Alkali metal electrochemical cell with improved energy density

• US 5,716,728 A
• Filed: 11/04/1996
• Issued: 02/10/1998
• Est. Priority Date: 11/04/1996
• Status: Expired due to Term

• Current Assignee: Greatbatch Limited (Greatbatch Incorporated)
• Original Assignee: Wilson Greatbatch Technologies, Inc.
• Inventors: Takeuchi, Esther S., Smesko, Sally Ann, Paulot, William M.
• Primary Examiner(s): NUZZOLILLO, MARIA
• Application Number:
  US08/742,670
• Time in Patent Office: 463 Days
• Field of Search: 429/60, 429/218, 429/194, 429/233, 429/245, 29/623.1
• US Class Current: 429/60
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 6/04 Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/14 Cells with non-aqueous electrolyte
• 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
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

Abstract

An alkali metal/solid cathode electrochemical cell, particularly a Li/CF_x cell, having an electrolyte-to-cathode (E/C) weight ratio of about 0.94 to 0.96, and an anode-to-cathode (A/C) capacity ratio of about 1.03, is described. These ratios provide the cell with an improvement of about 6.7% in terms of volumetric energy density and about 11.9% in terms of gravimetric energy density over prior art Li/CF_x cells.

Claims

1. An electrochemical cell, which comprises:

a) an anode comprising an anode active material;

b) a cathode operatively associated with the anode, wherein the cathode comprises a cathode active material; and

c) an electrolyte solution activating the anode and the cathode, wherein the anode active material and the cathode active material are present in the cell in an anode-to-cathode capacity ratio of about 1.03 and wherein the electrolyte and the

cathode active material are present in the cell in

an electrolyte-to-cathode weight ratio of about 0.94 to 0.96.

2. The electrochemical cell of claim 1 wherein the cathode active material comprises fluorinated carbon.

3. The electrochemical cell of claim 2 wherein the fluorinated carbon is present in the cathode active mixture in about 80% to about 95%, by weight, remainder being at least one of a binder material and a conductive additive.

4. The electrochemical cell of claim 3 wherein the binder material is a fluoro-resin powder.

5. The electrochemical cell of claim 3 wherein the conductive additive is selected from the group consisting of carbon, graphite powder and acetylene black and metallic powder selected from the group consisting of titanium, aluminum, nickel and stainless steel, and mixtures thereof.

6. The electrochemical cell of claim 1 wherein the cathode further includes a current collector selected from the group consisting of titanium, stainless steel, tantalum, platinum and gold.

7. The electrochemical cell of claim 6 wherein the cathode current collector is provided with a layer of carbonaceous paint.

8. The electrochemical cell of claim 1 wherein the anode comprises an alkali metal.

9. The electrochemical cell of claim 8 wherein the alkali metal is lithium.

10. The electrochemical cell of claim 1 wherein the anode further includes a current collector selected from the group consisting of titanium, nickel, copper, tungsten and tantalum.

11. The electrochemical cell of claim 1 wherein the anode contacts the casing in a case-negative configuration.

12. The electrochemical cell of claim 1 wherein the electrolyte solution operatively associated with the anode and the cathode comprises an ion-forming alkali metal salt dissolved in a nonaqueous solvent, wherein the alkali metal of the salt is similar to the alkali metal comprising the anode.

13. The electrochemical cell of claim 12 wherein the alkali metal of the anode comprises lithium and the ion-forming alkali metal salt comprising the electrolyte solution is selected from the group consisting of LiPF₆, LiAsF₆, LiSbF₆, LiBF₄, LiClO₄, LiAlCl₄, LiGaCl₄, LiC(SO₂ CF₃)₃, LiN(SO₂ CF₃) and LiCF₃ SO₃, and mixtures thereof.

14. The electrochemical cell of claim 13 wherein the nonaqueous solvent comprises at least one organic solvent selected from the group consisting of tetrahydrofuran, methyl acetate, diglyme, triglyme, tetraglyme, dimethyl carbonate, 1,2-dimethoxyethane, diethyl carbonate, acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, propylene carbonate, ethylene carbonate, γ

-valerolactone, γ

-butyrolactone and N-methyl-pyrrolidinone, and mixtures thereof.

15. The electrochemical cell of claim 1 wherein a separator is provided between the anode and the cathode to prevent internal short circuit contact between them, and wherein the separator comprises a laminate of a non-woven material and a microporous membrane.

16. The electrochemical cell of claim 15 wherein the separator comprises a non-woven polypropylene layer and a polypropylene membrane.

17. The electrochemical cell of claim 16 wherein the non-woven polypropylene layer faces the cathode and the polypropylene membrane faces the anode.

18. The electrochemical cell of claim 1 housed in a conductive casing comprising a material selected from the group consisting of titanium, stainless steel, milled steel, nickel, nickel-plated milled steel and aluminum.

19. The electrochemical cell of claim 1 wherein the anode comprises lithium anode active material in electrical contact with a nickel current collector and the cathode comprises fluorinated cathode active material in electrical contact with a titanium current collector and wherein the anode and the cathode are activated with the electrolyte solution comprising 1.0 M LiBF₄ in γ

-butyrolactone and housed in a conductive casing comprising titanium.

20. An electrochemical cell, which comprises:

a) an anode comprising lithium;

b) a cathode operatively associated with the anode, wherein the cathode comprises fluorinated carbon as a cathode active material; and

c) an electrolyte solution activating the anode and the cathode, the electrolyte solution comprising an ion-forming lithium salt dissolved in a nonaqueous solvent wherein the lithium and the fluorinated carbon are present in the cell in an anode-to-cathode capacity ratio of about 1.03 and wherein the electrolyte solution and the fluorinated carbon are present in the cell in an electrolyte-to-cathode weight ratio of about 0.94 to 0.96.

