Lithium-containing phosphates, methods of preparation, and uses thereof

• US 20040086784A1
• Filed: 10/06/2003
• Published: 05/06/2004
• Est. Priority Date: 09/23/1996
• Status: Abandoned Application

• Current Assignee: Jeremy Barker, Saidi M. Yazid
• Original Assignee: Jeremy Barker, Saidi M. Yazid
• Inventors: Barker, Jeremy, Saidi, M. Yazid
• Application Number:
  US10/681,563
• Publication Number:
  US 20040086784A1
• Time in Patent Office: Days
• US Class Current: 429/231.5
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• 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 2004/027 Negative electrodes
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/0459 Electrochemical doping, intercalation, occlusion or alloying
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The invention provides an electrochemical cell which comprises a first electrode and a second electrode which is a counter electrode to said first electrode. The first electrode comprises a phosphorous compound of the nominal general formula Li₃E′_aE″_b(PO₄)₃, desirably at least one E is a metal; and preferably, Li₃M′M″(PO₄)₃. E′ and E″ are the same or different from one another, where at least one of E′ and E″ has more than one oxidation state.

Claims

1. A mixture, comprising:

a compound represented by the nominal formula Li₃V₂(PO₄)₃, and an electrically conductive diluent.

2. The mixture of claim 1, wherein electrically conductive diluent is carbon.

3. The mixture of claim 1, wherein electrically conductive diluent is carbon black.

4. The mixture of claim 3, wherein the carbon black has a BET average surface area of 70±

5 m²/gr.

5. The mixture of claim 1, further comprising a binder.

6. The mixture of claim 5, wherein the binder is selected from the group consisting of an ethylene propylene diene termonomer, polyvinylidene difluoride, an ethylene acrylic acid copolymer, and an ethylene vinyl acetate copolymer.

7. The mixture of claim 1, wherein the compound has an XRD pattern corresponding to FIG. 6.

8. An electrode, comprising:

an electrode active material represented by the nominal formula Li₃V₂(PO₄)₃; and

an electrically conductive diluent.

9. The electrode of claim 8, wherein the electrically conductive diluent is carbon.

10. The electrode of claim 8, wherein the electrically conductive diluent is carbon black.

11. The electrode of claim 10, wherein the carbon black has a BET average surface area of 70±

5 m²/gr.

12. The electrode of claim 10, wherein the electrode comprises from 5 to 30% by weight carbon black.

13. The electrode of claim 8, further comprising a binder.

14. The electrode of claim 13, wherein the binder is selected from the group consisting of an ethylene propylene diene termonomer, polyvinylidene difluoride, an ethylene acrylic acid copolymer, and an ethylene vinyl acetate copolymer.

15. The electrode of claim 13, wherein the electrode comprises from 3 to 20% by weight binder.

16. The electrode of claim 8, wherein the electrode active material has an XRD pattern corresponding to FIG. 6.

17. A battery, comprising:

a first electrode comprising an electrode active material in a first condition represented by the nominal formula Li<sub>3−

x</sub>V₂(PO₄)₃, the first electrode further comprising an electrically conductive diluent;

a second electrode comprising an intercalation active material; and

an electrolyte;

wherein in the first condition x=0, and in a second condition 0<

x≦

3 and at least one V has an oxidation state higher than its oxidation state in the first condition.

18. The battery of claim 17, wherein the electrically conductive diluent is carbon.

19. The battery of claim 17, wherein the electrically conductive material is carbon black.

20. The electrode of claim 19, wherein the carbon black has a BET average surface area of 70±

5 m²/gr.

21. The electrode of claim 19, wherein the electrode comprises from 5 to 30% by weight carbon black.

22. The battery of claim 17, wherein the first electrode further comprises a binder.

23. The battery of claim 22, wherein the binder is selected from the group consisting of an ethylene propylene diene termonomer, a polyvinylidene difluoride, an ethylene acrylic acid copolymer, and an ethylene vinyl acetate copolymer.

24. The battery of claim 22, wherein the first electrode comprises from 3 to 20% by weight binder.

25. The battery of claim 17, wherein the intercalation active material is selected from the group consisting of a transition metal oxide, a metal chalcogenide, carbon, graphite, and mixtures thereof.

26. The battery of claim 25, wherein the second electrode comprises graphite.

27. The battery of claim 25, wherein the electrically conductive diluent of the first electrode is carbon.

28. The battery of claim 25, wherein the electrically conductive diluent of the first electrode is carbon black.

29. The battery of claim 28, wherein the carbon black has a BET average surface area of 70±

5 m²/gr.

30. The battery of claim 17, wherein the electrode active material of the first electrode has an XRD pattern corresponding to FIG. 6.

31. A method of making a lithium-vanadium-phosphate compound, comprising the steps of:

forming a mixture of a lithium-containing compound, at least one vanadium oxide compound, and a phosphoric acid-containing compound; and

heating the mixture at a temperature and for a time sufficient to form a lithium-vanadium-phosphate compound.

