Alkali/transition metal halo--and hydroxy-phosphates and related electrode active materials Number:6,777,132 from the United States Patent and Trademark Office (PTO) owispatent The present invention relates to novel electrode active materials represented by the general formula A.sub.a M.sub.b (XY.sub.4).sub.c Z.sub.d, wherein: (a) A is one or more alkali metals, and 0<a.ltoreq.8; (b) M is at least one metal capable of undergoing oxidation to a higher valence state, and 1.ltoreq.b.ltoreq.3; (c) XY.sub.4 is selected from the group consisting of X'O.sub.4-x Y'.sub.x, X'O.sub.4-y Y'.sub.2y, X"S.sub.4, 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.ltoreq.x<3, 0<y<4, and 0<c.ltoreq.3; and (d) Z is OH, a halogen, or mixtures thereof, and 0<d.ltoreq.6.<H phosphates, transition, Alkali, transiti, 6777132.html, Patent, pto, 6777132

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

Abstract: The present invention relates to novel electrode active materials represented by the general formula A.sub.a M.sub.b (XY.sub.4).sub.c Z.sub.d, wherein: (a) A is one or more alkali metals, and 0<a.ltoreq.8; (b) M is at least one metal capable of undergoing oxidation to a higher valence state, and 1.ltoreq.b.ltoreq.3; (c) XY.sub.4 is selected from the group consisting of X'O.sub.4-x Y'.sub.x, X'O.sub.4-y Y'.sub.2y, X"S.sub.4, 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.ltoreq.x<3, 0<y<4, and 0<c.ltoreq.3; and (d) Z is OH, a halogen, or mixtures thereof, and 0<d.ltoreq.6.

Patent Number: 6,777,132 Issued on 08/17/2004 to Barker, et al.

Inventors: Barker; Jeremy (Shipton-under-Wychwood, GB), Saidi; M. Yazid (Henderson, NV), Swoyer; Jeffrey L. (Henderson, NV)
Assignee: Valence Technology, Inc. (Henderson, NV)

Appl. No.: 10/014,822

Filed: October 26, 2001

Related U.S. Patent Documents


Application Number	Filing Date	Patent Number	Issue Date
559861	Apr., 2000	6387568

Current U.S. Class: 429/231.1 ; 429/231.2; 429/231.3

Current International Class: C01B 25/00 (20060101); C01B 25/455 (20060101); H01M 4/58 (20060101); H01M 4/02 (20060101); H01M 10/36 (20060101); H01M 10/40 (20060101)

Field of Search: 429/218.1,231.1,231.2,231.3

References Cited [Referenced By]

U.S. Patent Documents


3736184	May 1973	Dey et al.
4009092	February 1977	Taylor
4049891	September 1977	Hong et al.
4098687	July 1978	Yang
4194062	March 1980	Carides et al.
4260668	April 1981	Lecerf et al.
4434216	February 1984	Joshi et al.
4464447	August 1984	Lazzari et al.
4477541	October 1984	Fraioli
4512905	April 1985	Clearfield et al.
4668595	May 1987	Yoshino et al.
4683181	July 1987	Armand et al.
4690877	September 1987	Gabano et al.
4707422	November 1987	de Neufville et al.
4792504	December 1988	Schwab et al.
4803137	February 1989	Miyazaki et al.
4830939	May 1989	Lee et al.
4925752	May 1990	Fauteux et al.
4935317	June 1990	Fauteux et al.
4985317	January 1991	Adachi et al.
4990413	February 1991	Lee et al.
5011501	April 1991	Shackle et al.
5028500	July 1991	Fong et al.
5037712	August 1991	Shackle et al.
5130211	July 1992	Wilkinson et al.
5232794	August 1993	Krumpelt et al.
5262253	November 1993	Golovin
5262548	November 1993	Barone
5296436	March 1994	Bortinger
5300373	April 1994	Shackle
5326653	July 1994	Chang
5399447	March 1995	Chaloner-Gill et al.
5411820	May 1995	Chaloner-Gill
5418090	May 1995	Koksbang et al.
5418091	May 1995	Gozdz et al.
5435054	July 1995	Tonder et al.
5456000	October 1995	Gozdz et al.
5460904	October 1995	Gozdz et al.
5463179	October 1995	Chaloner-Gill et al.
5482795	January 1996	Chaloner-Gill
5508130	April 1996	Golovin
5514490	May 1996	Chen et al.
5538814	July 1996	Kamauchi et al.
5540741	July 1996	Gozdz et al.
5541020	July 1996	Golovin et al.
5620810	April 1997	Golovin et al.
5643695	July 1997	Barker et al.
5660948	August 1997	Barker
5695893	December 1997	Arai et al.
5700298	December 1997	Shi et al.
5712059	January 1998	Barker et al.
5721070	February 1998	Shackle
5804335	September 1998	Komauchi
5830602	November 1998	Barker et al.
5851504	December 1998	Barker et al.
5869207	February 1999	Saidi et al.
5871866	February 1999	Barker et al.
5910382	June 1999	Goodenough et al.
6004697	December 1999	Thackeray et al.
6020087	February 2000	Gao
6103419	August 2000	Saidi et al.
6136472	October 2000	Barker et al.
6153333	November 2000	Barker
6183718	February 2001	Barker et al.
6306215	October 2001	Larkin
6387568	May 2002	Barker et al.
6514640	February 2003	Armand et al.
2001/0055718	December 2001	Li et al.

