Lithium anodes for electrochemical cells

• US 8,105,717 B2
• Filed: 10/31/2007
• Issued: 01/31/2012
• Est. Priority Date: 11/23/1999
• Status: Expired due to Term

• Current Assignee: Sion Power Corporation
• Original Assignee: Sion Power Corporation
• Inventors: Skotheim, Terje A., Sheehan, Christopher J., Mikhaylik, Yuriy V., Affinito, John
• Primary Examiner(s): Michener, Jennifer
• Assistant Examiner(s): WILLS, MONIQUE M
• Application Number:
  US11/932,499
• Publication Number:
  US 20080057397A1
• Time in Patent Office: 1,553 Days
• Field of Search: 429/231.95, 429/77, 429/212, 429/209, 429/214, 429/215, 429/247, 429/144, 429/145
• US Class Current: 429/231.95
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• 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 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0421 involving vapour deposition
• CPC Class Codes: H01M 4/0426 Sputtering
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/366 as layered products
• 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 4/387 Tin or alloys based on tin
• CPC Class Codes: H01M 4/581 Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/5815 : Sulfides
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: H01M 4/628 : Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: H01M 50/46 : Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 6/14 : Cells with non-aqueous electrolyte
• CPC Class Codes: H01M 6/18 : with solid electrolyte
• 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

Provided is an anode for use in electrochemical cells, wherein the anode active layer has a first layer comprising lithium metal and a multi-layer structure comprising single ion conducting layers and polymer layers in contact with the first layer comprising lithium metal or in contact with an intermediate protective layer, such as a temporary protective metal layer, on the surface of the lithium-containing first layer. Another aspect of the invention provides an anode active layer formed by the in-situ deposition of lithium vapor and a reactive gas. The anodes of the current invention are particularly useful in electrochemical cells comprising sulfur-containing cathode active materials, such as elemental sulfur.

Claims

1. An anode for an electrochemical cell comprising:

a first lithium metal layer;

a second lithium metal layer;

one or more protective layers positioned between the first and second lithium metal layers; and

one or more protective layers adjacent the second lithium metal layer on a side opposite the first lithium metal layer,

wherein;

at least one of the protective layers is a gaseous treatment layer, and

at least one of the protective layers comprises a polymer layer comprising a salt, wherein the polymer layer protects at least the first lithium metal layer from reaction with an electrolyte used with the anode and/or is positioned between the first and second lithium metal layers.

2. The anode of claim 1, further comprising a substrate, the substrate in contact with at least one lithium metal layer on a side opposite an electrolyte in an electrochemical cell.

3. The anode of claim 1, wherein an outer layer of the anode is a lithium layer.

4. The anode of claim 1, wherein an outer layer of the anode comprises a gaseous treatment layer.

5. The anode of claim 1, wherein the gaseous treatment layer comprises a reactive gas treatment layer formed by the reaction of a reactive gaseous material selected from CO₂, SO₂, and acetylene.

6. The anode of claim 1, wherein the gaseous treatment layer comprises a plasma CO₂ treatment layer.

7. The anode of claim 1, wherein the gaseous treatment layer comprises a SO₂ treatment layer.

8. The anode of claim 1, wherein the gaseous treatment layer comprises an acetylene treatment layer.

9. The anode of claim 1, wherein the gaseous treatment layer comprises lithium co-deposited with at least one of CO₂, SO₂, acetylene, ethylene, nitrogen, hydrocarbons, alkyl phosphate esters, alkyl sulfite esters and alkyl sulfate esters.

10. The anode of claim 1, wherein the gaseous treatment layer comprises lithium co-deposited with CO₂ or acetylene.

11. The anode of claim 1, wherein the gaseous treatment layer comprises lithium co-deposited with CO₂.

12. The anode of claim 1, wherein the gaseous treatment layer comprises a reaction product of a gas and a lithium metal layer, and wherein the reaction product comprises between 0.2% and 5.0% by weight of the lithium metal layer.

35. The anode of claim 1, wherein the polymer layer protects at least the first lithium metal layer from reaction with an electrolyte used with the anode.

36. The anode of claim 1, wherein the polymer layer is positioned between the first and second lithium metal layers.

39. The anode of claim 1, wherein at least one of the protective layers is a single ion conductive layer that is conductive to lithium ions.

40. The anode of claim 39, wherein the single ion conductive layer is a ceramic layer.

41. The anode of claim 39, wherein the single ion conductive layer has a thickness between about 5 nanometers and about 5000 nanometers.

42. The anode of claim 39, wherein the single ion conductive layer has a thickness between about 10 nanometers and about 1000 nanometers.

43. The anode of claim 1, wherein the polymer layer comprises a polyacrylate.

13. An anode for a nonaqueous electrochemical cell, comprising:

an anode active layer comprising lithium metal;

a multi-layer structure in contact with the anode active layer, wherein the multi-layer structure comprises three or more layers, and wherein at least one of the three or more layers comprises a single ion conducting material and at least one of the three or more layers comprises a polymer comprising a salt that is covered by a protective layer that protects the anode active layer from reaction with an electrolyte used with the anode; and

a lithiated metal alloy layer in contact with at least one layer of the multi-layer structure, wherein the metal alloy layer is separated from the anode active layer by at least one layer of the multi-layer structure.