32. The method of claim 31, wherein the lithium-containing compound is selected from the group consisting of lithium acetate, lithium hydroxide, lithium nitrate, and lithium carbonate.

33. The method of claim 31, wherein the at least one vanadium oxide compound is selected from the group consisting of V₂O₅ and V₂O₃.

34. The method of claim 31, wherein the wherein the at least one vanadium oxide compound is V₂O₃.

35. The method of claim 31, wherein the phosphoric acid-containing compound is ammonium phosphate.

36. The method of claim 31, wherein the step of forming a mixture further comprises blending the mixture together with a solvent to form a wet mixture, wherein the wet mixture is heated at a temperature and for a time sufficient to form the lithium-vanadium-phosphate compound.

37. The method of claim 36, wherein the solvent is selected from the group consisting of xylene and methanol.

38. The method of claim 36, wherein the step of forming a mixture further comprises the steps of drying the wet mixture to form a dry mixture, and pressing the dry mixture into pellets, wherein the pellets are heated at a temperature and for a time sufficient to form the compound.

39. The method of claim 31, wherein the step of heating the mixture further comprises heating the mixture in a non-oxidizing, reducing atmosphere.

40. The method of claim 39, wherein the reducing atmosphere is a hydrogen atmosphere.

41. The method of claim 31, wherein the lithium-vanadium-phosphate compound has an XRD pattern corresponding to FIG. 6.

42. A method of making a compound represented by the nominal formula Li₃V₂(PO₄)₃, comprising the steps of:

forming a mixture of a lithium-containing compound, at least one vanadium oxide compound, and a phosphoric acid-containing compound, in proportions to provide a compound represented by the nominal formula Li₃V₂(PO₄)₃; and

heating the mixture at a temperature and for a time sufficient to form the compound.

43. The method of claim 42, wherein the lithium-containing compound is selected from the group consisting of lithium acetate, lithium hydroxide, lithium nitrate, and lithium carbonate.

44. The method of claim 42, wherein the at least one vanadium oxide compound is selected from the group consisting of V₂O₅ and V₂O₃.

45. The method of claim 42, wherein the at least one vanadium oxide compound is V₂O₃.

46. The method of claim 42, wherein the phosphoric acid-containing compound is ammonium phosphate.

47. The method of claim 42, wherein the step of forming a mixture further comprises blending the mixture together with a solvent to form a wet mixture, wherein the wet mixture is heated at a temperature and for a time sufficient to form the lithium-vanadium-phosphate compound.

48. The method of claim 47, wherein the solvent is selected from the group consisting of xylene and methanol.

49. The method of claim 47, wherein the step of forming a mixture further comprises the steps of drying the wet mixture to form a dry mixture, and pressing the dry mixture into pellets, wherein the pellets are heated at a temperature and for a time sufficient to form the compound.

50. The method of claim 42, wherein the step of heating the mixture further comprises heating the mixture in a non-oxidizing, reducing atmosphere.

51. The method of claim 50, wherein the reducing atmosphere is a hydrogen atmosphere.

52. The method of claim 42, wherein the compound has an XRD pattern corresponding to FIG. 6.

53. A compound represented by the nominal formula Li₃V₂(PO₄)₃, made by a process comprising the steps of:

forming a mixture of a lithium-containing compound, at least one vanadium oxide compound, and a phosphoric acid-containing compound, in proportions to provide a compound represented by the nominal formula Li₃V₂(PO₄)₃; and

heating the mixture at a temperature and for a time sufficient to form the compound.

54. The compound of claim 53, wherein the lithium-containing compound is selected from the group consisting of lithium acetate, lithium hydroxide, lithium nitrate, and lithium carbonate.

55. The compound of claim 53, wherein the at least one vanadium oxide compound is selected from the group consisting of V₂O₅ and V₂O₃.

56. The compound of claim 53, wherein the phosphoric acid-containing compound is ammonium phosphate.

57. The compound of claim 53, wherein the step of forming a mixture further comprises blending the mixture together with a solvent to form a wet mixture, wherein the wet mixture is heated at a temperature and for a time sufficient to form the lithium-vanadium-phosphate compound.

58. The compound of claim 57, wherein the solvent is selected from the group consisting of xylene and methanol.

59. The compound of claim 57, wherein the step of forming a mixture further comprises the steps of drying the wet mixture to form a dry mixture, and pressing the dry mixture into pellets, wherein the pellets are heated at a temperature and for a time sufficient to form the compound.

60. The compound of claim 53, wherein the step of heating the mixture further comprises heating the mixture in a non-oxidizing, reducing atmosphere.

61. The compound of claim 60, wherein the reducing atmosphere is a hydrogen atmosphere.

62. The compound of claim 53, wherein the compound has an XRD pattern corresponding to FIG. 6.