Foreign Patent Documents


0 680 106	Nov., 1995	EP
0 849 817	Jun., 1998	EP
1 049 182	Nov., 2000	EP
1 093 172	Apr., 2001	EP
61-263069	Nov., 1986	JP
06-251764	Sep., 1994	JP
09-171827	Jun., 1997	JP
2001 052733	Feb., 2001	JP
2001 085010	Mar., 2001	JP
WO 98/12761	Mar., 1998	WO
WO 99/30378	Jun., 1999	WO
WO 00/01024	Jan., 2000	WO
WO 00/31812	Jun., 2000	WO
WO 00/57505	Sep., 2000	WO
WO 01/13443	Feb., 2001	WO
WO 01/53198	Jul., 2001	WO
WO 01/54212	Jul., 2001	WO
WO 01/84655	Nov., 2001	WO
WO 02/44084	Jun., 2002	WO
WO 02/097907	Dec., 2002	WO

Other References

http://www.webmineral.com/data/Griphite.shtml.* .
Rinaldi, "The crystal structure of griphite, complex phosphate not a garnetoid", Bulletin de Mineralogie (1978) 101(5-6, 543-7.* .
Andersson, A., et al., "Thermal Stability of LiFePO.sub.4 -Based Cathodes" Electrochemical and Solid State Matters, vol. 3(2), pp. 66-68 (2000). .
Amine, K., et al., "Olivine LiCoPO.sub.4 as 4.8 V Electrode Material For Lithium Batteries" Electrochemical and Solid-State Letters, vol. 3(4), pp. 178-179 (2000). .
Kirby, et al., "Crystal Structure of Potassium Aluminum Fluoride Phosphate KAIFPO.sub.4 " Zeits. Kristall., p. 956 (1995). .
Nagornyi, et al., "Preparation and Structure of the New Fluoride Phosphate Na.sub.5 CrF.sub.2 (PO.sub.4).sub.2 " Russ. J. Inorg. Chem., vol. 35, p. 470 (1990). .
Arlt, et al., "Na.sub.5 AlF.sub.2 (PO.sub.4).sub.2 : Darstellung, Kristallstruktur und Lonenleitfahigkeit" Z. Anorg. Allg. Chem., vol. 179, p. 547 (1987). .
www.webmineral.com/data/Amblygonite.shtml. .
www.webmineral.com/data/Lacroixite.shtml. .
www.webmineral.com/data/Montebrasite.shtml. .
www.webmineral.com/data/Travorite.shtml. .
International Search Report for PCT/US97/1544. .
Rangan, K, et al., "New Titanium-Vanadium Phosphates of Nasicon and Langbeinite Structures, and Differences Between the Two Structures Toward Deintercalation of Alkali Metal" Journal of Solid State Chemistry, vol. 109, pp. 116-121 (1994). .
Delmas, C., et al., "The Nasicon-Type Titanium Phosphates ATi.sub.2 (PO.sub.4).sub.3 (A=Li, Na) as Electrode Materials" Solid State Ionics, vol. 28-30, pp. 419-423 (1988). .
Hagenmuller, P., et al., "Intercalation in 3D-Skeleton Structures: Ionic and Electronic Features" Mat. Res. Soc. Symp. Proc., vol. 210, pp. 232-334 (1991). .
Chem. Abstrs. Svs., XP 2048304 (1997). .
Padhi et al., "Lithium Intercalation into NASICON-Type Mixed Phosphates: . . . and Li.sub.2 FeTi(PO.sub.4).sub.3 " 37.sup.th Power Sources Conference, Cherry Hill, New Jersey, Conference Dates: Jun. 17-20, 1996; published Oct. 15, 1996. .
Sisler, H., et al., "Chemistry: A Systematic Approach" Oxford University Press, p. 746 (1980). .
Gopalakrishnan, J., et al., "V.sub.2 PO.sub.4 :A Novel NASICON-Type Vanadium Phosphate Synthesized by Oxidative Deintercalation of odium from Na.sub.3 V.sub.2 PO.sub.4 " Chemistry of Materials, vol. 4(4), pp. 745-747(1992). .
Delmas, C., "The Chemical Short Circuit Method. An Improvement in the Intercalation-Deintercalation Techniques" Mat. Res. Bull., vol. 23, pp. 65-72 (1988). .
Ivanov-Schitz, A., et al., "Electrical and Interfacial Properties of a Li.sub.3 Fe.sub.2 (PO.sub.4).sub.3 Single Crystal with Silver Electrodes" Solid State Ionics, vol. 91, pp. 93-99 (1996). .
Cretin, M., et al., "Study of Li.sub.1+x Al.sub.x Ti.sub.2-x (PO.sub.4).sub.3 for Li.sup.+ Potentiometric Sensors" Journal of the European Ceramic Society, vol. 15, pp. 1149-1156 (1995). .