21. The electrochemical cell of claim 20 wherein the fluorinated carbon is present in the cathode active mixture in about 80% to about 95%, by weight, remainder being at least one of a binder material and a conductive additive.

22. The electrochemical cell of claim 20 wherein the cathode further includes a current collector comprising titanium and the anode further includes a current collector comprising nickel.

23. The electrochemical cell of claim 22 wherein the cathode current collector is provided with a layer of carbonaceous paint.

24. The electrochemical cell of claim 20 wherein the ion-forming lithium salt comprising the electrolyte solution is selected from the group consisting of LiPF₆, LiAsF₆, LiSbF₆, LiBF₄, LiClO₄, LiAlCl₄, LiGaCl₄, LiC(SO₂ CF₃)₃, LiN(SO₂ CF₃) and LiCF₃ SO₃, and mixtures thereof.

25. The electrochemical cell of claim 20 wherein the nonaqueous solvent comprises at least one organic solvent selected from the group consisting of tetrahydrofuran, methyl acetate, diglyme, triglyme, tetraglyme, dimethyl carbonate, 1,2-dimethoxyethane, diethyl carbonate, acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, propylene carbonate, ethylene carbonate, γ

-valerolactone, γ

-butyrolactone and N-methyl-pyrrolidinone, and mixtures thereof.

26. The electrochemical cell of claim 20 wherein a separator is provided between the anode and the cathode to prevent internal short circuit contact between them, and wherein the separator comprises a laminate of a non-woven material and a microporous membrane.

27. The electrochemical cell of claim 26 wherein the separator laminate comprises a non-woven polypropylene layer and a polypropylene membrane.

28. The electrochemical cell of claim 27 wherein the non-woven polypropylene layer faces the cathode and the polypropylene membrane faces the anode.

29. The electrochemical cell of claim 20 is housed in a conductive casing comprising a material selected from the group consisting of titanium, stainless steel, mild steel, nickel, nickel-plated mild steel and aluminum.

30. The electrochemical cell of claim 20 wherein the lithium is in electrical contact with a nickel current collector and the fluorinated carbon is in electrical contact with a titanium current collector and wherein the anode and the cathode are activated with the electrolyte solution comprising 1.0 M LiB₄ in γ

-butyrolactone and housed in a conductive casing comprising titanium.

31. A method of providing an electrochemical cell, comprising the steps of:

a) providing a casing;

b) providing an anode comprising an anode active material;

c) providing a cathode comprised of a cathode active material;

d) operatively associating the anode with the cathode housed inside the casing with the anode active material and the cathode active material in an anode-to-cathode capacity ratio of about 1.03 and wherein the anode and the cathode are connected to respective terminals; and

e) activating the anode and the cathode with an electrolyte filled into the casing, wherein the electrolyte and the cathode active material are present in the cell in an electrolyte-to-cathode weight ratio of about 0.94 to 0.96.

32. The method of claim 31 including providing the cathode active material comprised of fluorinated carbon.

33. The method of claim 31 including providing the fluorinated carbon present in the cathode in about 80% to about by weight, remainder being at least one of a binder material and a conductive additive.

34. The method of claim 31 including providing the cathode having a current collector selected from the group consisting of titanium, stainless steel, tantalum, platinum and gold.

35. The method of claim 34 including providing the cathode current collector with a layer of carbonaceous paint.

36. The method of claim 31 including providing the anode comprised of an alkali metal.

37. The method of claim 31 including providing the anode having a current collector selected from the group consisting of titanium, nickel, copper, tungsten and tantalum.

38. The method of claim 31 including providing the cathode current collector comprised of titanium.

39. The method of claim 31 including providing the electrolyte solution operatively associated with the anode and the cathode comprising an ion-forming alkali metal salt dissolved in a nonaqueous solvent, wherein the alkali metal of the salt is similar to an alkali metal comprising the anode.

40. The method of claim 39 including providing the anode comprised of lithium and selecting the ion-forming alkali metal salt comprising the electrolyte solution from the group consisting of LiPF₆, LiAsF₆, LiSbF₆, LiBF₄, LiClO₄, LiAlCl₄, LiGaCl₄, LiC(SO₂ CF₃)₃, LiN(SO₂ CF₃) and LiCF₃ SO₃, and mixtures thereof.

41. The method of claim 39 including providing the nonaqueous solvent comprising at least one organic solvent selected from the group consisting of tetrahydrofuran, methyl acetate, diglyme, triglyme, tetraglyme, dimethyl carbonate, 1,2-dimethoxyethane, diethyl carbonate, acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, propylene carbonate, ethylene carbonate, γ

-valerolactone, γ

-butyrolactone and N-methyl-pyrrolidinone, and mixtures thereof.

42. The method of claim 31 including providing a separator between the anode and the cathode to prevent internal short circuit conditions and further including providing the separator comprising a a non-woven material and a microporous membrane.

43. The method of claim 42 including providing the separator comprising a non-woven polypropylene layer and a polypropylene membrane.

44. The method of claim 43 including providing the non-woven polypropylene layer facing the cathode and the polypropylene layer facing the anode.

45. The method of claim 31 including providing the casing comprising a conductive material selected from the group consisting of titanium, stainless steel, milled steel, nickel, nickel-plated milled steel and aluminum.

46. The method of claim 31 including providing lithium as the anode active material contacting a nickel current collector and fluorinated carbon as the cathode active material contacting a titanium current collector and activating the anode and the cathode with the electrolyte comprising 1.0 M LiBF₄ in γ

-butyrolactone and further including housing the cell in a conductive casing comprising titanium.