metal layer, and

wherein bonding at least the active metal laminate and the barrier layer laminate comprises (a) bonding a second active metal layer to the bonding layer of the active metal laminate and (b) bonding the barrier layer of the barrier layer laminate to the single active metal layer of the active metal laminate.

51. The method of claim 48, wherein the barrier layer laminate further comprises a second active metal layer disposed on a side of the barrier layer opposite the substrate.

52. The method of claim 51,

wherein the active metal laminate comprises the bonding layer and a single active metal layer, and

wherein bonding at least the active metal laminate and the barrier layer laminate comprises bonding the second active metal layer to the bonding layer of the active metal laminate.

53. The method of claim 52, wherein the active metal laminate further comprises a current collector affixed to a side of the single active metal layer that is opposite the bonding layer.

54. The method of claim 48,wherein the barrier layer laminate further comprises (a) a second active metal layer disposed on a side of the barrier layer opposite the substrate and (b) a second bonding layer disposed on a side of the second active metal layer opposite the barrier layer.

55. The method of claim 54,

wherein the active metal laminate comprises the bonding layer and a single active metal layer, and

wherein bonding at least the active metal laminate and the barrier layer laminate comprises bonding the second bonding layer of the barrier layer laminate to the bonding layer of the active metal laminate.

56. The method of claim 55, wherein the active metal laminate further comprises a current collector affixed to a side of the single active metal layer that is opposite the bonding layer.

57. A method of fabricating an active metal electrode including a barrier layer forming a substantially impervious layer which is conductive to ions of the active metal, the method comprising:

(a) forming the barrier layer on a metal bonding layer to create a barrier layer laminate, the bonding layer being capable of forming a bond with the active metal; and

(b) bonding the barrier layer laminate to a layer of active metal by affixing the active metal layer to the bonding layer of the barrier layer laminate.

58. The method of claim 57, wherein the bonding layer is an aluminum foil or an aluminum alloy foil.

59. The method of claim 57, wherein the active metal is lithium or a lithium alloy.