Chem. Abstrs. Svs., XP 2048305 (1995). .
Patent Abstracts of Japan, vol. 94, No. 64 (1994) (Abstract for JP 06-251764). .
Okada, S., et al., "Fe.sub.2 (SO.sub.4).sub.3 as a Cathode Material for Rechargeable Lithium Batteries" (Date and name of publication unknown). .
Adachi, G., et al., "Lithium-ion Conductive Solid Electrolyte" Chemical Abstracts 112 129692 (1981). .
Delmas, C., et al., "A Nasicon-type Phase as Intercalation Electrode: Sodium Titanium Phosphate (NaTi.sub.2 (PO.sub.4).sub.3)" Mater. Res. Bull., vol. 22(5) pp. 631-9 (1987). .
Nanjundaswamy, K.S., et al., "Synthesis, Redox Potential Evaluation and Electrochemical Characteristics of NASICON-Related-3D Framework Compounds" Solid State Ionics, vol. 92, pp. 1-10 (1996). .
Nadiri, A., et al., "Lithium Intercalation in Lithium Titanium Phosphate (LiTi.sub.2 (PO.sub.4).sub.3)" C. R. Acad. Sci., ser. 2, vol. 304(9), pp. 415-418 (1987) (Abstract Only). .
Cotton et al., "Advanced Inorganic Chemistry: A Comprehensive Text" Interscience Publishers, 3.sup.rd Edition, pp. 864-868. .
Linden, D., "Handbook of Batteries" McGraw Hill, 2.sup.nd Edition, pp. 36.4-36.9. .
Bykov et al., Superionic Conductors Li.sub.3 M.sub.2 (PO.sub.4).sub.3 (M=Fe, Sc, Cr): Synthesis and Electrophysical Properties Solid State Ionics, vol. 138, pp. 31-52 (1990). .
Genkina, et al., "Crystal Structure of Synthetic Tavorite LiFe[PO.sub.4 ](OH,F)" Kristallografiya, vol. 29(1), pp. 50-55 (1984). .
Genkina, et al., "Phase Formation and Crystallochemistry of Phosphates" Izv. Akad. .
Dutreilh, et al., "Synthesis and Crystal Structure of a New Lithium Nickel Fluorophosphates Li.sub.2 [NiF(PO.sub.4)]. . . " Journal of Solid State Chemistry, vol. 142, pp. 1-5 (1999). .
M-T Averbuch-Pouchot, et al., "Topics in Phosphate Chemistry" World Scientific Publishing Co., Singapore, pp. 106-119 (1996). .
Loiseau, et al., "NH.sub.4 FePO.sub.4 F: Structural Study and Magnetic Properties" Journal of Solid State Chemistry III, pp. 390-396 (1994). .
LeMeins, et al., "Phase Transitions in the Na.sub.3 M.sub.2 (PO4)F.sub.3 Family (M=Al.sup.3+, V.sup.3+, Cr.sup.3+, Fe.sup.3+, Ga.sup.3+): Synthesis, thermal and Structural, and Magnetic Studies" Journal of Solid State Chemistry, vol. 148, pp. 260-277 (1999). .
Moss, et al., "On the X-Ray Identification of Amblygonite and Montebrasite" Mineralogical Magazine, vol. 37, No. 287, pp. 414-422 (1969). .
Padhi, A.K., et al., "Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries" J. Electrochem. Soc., vol. 144(4), pp. 1188-1194 (1997). .
Yukabovich, et al., "The Mixed Anionic Framework in the Structure of Na.sub.2 {MnF[PO.sub.4 ]}" Acta Crystallographia Section C; Crystal Structure Communications, vol. C53(4), pp. 395-397 (1997). .
LeMeins, et al., "Ionic Conductivity of Crystalline and Amorphous Na.sub.3 Al.sub.2 (PO.sub.4)F.sub.3 " Solid State Ionics Diffusion Reactions, vol. 111, pp. 67-75 (1998). .
PCT International Search Report PCT/US01/08132 dated Sep. 27, 2001. .
Reddy and Hossain, (Editor Linden), "Rechargeable Lithium Batteries (Ambient Temperature)" Handbood of Batteries, 3.sup.rd Edition, pp. 34.1-34.62. .
Rinaldi, "The Crystal Structure of Griphite, Complex Phosphate Not a Garnetoid" Bulletin de Mineralogie, 101(5-6), pp. 453-457 (1978). .
International Search Report for PCT/US02/33510..

