LITHIUM ANODES FOR ELECTROCHEMICAL CELLS

• US 20080057397A1
• Filed: 10/31/2007
• Published: 03/06/2008
• Est. Priority Date: 11/23/1999
• Status: Active Grant

• Current Assignee: Sion Power Corporation
• Original Assignee: Sion Power Corporation
• Inventors: Skotheim, Terje, Mikhaylik, Yuriy, Affinito, John, Sheehan, Christopher
• Granted Patent: US 8,105,717 B2
• Time in Patent Office: Days
• US Class Current: 429/212
• 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 an anode active layer

(a) one or more lithium metal layers;

and

(b) one or more gaseous treatment layers;

wherein the anode comprises alternating layers of lithium metal layers and gaseous treatment layers.

2. The anode of claim 1, further comprising a substrate, the substrate in contact with a anode active layer on the side opposite to the electrolyte in an electrochemical cell.

3. The anode of claim 1, wherein the first layer of the anode active layer comprises lithium metal.

4. The anode of claim 1, wherein the outer layer of the anode active layer is a lithium layer

5. The anode of claim 1, wherein the outer later of the anode comprises a gaseous treatment layer.

6. The anode of claim 1, wherein the gaseous treatment layer comprises a reactive gas treatment layer, wherein the reactive gaseous material is selected from CO₂, SO₂, and acetylene.

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

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

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

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

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

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

13. The anode of claim 9, wherein the gaseous treatment layer comprises between 0.2% and 5.0% by weight of gaseous material.

14. The anode of claim 1, wherein the outer layer of the anode on the side facing the electrolyte in an electrochemical cell is an intermediate layer, wherein intermediate layer is a temporary protective metal layer.

15. The anode of claim 14, wherein the temporary protective metal layer comprises a metal selected from the group consisting of copper, magnesium, aluminum, silver, gold, lead, cadmium, bismuth, indium, gallium, germanium, zinc, tin, and platinum.

16. The anode of claim 1, wherein the outer layer of the anode on the side facing the electrolyte in an electrochemical cell is an intermediate layer, wherein the intermediate layer comprises a supercritical fluid CO₂ treatment layer.

17. The anode of claim 1, wherein the thickness of the anode active layer is 2 to 200 microns.

18. The anode of claim 2, wherein the substrate is selected from the group consisting of metal foils, polymer films, metallized polymer films, electrically conductive polymer films, polymer films having an electrically conductive coating, electrically conductive polymer films having an electrically conductive metal coating, and polymer films having conductive particles dispersed therein.

19. The anode of claim 1, wherein the anode further comprises a multilayer structure in contact with the anode active layer on the side of the anode facing the electrolyte in an electrochemical cell, wherein the multilayer structure comprises one or more polymer layers and one or more single ion conducting layers.

20. The anode of claim 19, wherein the single ion conducting material comprises a material selected from inorganic materials, organic material and mixed organic-inorganic polymeric materials.

21. The anode of claim 19, wherein the single ion conducting material of the multi-layer structure comprises a glass selected from the group consisting of 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.

22. The anode of claim 19, 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.

23. The anode of claim 19, 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.

24. An electrochemical cell comprising:

(a) the anode of claim 1;

(b) a cathode; and

(c) a non-aqueous electrolyte interposed between the anode and the cathode.

25. The cell of claim 24 wherein the cathode comprises an electroactive sulfur-containing material.

26. A method of making an anode for an electrochemical cell comprising depositing alternate layers of lithium metal and gaseous treatment layers on a substrate.

27. An anode for a nonaqueous electrochemical cell comprising:

(i) an anode active layer comprising lithium metal; and

(ii) a multi-layer structure in contact with the anode active layer;

wherein the multi-layer structure comprises three or more layers, 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; and

(iii) a lithiated metal alloy layer in contact with at least one of the layers of the multilayer structure.

28. The anode of claim 27, wherein the lithiated metal alloy layer comprises about 0.5% to about 20% by weight lithium.

29. The anode of claim 27, 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.

30. The anode of claim 27, wherein the lithiated metal alloy comprises a metal selected from the group consisting of Zn, Mg, Sn, and Al.

31. The anode of claim 27, wherein the thickness of the lithiated metal alloy layer is between about 10 nm and about 1000 nm.

321. The anode of claim 27, wherein the lithiated metal alloy layer is between a polymer layer and a single ion conducting layer of the multi-layer structure.

33. The anode of claim 27, wherein the lithiated metal alloy layer is between two polymer layers of the multi-layer structure.

34. The anode of claim 27, wherein the lithiated metal alloy layer is between two single ion conducting layers of the multi-layer structure.

35. The anode of claim 27, wherein the lithiated metal alloy layer is the outer layer of the multi-layer structure, on the side opposite to the anode active layer.

36. The anode of claim 27, wherein the thickness of the anode active layer is 2 to 200 microns.

37. The anode of claim 27, wherein the thickness of the multi-layer structure is 0.5 to 10 microns.

38. The anode of claim 27, wherein the multi-layer structure comprises four or more layers.

39. The anode of claim 27, wherein the single ion conducting material comprises a material selected from inorganic materials, organic material and mixed organic-inorganic polymeric materials.

40. The anode of claim 27, wherein the single ion conducting material of the multi-layer structure comprises a glass selected from the group consisting of 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.

41. The anode of claim 27, 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.

42. The anode of claim 27, 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.

43. The anode of claim 27, wherein the anode further comprises a substrate, the substrate in contact with the anode active layer on the side opposite to the multi-layered structure.

44. An electrochemical cell comprising:

(a) a cathode;

(b) the anode of claim 27;

(c) a non-aqueous electrolyte interposed between the anode and the cathode.

45. The cell of claim 44, wherein the cathode comprises an electroactive sulfur-containing material.

46. The cell of claim 44, wherein the electroactive sulfur-containing material comprises elemental sulfur.