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

• US 6,777,132 B2
• Filed: 10/26/2001
• Issued: 08/17/2004
• Est. Priority Date: 04/27/2000
• Status: Expired due to Fees

• 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.
• Primary Examiner(s): CHANEY, CAROL DIANE
• Application Number:
  US10/014,822
• Publication Number:
  US 20030027049A1
• Time in Patent Office: 1,026 Days
• Field of Search: 429/218.1, 429/231.1, 429/231.2, 429/231.3
• US Class Current: 429/231.1
• 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

The present invention relates to novel electrode active materials represented by the general formula A_aM_b(XY₄)_cZ_d, wherein:

(a) A is one or more alkali metals, and 0<a≦8;

(b) M is at least one metal capable of undergoing oxidation to a higher valence state, and 1≦b≦3;

(c) XY₄ is selected from the group consisting of X′O_4−xY′_x, X′O_4−yY′_2y, X″S₄, and a mixture 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, 0<y<4, and 0<c≦3; and

(d) Z is OH, a halogen, or mixtures thereof, and 0<d≦6.

Claims

1. An electrode active material represented by the general formula:

2. The electrode active material according to claim 1, wherein A is Li.

3. The electrode active material according to claim 1, wherein a=3+2x+d.

4. The electrode active material according to claim 1, wherein a is 0.1 to about 6.

5. The electrode active material according to claim 1, wherein a is from about 2 to about 6.

6. The electrode active material according to claim 1, wherein a is from about 3 to about 6.

7. The electrode active material according to claim 1, wherein M comprises a transition metal selected from Groups 4 to 11 of the Periodic Table.

8. The electrode active material according to claim 7, wherein M is a +3 oxidation state transition metal selected from Groups 4 to 11 of the Periodic Table.

9. The electrode active material according to claim 7, wherein M is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

10. The electrode active material according to claim 1, wherein M is M′

M″

, wherein M′

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

M″

is at least one element selected from Groups 2, 3, 12, 13, and 14 of the Periodic Table.

11. The electrode active material according to claim 10, wherein M′

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

12. The electrode active material according to claim 11, wherein M′

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

13. The electrode active material according to claim 11, wherein M″

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

14. The electrode active material according to claim 11, wherein M″

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

15. The electrode active material according to claim 10, wherein M″

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

16. The electrode active material according to claim 1, wherein Z comprises F.

17. The electrode active material according to claim 1, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

18. The electrode active material according to claim 1, wherein d is from 0.1 to about 6.

19. The electrode active material according to claim 1, wherein d is from about 2 to about 6.

20. The electrode active material according to claim 1, wherein d is from about 3 to about 6.

21. A battery, comprising:

a first electrode comprising electrode active material represented by the general formula;

22. The battery according to claim 21, wherein A is Li.

23. The battery according to claim 21, wherein a=3+2x+d.

24. The battery according to claim 21, wherein a is 0.1 to about 6.

25. The battery according to claim 21, wherein a is from about 2 to about 6.

26. The battery according to claim 21, wherein a is from about 3 to about 6.

27. The battery according to claim 21, wherein M comprises a transition metal selected from Groups 4 to 11 of the Periodic Table.

28. The battery according to claim 27, wherein M is a +3 oxidation state transition metal selected from Groups 4 to 11 of the Periodic Table.

29. The battery according to claim 27, wherein M is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.

30. The battery according to claim 21, wherein M is M′

M″

, wherein M′

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

M″

is at least one element selected from Groups 2, 3, 12, 13, and 14 of the Periodic Table.

31. The battery according to claim 30, wherein M′

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

32. The battery according to claim 31, wherein M′

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

33. The battery according to claim 31, wherein M″

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

34. The battery according to claim 33, wherein M″

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

35. The battery according to claim 30, wherein M″

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

36. The battery according to claim 21, wherein Z comprises F.

37. The battery according to claim 21, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

38. The battery according to claim 21, wherein d is from 0.1 to about 6.

39. The battery according to claim 21, wherein d is from about 2 to about 6.

40. The battery according to claim 21, wherein d is from about 3 to about 6.

41. The battery according to claim 21, wherein the second electrode comprises a material selected from the group consisting of a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.

42. The battery according to claim 41, wherein the electrolyte comprises a solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropylcarbonate, ethyl methyl carbonate, butylene carbonate, γ

-butyrolactone, triglyme, tetraglyme, a lactone, an ester, dimethylsulfoxide, dioxolane, sulfolane, and mixtures thereof.