Primary Examiner: Chaney; Carol
Attorney, Agent or Firm: Ross; Michael D. Williams; Roger A. Kovacevic; Cynthia S.

Parent Case Text

This application is a continuation-in-part of U.S. patent application Ser. No. 09/559,861, filed Apr. 27, 2000 now U.S. Pat. No. 6,387,568.

Claims

What is claimed is:

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

wherein, (a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a.ltoreq.8; (b) M comprises one or more metals, wherein at least one of the one or more metals is capable of undergoing oxidation to a higher valence state, and 1.ltoreq.b.ltoreq.3; (c) 0<x<3; and (d) Z is selected from the group consisting of a hydroxyl, a halogen, and mixtures thereof, and 0 6; wherein A, M, Z, a, b, x and d are selected so as to maintain electroneutrality of the electrode active material.

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, .gamma.-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 LiAsF.sub.6, LiPF.sub.6, LiClO.sub.4, LiB(C.sub.6 H.sub.5).sub.4, LiAlCl.sub.4, LiBr, and mixtures thereof.

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

wherein, (a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a.ltoreq.8; (b) M comprises two or more transition metals selected from Groups 4 through 11 of the Periodic Table, and 1.ltoreq.b.ltoreq.3; (c) 0.ltoreq.x.ltoreq.3; and (d) Z is selected from the group consisting of a hydroxyl, a halogen, and mixtures thereof, and 0<d.ltoreq.6; wherein A, M, Z, a, b, x and d are selected so as to maintain electroneutrality of the electrode active material.

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, .gamma.-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 LiAsF.sub.6, LiPF.sub.6, LiClO.sub.4, LiB(C.sub.6 H.sub.5).sub.4, LiAlCl.sub.4, 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, .gamma.-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 LiAsF.sub.6, LiPF.sub.6, LiClO.sub.4, LiB(C.sub.6 H.sub.5).sub.4, LiAlCl.sub.4, LiBr, and mixtures thereof.

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

wherein, (a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, 0<a.ltoreq.8, and a=3+2x+d; (b) M comprises one or more metals, wherein at least one of the one or more metals is capable of undergoing oxidation to a higher valence state, and 1.ltoreq.b.ltoreq.3; (c) 0.ltoreq.x.ltoreq.3; and (d) Z is selected from the group consisting of a hydroxyl, a halogen, and mixtures thereof, and 0<d.ltoreq.6; wherein A, M, Z, a, b, x and d are selected so as to maintain electroneutrality of the electrode active material.

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, .gamma.-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 LiAsF.sub.6, LiPF.sub.6, LiClO.sub.4, LiB(C.sub.6 H.sub.5).sub.4, LiAlCl.sub.4, LiBr, and mixtures thereof.