14. The anode of claim 13, wherein the lithiated metal alloy layer comprises about 0.5% to about 20% by weight lithium.

15. The anode of claim 13, wherein the lithiated metal alloy layer comprises a metal selected from the group consisting of Al, Zn, Mg, Ag, Pb, Cd, Bi, Ga, In, Ge and Sn.

16. The anode of claim 13, wherein the lithiated metal alloy comprises a metal selected from the group consisting of Zn, Mg, Sn, and Al.

17. The anode of claim 13, wherein the thickness of the lithiated metal alloy layer is between about 10 nm and about 1000 nm.

18. The anode of claim 13, wherein the lithiated metal alloy layer is positioned between a polymer layer and a single ion conducting layer of the multi-layer structure.

19. The anode of claim 13, wherein the lithiated metal alloy layer is positioned between two polymer layers of the multi-layer structure.

20. The anode of claim 13, wherein the lithiated metal alloy layer is positioned between two single ion conducting layers of the multi-layer structure.

21. The anode of claim 13, wherein the lithiated metal alloy layer is an outer layer of the multi-layer structure, on a side opposite the anode active layer.

22. The anode of claim 13, wherein the thickness of the anode active layer is between about 2 and 200 microns.

23. The anode of claim 13, wherein the thickness of the multi-layer structure is between about 0.5 and 10 microns.

24. The anode of claim 13, wherein the multi-layer structure comprises four or more layers.

25. The anode of claim 13, wherein the single ion conducting material comprises a material selected from inorganic materials, organic material and mixed organic-inorganic polymeric materials.

26. The anode of claim 13, wherein the single ion conducting material of the multi-layer structure comprises a glass selected from the group consisting of lithium nitride, lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorus oxynitrides, lithium silicosulfides, lithium germanosulfides, lithium lanthanum oxides, lithium tantalum oxides, lithium niobium oxides, lithium titanium oxides, lithium borosulfides, lithium aluminosulfides, and lithium phosphosulfides, and combinations thereof.

27. The anode of claim 13, wherein the polymer of the multi-layer structure comprises a polymer selected from the group consisting of electrically conducting polymers, ionically conductive polymers, sulfonated polymers, and hydrocarbon polymers.

28. The anode of claim 13, wherein the polymer of the multi-layer structure is formed from the polymerization of one or more acrylate monomers selected from the group consisting of alkyl acrylates, glycol acrylates, and polyglycol acrylates.

29. The anode of claim 13, wherein the anode further comprises a substrate, the substrate being in contact with the anode active layer on the side opposite to the multi-layered structure.

30. The anode of claim 13, wherein the lithiated metal alloy layer forms one of the three or more layers of the multi-layer structure.

31. The anode of claim 13, wherein at least one layer of the multi-layer structure comprises a lithiated single-ion conductive material that selectively or exclusively allows passage of lithium ions.

32. The anode of claim 13, wherein at least one layer of the multi-layer structure comprises lithium nitride.

33. The anode of claim 13, wherein the salt comprises a lithium salt.

34. An anode for an electrochemical cell comprising:

a first anode active layer comprising lithium metal;

a second anode active layer comprising lithium metal; and

one or more protective layers positioned between the first and second anode active layers, wherein at least one of the one or more protective layer protects at least the first anode active layer from reaction with an electrolyte used with the anode, and at least one of the one or more protective layers comprises a polymer layer comprising a salt, wherein the polymer layer is covered by a protective layer or by one of the first and second anode active layers.

37. The anode of claim 34, wherein the polymer layer is covered by a protective layer.

38. The anode of claim 34, wherein the polymer layer is covered by one of the first and second anode active layers.

44. The anode of claim 34, wherein at least one of the one or more protective layers is a single ion conductive layer that is conductive to lithium ions.

45. The anode of claim 44, wherein the single ion conductive layer is a ceramic layer.

46. The anode of claim 45, wherein the single ion conductive layer comprises lithium nitride.

47. The anode of claim 44, wherein the single ion conductive layer has a thickness between about 5 nanometers and about 5000 nanometers.

48. The anode of claim 47, wherein the single ion conductive layer has a thickness between about 10 nanometers and about 1000 nanometers.

49. The anode of claim 34, wherein at least one of the one or more protective layers comprises a single ion conducting material comprising a material selected from inorganic materials, organic materials and mixed organic-inorganic polymeric materials.

50. The anode of claim 49, wherein the single ion conducting material comprises a glass selected from the group consisting of lithium nitride, lithium silicates, lithium borates, lithium aluminates, lithium phosphates, lithium phosphorus oxynitrides, lithium silicosulfides, lithium germanosulfides, lithium lanthanum oxides, lithium tantalum oxides, lithium niobium oxides, lithium titanium oxides, lithium borosulfides, lithium aluminosulfides, and lithium phosphosulfides, and combinations thereof.

51. The anode of claim 34, wherein the polymer layer comprises a polymer selected from the group consisting of electrically conducting polymers, ionically conductive polymers, sulfonated polymers, and hydrocarbon polymers.

52. The anode of claim 34, wherein the polymer layer is formed from the polymerization of one or more acrylate monomers selected from the group consisting of alkyl acrylates, glycol acrylates, and polyglycol acrylates.

53. The anode of claim 34, wherein the polymer layer comprises a polyacrylate.