Alkali/transition metal halo - and hydroxy-phosphates and related electrode active materials

• US 20030027049A1
• Filed: 10/26/2001
• Published: 02/06/2003
• Est. Priority Date: 04/27/2000
• Status: Active Grant

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Saidi, M. Yazid, Swoyer, Jeffrey L.
• Granted Patent: US 6,777,132 B2
• Time in Patent Office: Days
• US Class Current: 429/231.95
• CPC Class Codes: C01B 25/455 containing halogen completely halogenated alkali metal phosphates C01D, e.g. lithium hexafluorophosphate C01D15/005
• 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 2004/028 Positive electrodes
• 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 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/623 fluorinated polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

from Groups 2, 3, 12, 13, or 14 of the Periodic Table. Preferred embodiments include those having where c=1, those where c=2, and those where c=3. Preferred embodiments include those where a ≦1 and c=1, those where a=2 and c=1, and those where a≧3 and c=3. This invention also provides electrodes comprising an electrode active material of this invention, and batteries that comprise a first electrode having an electrode active material of this invention; a second electrode having a compatible active material; and an electrolyte.

Claims

1. An electrode active material comprising a compound of the formula

A_aM_b(XY₄)_cZ_d,

wherein

(a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<

a≦

8;

(b) M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦

b≦

3;

(c) XY₄ is selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y′

_2y, X″

S₄, and mixtures thereof, where X′

is P, As, Sb, Si, Ge, S, and mixtures thereof;

X″

is P, As, Sb, Si, Ge and mixtures thereof;

Y′

is halogen;

0≦

x<

3; and

0<

y<

4; and

0<

c≦

3;

(d) Z is OH, halogen, or mixtures thereof, and 0<

d≦

6; and

wherein M, X, Y, Z, a, b, c, d, x and y are selected so as to maintain electroneutrality of said compound.

2. An electrode active material according to claim 1, wherein c=1.

3. An electrode active material according to claim 2, wherein 0.1≦

a≦

3, and 0.1≦

d≦

3.

4. An electrode material according to claim 3, wherein 1≦

a≦

3, and 1≦

d≦

3.

5. An electrode active material according to claim 2, wherein said active material has an olivine structure.

6. An electrode active material according to claim 1, wherein c=3.

7. An electrode active material according to claim 6, wherein 2≦

a≦

6, and 2≦

d≦

6.

8. An electrode active material according to claim 7, wherein 3≦

a≦

6, and 3≦

d≦

6.

9. An electrode active material according to claim 6, wherein said active material has a NASICON structure.

10. An electrode active material according to claim 1, wherein A comprises Li.

11. An electrode active material according to claim 1, wherein A is selected from the group consisting of Na, K, mixtures thereof, and mixtures thereof with Li.

12. An electrode active material according to claim 11, wherein A comprises Na.

13. An electrode active material according to claim 1, wherein M comprises two or more transition metals from Groups 4 to 11 of the Periodic Table.

14. An electrode active material according to claim 13, wherein said transition metals are selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, and Cr.

15. An electrode active material according to claim 1, wherein M comprises M′

M″

, where M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table; and

M″

is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table.

16. An electrode active material according to claim 15, wherein M′

is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

17. An electrode active material according to claim 16, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

18. An electrode active material according to claim 15, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.

19. An electrode active material according to claim 18, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

20. An electrode active material according to claim 1, wherein X′

comprises As, Sb, Si, Ge, S, and mixtures thereof; and

X″

comprises As, Sb, Si, Ge and mixtures thereof.

21. An electrode active material according to claim 20, wherein X′

comprises Si, and X″

comprises Si.

22. An electrode active material according to claim 1, wherein XY₄ is selected from the group consisting Of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y_2y, X″

S₄, and mixtures thereof, where X′

is P and X″

is P; and

0<

x<

3; and

0<

y<

4.

23. An electrode active material according to claim 1, wherein XY₄ is selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y′

_2y, X″

S₄, and mixtures thereof, where X′

is P, As, Sb, Si, Ge, S, and mixtures thereof;

X″

is P, As, Sb, Si, Ge and mixtures thereof;

Y′

is halogen;

0<

x<

3; and

0<

y<

4.

24. An electrode active material according to claim 1, wherein Y′

is F.