Description

FIELD OF THE INVENTION

This invention relates to electrode active materials, electrodes, and batteries. In particular, this invention relates to active materials comprising lithium or other alkali metals, transition metals, phosphates or similar moieties, and halogen or hydroxyl moieties.

BACKGROUND OF THE INVENTION

A wide variety of electrochemical cells, or "batteries," are known in the art. In general, batteries are devices that convert chemical energy into electrical energy, by means of an electrochemical oxidation-reduction reaction. Batteries are used in a wide variety of applications, particularly as a power source for devices that cannot practicably be powered by centralized power generation sources (e.g., by commercial power plants using utility transmission lines).

Batteries can be generally described as comprising three components: an anode, that contains a material that is oxidized (yields electrons) during discharge of the battery (i.e., while it is providing power); a cathode that contains a material that is reduced (accepts electrons) during discharge of the battery; and an electrolyte that provides for transfer of ions between the cathode and anode. During discharge, the anode is the negative pole of the battery, and the cathode is the positive pole. Batteries can be more specifically characterized by the specific materials that make up each of these three components. Selection of these components can yield batteries having specific voltage and discharge characteristics that can be optimized for particular applications.

Batteries can also be generally categorized as being "primary," where the electrochemical reaction is essentially irreversible, so that the battery becomes unusable once discharged; and "secondary," where the electrochemical reaction is, at least in part, reversible so that the battery can be "recharged" and used more than once. Secondary batteries are increasingly used in many applications, because of their convenience (particularly in applications where replacing batteries can be difficult), reduced cost (by reducing the need for replacement), and environmental benefits (by reducing the waste from battery disposal).

There are a variety of secondary battery systems known in the art. Among the most common systems are lead-acid, nickel-cadmium, nickel-zinc, nickel-iron, silver oxide, nickel metal hydride, rechargeable zinc-manganese dioxide, zinc-bromide, metal-air, and lithium batteries. Systems containing lithium and sodium afford many potential benefits, because these metals are light in weight, while possessing high standard potentials. For a variety of reasons, lithium batteries are, in particular, commercially attractive because of their high energy density, higher cell voltages, and long shelf-life.

Lithium batteries are prepared from one or more lithium electrochemical cells containing electrochemically active (electroactive) materials. Among such batteries are those having metallic lithium anodes and metal chalcogenide (oxide) cathodes, typically referred to as "lithium metal" batteries. The electrolyte typically comprises a salt of lithium dissolved in one or more solvents, typically nonaqueous aprotic organic solvents. Other electrolytes are solid electrolytes (typically polymeric matrixes) that contain an ionic conductive medium (typically a lithium containing salt dissolved in organic solvents) in combination with a polymer that itself may be ionically conductive but electrically insulating.

Cells having a metallic lithium anode and metal chalcogenide cathode are charged in an initial condition. During discharge, lithium metal yields electrons to an external electrical circuit at the anode. Positively charged ions are created that pass through the electrolyte to the electrochemically active (electroactive) material of the cathode. The electrons from the anode pass through the external circuit, powering the device, and return to the cathode.

Another lithium battery uses an "insertion anode" rather than lithium metal, and is typically referred to as a "lithium ion" battery. Insertion or "intercalation" electrodes contain materials having a lattice structure into which an ion can be inserted and subsequently extracted. Rather than chemically altering the intercalation material, the ions slightly expand the internal lattice lengths of the compound without extensive bond breakage or atomic reorganization. Insertion anodes contain, for example, lithium metal chalcogenide, lithium metal oxide, or carbon materials such as coke and graphite. These negative electrodes are used with lithium-containing insertion cathodes. In their initial condition, the cells are not charged, since the anode does not contain a source of cations. Thus, before use, such cells must be charged in order to transfer cations (lithium) to the anode from the cathode. During discharge the lithium is then transferred from the anode back to the cathode. During subsequent recharge, the lithium is again transferred back to the anode where it reinserts. This back-and-forth transport of lithium ions (Li.sup.+) between the anode and cathode during charge and discharge cycles had led to these cells as being called "rocking chair" batteries.

