Alkali transition metal phosphates and related electrode active materials

• US 20030170542A1
• Filed: 03/06/2002
• Published: 09/11/2003
• Est. Priority Date: 03/06/2002
• Status: Active Grant

• Current Assignee: Lithium Werks Technology BV
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Saidi, M. Yazid, Swoyer, Jeffrey L.
• Granted Patent: US 6,815,122 B2
• Time in Patent Office: Days
• US Class Current: 429/231.9
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01B 33/20 Silicates persilicates C01B15/14 ; containing aluminium C01B33/26
• 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 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• 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 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 50/426 Fluorocarbon polymers
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Electrode active materials comprising lithium or other alkali metals, a transition metal, and a phosphate or similar moiety, of the formula:

A_a+xM_bP_1-xSi_xO₄

wherein

(a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a<1.0 and 0≦x≦1;

(b) M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, where 0<b≦2; and

wherein M, a, b, and x are selected so as to maintain electroneutrality of said compound. In a preferred embodiment, M comprises at least one transition metal selected from Groups 4 to 11 of the Periodic Table. In another preferred embodiment, M comprises M′_cM″_d, 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, and c+d=b. Preferably, 0.1≦a≦0.8. Preferred embodiments include those having a structure similar to the mineral olivine (herein “olivines”). 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; and an electrolyte.

Claims

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

A_a+xM_bP_1-xSi_xO₄

wherein

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

a<

1 and 0≦

x≦

1;

(b) M comprises one or more metals, comprising at least one metal which is capable of oxidation to a higher valence state, where 0<

b≦

2; and

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

2. An electrode active material according to claim 1, wherein 0.1≦

a≦

0.9.

3. An electrode active material according to claim 1, wherein 1.0≦

b≦

1.5.

4. An electrode active material according to claim 1, wherein M comprises a +3 oxidation state transition metal.

5. An electrode active material according to claim 1, wherein M comprises a +2 oxidation state transition metal.

6. An electrode active material according to claim 1, wherein M is M′

_cM″

_d, wherein M′

0 comprises one or more transition metal from Groups 4 to 11 of the Periodic Table;

M″

is at least one element selected from Group 2, 12, 13, or 14 of the Periodic Table; and

c+d=b.

7. An electrode active material according to claim 6, wherein 0<

(c+d)≦

2.

8. An electrode active material according to claim 7, wherein 1.0≦

(c+d)≦

1.5.

9. An electrode active material according to claim 4, wherein M′

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

10. An electrode active material according to claim 4, wherein M″

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

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

40. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 1.

45. 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.

46. A lithium battery of claim 45, wherein said first electrode is a cathode, and said second electrode is an insertion anode.

47. A lithium battery of claim 46, wherein said second electrode comprises a metal oxide, metal chalcogenide, carbon, graphite and mixtures thereof.

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

Li_aM′

_cM″

_dPO₄

wherein

(a) 0<

a<

1;

(b) M′

comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, where c>

0;

(c) M″

comprises one or more non-transition metals, where d>

0; and

wherein 0.8≦

(c+d)≦

1.5, and M′

, M″

, a, c, and are selected so as to maintain electroneutrality of said compound.

13. An electrode active material according to claim 12, wherein M′

is a +2 oxidation state transition metal.

14. An electrode active material according to claim 13, wherein M′

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

15. An electrode active material according to claim 12, wherein M″

is a +2 or +3 oxidation state non-transition metal.

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

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

17. An electrode active material according to claim 12, wherein M″

is a +3 oxidation state transition metal.

18. An electrode active material according to claim 17, wherein M″

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

41. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 12.

48. A lithium battery comprising

(a) a first electrode comprising an active material according to claim 12,

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

and

(c) an electrolyte between said electrodes.

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

A_aM¹_eM²_fM³_gPO₄

wherein

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

a<

1;

(b) M¹ is a +2 oxidation state transition metal, where e>

0;

(c) M² is a +2 oxidation state non-transition metal; and

(d) M³ is a +3 oxidation state non-transition metal; and

wherein a+2e+2f+3g=3.

20. An electrode active material according to claim 19, wherein M¹ is selected from the group consisting of Fe, Co, Ni, Ti, V, Cr, Mn, and mixtures thereof.

21. An electrode active material according to claim 19, wherein M² is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.

22. An electrode active material according to claim 19, wherein M³ is selected from the group consisting of B, Al, Ga, In and mixtures thereof.

23. An electrode active material according to claim 19, wherein 0<

(e+f+g)≦

2.

24. An electrode active material according to claim 23, wherein 0.8≦

(e+f+g)≦

1.5.

25. An electrode active material according to claim 24, wherein 1.0≦

(e+f+g)≦

1.5.

42. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 19.

49. A lithium battery comprising

(a) a first electrode comprising an active material according to claim 19,

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

and

(c) an electrolyte between said electrodes.

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

A_a+xM′

_1+(x/2)M″

_(1-a)/2P_1-xSi_xO₄

wherein

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

a<

1.0 and x=0;

(b) M′

comprises one or more +2 oxidation state transition metals; and

(c) M″

comprises one or more +2 oxidation state non transition metals;

wherein M′

, M″

, a, and x are selected so as to maintain electroneutrality of said compound.

27. An electrode active material according to claim 26, wherein A is Li.

29. An electrode active material according to claim 26, wherein M″

is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.

30. An electrode active material according to claim 29, wherein M″

is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.

43. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 26.

50. A lithium battery comprising

(a) a first electrode comprising an active material according to claim 26,

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

and

(c) an electrolyte between said electrodes.

28. An electrode active material according to clam 26, wherein M′

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

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

A_a+xM′

_1+(x/2)M″

_(1-a)/3P_1-xSi_xO₄

wherein

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

a<

1.0 and x=0;

(b) M′

comprises one or more +2 oxidation state metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state; and

(c) M″

comprises one or more +3 oxidation state metals;

wherein M′

, M″

, a, and x are selected so as to maintain electroneutrality of said compound.

32. A n electrode active material according to claim 31, wherein A is Li.

33. An electrode active material according to claim 32, wherein M″

comprises a +3 oxidation state transition metal.

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

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

35. An electrode active material according to claim 31, wherein M″

is a +3 oxidation state non-transition metal.

36. An electrode active material according to claim 35, wherein M″

is selected from the group consisting of B, Al, Ga, In, and mixtures thereof.

37. An electrode active material according to claim 31, wherein M′

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

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

further comprises a +2 oxidation state non transition metal.

39. An electrode active material according to claim 38, wherein said non-transition metal is selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ra, and mixtures thereof.

44. An electrode comprising a binder;

an electrically conductive carbonaceous material; and

an active material of claim 31.

51. A lithium battery comprising

(a) a first electrode comprising an active material according to claim 31,

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

and

(c) an electrolyte between said electrodes.