25. An electrode active material according to claim 1, wherein XY₄ comprises X″

S₄.

26. An electrode active material according to claim 1, wherein Z comprises F.

27. An electrode active material according to claim 26, wherein Z is F.

28. An electrode active material according to claim 27, wherein XY₄ is selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y′

_2y, X″

S₄, and mixtures thereof, where X′

is P and X″

is P; and

0<

x<

3; and

0<

y<

4.

29. An electrode active material according to claim 1, wherein Z comprises OH.

30. An electrode active material according to claim 29, wherein X′

is P, and X″

is P.

31. An electrode active material according to claim 1, wherein X comprises Br or Cl.

32. An electrode active material according to claim 31, wherein X′

is P, and X″

is P.

85. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 1.

91. A lithium battery comprising:

(a) a first electrode comprising an active material according to claim 1,

(b) a second electrode which is a counter-electrode to said first electrode; and

(c) an electrolyte between said electrodes.

92. A lithium battery of claim 91, wherein said first electrode is a cathode, and said second electrode is an insertion anode.

93. A lithium battery of claim 92, wherein said second electrode comprises a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.

33. An electrode active material comprising a compound of the formula

Li_aM_b(PO₄)Z_d,

wherein

(a) 0.1<

a≦

4;

(b) M is M′

M″

, where M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table; and

M″

is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table, and 1≦

b≦

3; and

(c) Z comprises halogen, and 0.1<

d≦

4; and

wherein M, Z, a, b, and d are selected so as to maintain electroneutrality of said compound.

34. An electrode active material according to claim 33, wherein M′

is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

35. An electrode active material according to claim 34, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

36. An electrode active material according to claim 33, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.

37. An electrode active material according to claim 36, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

38. An electrode active material according to claim 33, wherein Z comprises F.

40. An electrode active material according to claim 37, wherein M comprises M′

M″

, where M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table; and

M″

is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table.

41. An electrode active material according to claim 40, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

42. An electrode active material according to claim 41, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

43. An electrode active material according to claim 40, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.

44. An electrode active material according to claim 43, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

86. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 33.

94. A lithium battery comprising:

(a) a first electrode comprising an active material according to claim 33,

(b) a second electrode which is a counter-electrode to said first electrode; and

(c) an electrolyte between said electrodes.

39. An electrode active material comprising a compound of the formula

Li_aM_b(PO₄)Z_d,

wherein

(a) 0.1<

a≦

4;

(b) M is one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦

b≦

3; and

(c) Z is OH or a mixture of OH and halogen, and 0.1<

d≦

4; and

wherein M, Z, a, b, and d are selected so as to maintain electroneutrality of said compound.

87. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 39.

95. A lithium battery comprising:

(a) a first electrode comprising an active material according to claim 39,

(b) a second electrode which is a counter-electrode to said first electrode; and

(c) an electrolyte between said electrodes.

45. An electrode active material comprising a compound of the formula

Li₂M(PO₄)Z_d,

wherein

(b) M is M′

<sub>1−

b</sub>M″

_b, where M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table; and

M″

is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table, and 0≦

b<

1; and

(c) Z comprises halogen, and 0.1<

d≦

2; and

wherein M, Z, b, and d are selected so as to maintain electroneutrality of said compound.

46. An electrode active material according to claim 45, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

47. An electrode active material according to claim 46, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

48. An electrode active material according to claim 45, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.

49. An electrode active material according to claim 48, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

50. An electrode active material according to claim 45, wherein Z comprises F.

51. An electrode active material according to claim 45, of the formula Li₂MPO₄F, wherein M is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, Zn, or mixtures thereof.

52. An electrode active material according to claim 51, wherein M is Fe, Co, Mn, or mixtures thereof.

53. An electrode active material according to claim 52, of the formula Li₂CoPO₄F or Li₂FePO₄F.

54. An electrode active material according to claim 45, wherein M′

is Fe or Co, M″

is Mg, and X is F.

55. An electrode active material according to claim 54, wherein M′

is Fe.

56. An electrode active material according to claim 55, of the formula Li₂Fe_0.9Mg_0.1PO₄F.

88. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 45.

96. A lithium battery comprising:

(a) a first electrode comprising an active material according to claim 45,

(b) a second electrode which is a counter-electrode to said first electrode; and

(c) an electrolyte between said electrodes.