43. The battery according to claim 42, wherein the electrolyte further comprises a lithium salt selected from the group consisting of LiAsF₆, LiPF₆, LiClO₄, LiB(C₆H₅)₄, LiAlCl₄, LiBr, and mixtures thereof.

44. An electrode active material represented by the general formula:

45. The electrode active material according to claim 44, wherein A is Li.

46. The electrode active material according to claim 44, wherein a is 0.1 to about 6.

47. The electrode active material according to claim 44, wherein a is from about 2 to about 6.

48. The electrode active material according to claim 44, wherein a is from about 3 to about 6.

49. The electrode active material according to claim 44, wherein M consists of two transition metals selected from Groups 4 through 11 of the Periodic Table.

50. The electrode active material according to claim 49, wherein M is consists of two transition metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Go, Ni, Cu, and mixtures thereof.

51. The electrode active material according to claim 44, wherein M comprises two or more transition metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Go, Ni, Cu, and mixtures thereof.

52. The electrode active material according to claim 44, wherein 0<

x<

3.

53. The electrode active material according to claim 44, wherein x=0.

54. The electrode active material according to claim 44, wherein x=3.

55. The electrode active material according to claim 44, wherein Z comprises F.

56. The electrode active material according to claim 44, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

57. The electrode active material according to claim 44, wherein d is from 0.1 to about 6.

58. The electrode active material according to claim 44, wherein d is from about 2 to about 6.

59. The electrode active material according to claim 44, wherein d is from about 3 to about 6.

60. A battery, comprising:

a first electrode comprising an electrode active material represented by the general formula;

61. The battery according to claim 60, wherein A is Li.

62. The battery according to claim 60, wherein a is 0.1 to about 6.

63. The battery according to claim 60, wherein a is from about 2 to about 6.

64. The battery according to claim 60, wherein a is from about 3 to about 6.

65. The battery according to claim 60, wherein M consists of two transition metals selected from Groups 4 through 11 of the Periodic Table.

66. The battery according to claim 65, wherein M is consists of two transition metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and mixtures thereof.

67. The battery according to claim 60, wherein M comprises two or more transition metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and mixtures thereof.

68. The battery according to claim 67, wherein M comprises two or more transition metals selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.

69. The battery according to claim 60, wherein 0<

x<

3.

70. The battery according to claim 60, wherein x=0.

71. The battery according to claim 60, wherein x=3.

72. The battery according to claim 60, wherein Z comprises F.

73. The battery according to claim 60, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

74. The battery according to claim 60, wherein d is from 0.1 to about 6.

75. The battery according to claim 60, wherein d is from about 2 to about 6.

76. The battery according to claim 60, wherein d is from about 3 to about 6.

77. The battery according to claim 60, wherein the second electrode comprises a material selected from the group consisting of a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.

78. The battery according to claim 77, wherein the electrolyte comprises a solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropylcarbonate, ethyl methyl carbonate, butylene carbonate, γ

-butyrolactone, triglyme, tetraglyme, a lactone, an ester, dimethylsulfoxide, dioxolane, sulfolane, and mixtures thereof.

79. The battery according to claim 78, wherein the electrolyte further comprises a lithium salt selected from the group consisting of LiAsF₆, LiPF₆, LiClO₄, LiB(C₆H₅)₄, LiAlCl₄, LiBr, and mixtures thereof.

80. A battery, comprising:

a first electrode comprising an electrode active material represented by the general formula;

81. The battery according to claim 80, wherein A is Li.

82. The battery according to claim 80, wherein a is 0.1 to about 6.

83. The battery according to claim 80, wherein a is from about 2 to about 6.

84. The battery according to claim 80, wherein a is from about 3 to about 6.

85. The battery according to claim 80, wherein M′

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

86. The battery according to claim 85, wherein M′

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

87. The battery according to claim 85, wherein M″

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

88. The battery according to claim 87, wherein M″

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

89. The battery according to claim 80, wherein M″

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

90. The battery according to claim 80, wherein M consists of M′

M″

, wherein M′

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

M″

is at least one element selected from Groups 2, 3, 12, 13, and 14 of the Periodic Table.

91. The battery according to claim 90, wherein M′

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

92. The battery according to claim 91, wherein M′

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

93. The battery according to claim 91, wherein M″

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

94. The battery according to claim 93, wherein M″

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

95. The battery according to claim 90, wherein M″

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

96. The battery according to claim 80, wherein 0<

x<

3.