A variety of materials have been suggested for use as cathode active materials in lithium batteries. Such materials include, for example, MoS.sub.2, MnO.sub.2, TiS.sub.2, NbSe.sub.3, LiCoO.sub.2, LiNiO.sub.2, LiMn.sub.2 O.sub.4, V.sub.6 O.sub.13, V.sub.2 O.sub.5, SO.sub.2, CuCl.sub.2. Transition metal oxides, such as those of the general formula Li.sub.x MO.sub.y, are among those materials preferred in such batteries having intercalation electrodes. Other materials include lithium transition metal phosphates, such as LiFePO.sub.4, and Li.sub.3 V(PO.sub.4).sub.3. Such materials having structures similar to olivine or NASICON materials are among those known in the art. Cathode active materials among those known in the art are disclosed in S. Hossain, "Rechargeable Lithium Batteries (Ambient Temperature)," Handbook of Batteries, 2d ed., Chapter 36, Mc-Graw Hill (1995); U.S. Pat. No. 4,194,062, Carides, et al., issued Mar. 18, 1980; U.S. Pat. No. 4,464,447, Lazzari, et al., issued Aug. 7, 1984; U.S. Pat. No. 5,028,500, Fong et al., issued Jul. 2, 1991; U.S. Pat. No. 5,130,211, Wilkinson, et al., issued Jul. 14, 1992; U.S. Pat. No. 5,418,090, Koksbang et al., issued May 23, 1995; U.S. Pat. No. 5,514,490, Chen et al., issued May 7, 1996; U.S. Pat. No. 5,538,814, Kamauchi et al., issued Jul. 23, 1996; U.S. Pat. No. 5,695,893, Arai, et al., issued Dec. 9, 1997; U.S. Pat. No. 5,804,335, Kamauchi, et al., issued Sep. 8, 1998; U.S. Pat. No. 5,871,866, Barker et al., issued Feb. 16, 1999; U.S. Pat. No. 5,910,382, Goodenough, et al., issued Jun. 8, 1999; PCT Publication WO/00/31812, Barker, et al., published Jun. 2, 2000; PCT Publication WO/00/57505, Barker, published Sep. 28, 2000; U.S. Pat. No. 6,136,472, Barker et al., issued Oct. 24, 2000; U.S. Pat. No. 6,153,333, Barker, issued Nov. 28, 2000; PCT Publication WO/01/13443, Barker, published Feb. 22, 2001; and PCT Publication WO/01/54212, Barker et al., published Jul. 26, 2001.

In general, such a cathode material must exhibit a high free energy of reaction with lithium, be able to intercalate a large quantity of lithium, maintain its lattice structure upon insertion and extraction of lithium, allow rapid diffusion of lithium, afford good electrical conductivity, not be significantly soluble in the electrolyte system of the battery, and be readily and economically produced. However, many of the cathode materials known in the art lack one or more of these characteristics. As a result, for example, many such materials are not economical to produce, afford insufficient voltage, have insufficient charge capacity, or lose their ability to be recharged over multiple cycles.

SUMMARY OF THE INVENTION

The invention provides electrode active materials comprising lithium or other alkali metals, a transition metal, a phosphate or similar moiety, and a halogen or hydroxyl moiety. Such electrode actives include those of the formula:

In a preferred embodiment, M comprises two or more transition metals from Groups 4 to 11 of the Periodic Table. In another preferred embodiment, 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 from Groups 2, 3, 12, 13, or 14 of the Periodic Table. Preferred embodiments include those where c=1, those where c=2, and those where c=3. Preferred embodiments include those where a.ltoreq.1 and c=1, those where a=2 and c=1, and those where a.gtoreq.3 and c=3. Preferred embodiments also include those having a structure similar to the mineral olivine (herein "olivines"), and those having a structure similar to NASICON (NA Super Ionic CONductor) materials (herein "NASICONs").

This invention also provides electrodes comprising an electrode active material of this invention. Also provided are 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. In a preferred embodiment, the novel electrode material of this invention is used as a positive electrode (cathode) active material, reversibly cycling lithium ions with a compatible negative electrode (anode) active material.

It has been found that the novel electrode materials, electrodes, and batteries of this invention afford benefits over such materials and devices among those known in the art. Such benefits include increased capacity, enhanced cycling capability, enhanced reversibility, and reduced costs. Specific benefits and embodiments of the present invention are apparent from the detailed description set forth herein. It should be understood, however, that the detailed description and specific examples, while indicating embodiments among those preferred, are intended for purposes of illustration only and are not intended to limited the scope of the inventi