57. An electrode active material comprising a compound of the formula

A_aM_b(XY₄)₃Z_d,

wherein

(a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 2≦

a≦

8;

(b) M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦

b≦

3;

(c) XY₄ is selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y′

_2y, X″

S₄, and mixtures thereof, where X′

is P, As, Sb, Si, Ge, S, and mixtures thereof;

X″

is P, As, Sb, Si, Ge and mixtures thereof;

Y′

is halogen;

0≦

x<

3; and

0<

y<

4;

(d) Z is OH, halogen, or mixtures thereof, and 0<

d≦

6; and

wherein M, X, Y, Z, a, b, d, x and y are selected so as to maintain electroneutrality of said compound.

58. An electrode active material according to claim 57, wherein A comprises Li.

59. An electrode active material according to claim 57, wherein A comprises Na, K, or mixtures thereof.

60. An electrode active material according to claim 57, wherein M comprises two or more transition metals from Groups 4 to 11 of the Periodic Table.

61. An electrode active material according to claim 60, wherein said transition metals are selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, and Cr, and mixtures thereof.

62. An electrode active material according to claim 57, wherein M comprises M′

M″

, where M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table; and

M″

is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table.

63. An electrode active material according to claim 62, wherein M′

is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

64. An electrode active material according to claim 63, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

65. An electrode active material according to claim 62, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.

66. An electrode active material according to claim 65, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

67. An electrode active material according to claim 57, wherein XY₄ is PO₄.

68. An electrode active material according to claim 57, wherein X′

comprises As, Sb, Si, Ge, S, and mixtures thereof;

X″

comprises As, Sb, Si, Ge and mixtures thereof; and

0<

x<

3.

69. An electrode active material according to claim 57, wherein Z comprises F.

70. An electrode active material according to claim 57, wherein Z comprises OH.

89. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 57.

97. A lithium battery comprising:

(a) a first electrode comprising an active material according to claim 57,

(b) a second electrode which is a counter-electrode to said first electrode; and

(c) an electrolyte between said electrodes.

98. A lithium battery of claim 97, wherein said first electrode is a cathode, and said second electrode is an insertion anode.

99. A lithium battery of claim 98, wherein said second electrode comprises a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.

71. An electrode active material comprising an active material of the formula

A_aM_b(XY₄)₂Z_d,

wherein

(a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0.1<

a≦

6;

(b) M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦

b≦

3;

(c) XY₄ is selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y′

_2y, X″

S₄, and mixtures thereof, where X′

is P, As, Sb, Si, Ge, S, and mixtures thereof;

X″

is P, As, Sb, Si, Ge and mixtures thereof;

Y′

is halogen;

0≦

x<

3; and

0<

y<

4; and

;

(d) Z is OH, halogen, or mixtures thereof, and 0<

d≦

6; and

wherein M, X, Y, Z, a, b, d, x and y are selected so as to maintain electroneutrality of said compound.

72. An electrode active material according to claim 71, wherein A comprises Li.

73. An electrode active material according to claim 71, wherein A comprises Na, K, or mixtures thereof.

74. An electrode active material according to claim 71, wherein M comprises two or more transition metals from Groups 4 to 11 of the Periodic Table.

75. An electrode active material according to claim 74, wherein said transition metals are selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, and Cr, and mixtures thereof.

76. An electrode active material according to claim 71, wherein M comprises M′

M″

, where M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table; and

M″

is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table.

77. An electrode active material according to claim 76, wherein M′

is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

78. An electrode active material according to claim 77, wherein M′

is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

79. An electrode active material according to claim 76, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.

80. An electrode active material according to claim 79, wherein M″

is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

81. An electrode active material according to claim 71, wherein XY₄ is PO₄.

82. An electrode active material according to claim 71, wherein X′

comprises As, Sb, Si, Ge, S, and mixtures thereof;

X″

comprises As, Sb, Si, Ge and mixtures thereof; and

0<

x<

3.

83. An electrode active material according to claim 71, wherein Z comprises F.

84. An electrode active material according to claim 71, wherein Z comprises OH.

90. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 71.

100. A lithium battery comprising:

(a) a first electrode comprising an active material according to claim 71,

(b) a second electrode which is a counter-electrode to said first electrode; and

(c) an electrolyte between said electrodes.