97. The battery according to claim 80, wherein x=0.

98. The battery according to claim 80, wherein x=3.

99. The battery according to claim 80, wherein Z comprises F.

100. The battery according to claim 80, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

101. The battery according to claim 80, wherein d is from 0.1 to about 6.

102. The battery according to claim 80, wherein d is from about 2 to about 6.

103. The battery according to claim 80, wherein d is from about 3 to about 6.

104. The battery according to claim 80, wherein the second electrode comprises a material selected from the group consisting of a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.

105. The battery according to claim 104, wherein the electrolyte comprises a solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropylcarbonate, ethyl methyl carbonate, butylene carbonate, γ

-butyrolactone, triglyme, tetraglyme, a lactone, an ester, dimethylsulfoxide, dioxolane, sulfolane, and mixtures thereof.

106. The battery according to claim 105, wherein the electrolyte further comprises a lithium salt selected from the group consisting of LiAsF₆, LiPF₆, LiClO₄, LiB(C₆H₅)₄, LiAlCl₄, LiBr, and mixtures thereof.

107. An electrode active material represented by the general formula:

108. The electrode active material according to claim 107, wherein A is Li.

109. The electrode active material according to claim 107, wherein a is 0.1 to about 6.

110. The electrode active material according to claim 107, wherein a is from about 2 to about 6.

111. The electrode active material according to claim 107, wherein a is from about 3 to about 6.

112. The electrode active material according to claim 107, wherein M comprises two or more transition metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Go, Ni, Cu, and mixtures thereof.

113. The electrode active material according to claim 107, wherein M is M′

M″

, wherein M′

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

M″

is at least one element selected from Groups 2, 3, 12, 13, and 14 of the Periodic Table.

114. The electrode active material according to claim 113, wherein M′

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

115. The electrode active material according to claim 114, wherein M′

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

116. The electrode active material according to claim 114, wherein M″

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

117. The electrode active material according to claim 116, wherein M″

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

118. The electrode active material according to claim 113, wherein M″

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

119. The electrode active material according to claim 107, wherein 0<

x<

3.

120. The electrode active material according to claim 107, wherein x=0.

121. The electrode active material according to claim 107, wherein x=3.

122. The electrode active material according to claim 107, wherein Z comprises F.

123. The electrode active material according to claim 107, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

124. The electrode active material according to claim 107, wherein d is from 0.1 to about 6.

125. The electrode active material according to claim 107, wherein d is from about 2 to about 6.

126. The electrode active material according to claim 107, wherein d is from about 3 to about 6.

127. A battery, comprising:

a first electrode comprising an electrode active material represented by the general formula;

128. The battery according to claim 127, wherein A is Li.

129. The battery according to claim 127, wherein a is 0.1 to about 6.

130. The battery according to claim 127, wherein a is from about 2 to about 6.

131. The battery according to claim 127, wherein a is from about 3 to about 6.

132. The battery according to claim 127, wherein M comprises two or more transition metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and mixtures thereof.

133. The battery according to claim 127, wherein M is M′

M″

, wherein M′

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

M″

is at least one element selected from Groups 2, 3, 12, 13, and 14 of the Periodic Table.

134. The battery according to claim 133, wherein M′

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

135. The battery according to claim 134, wherein M′

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

136. The battery according to claim 134, wherein M″

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

137. The battery according to claim 136, wherein M″

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

138. The battery according to claim 133, wherein M″

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

139. The battery according to claim 127, wherein 0<

x<

3.

140. The battery according to claim 127, wherein x=0.

141. The battery according to claim 127, wherein x=3.

142. The battery according to claim 127, wherein Z comprises F.

143. The battery according to claim 127, wherein Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.

144. The battery according to claim 127, wherein d is from 0.1 to about 6.

145. The battery according to claim 127, wherein d is from about 2 to about 6.

146. The battery according to claim 127, wherein d is from about 3 to about 6.

147. The battery according to claim 127, wherein b=2 and the second electrode comprises a material selected from the group consisting of a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.

148. The battery according to claim 147, wherein the electrolyte comprises a solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropylcarbonate, ethyl methyl carbonate, butylene carbonate, γ

-butyrolactone, triglyme, tetraglyme, a lactone, an ester, dimethylsulfoxide, dioxolane, sulfolane, and mixtures thereof.

149. The battery according to claim 148, wherein the electrolyte further comprises a lithium salt selected from the group consisting of LiAsF₆, LiPF₆, LiClO₄, LiB(C₆H₅)₄, LiAlCl₄, LiBr, and mixtures thereof.