LITHIUM-BASED ACTIVE MATERIALS AND PREPARATION THEREOF

• US 20030129492A1
• Filed: 01/18/2000
• Published: 07/10/2003
• Est. Priority Date: 01/18/2000
• Status: Active Grant

• Current Assignee: Lithium Werks Technology BV
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Saidi, M. Yazid
• Granted Patent: US 7,001,690 B2
• Time in Patent Office: Days
• US Class Current: 429/221
• 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 4/131 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 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• 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 4/623 fluorinated polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The invention provides novel lithium-mixed metal materials which, upon electrochemical interaction, release lithium ions, and are capable of reversibly cycling lithium ions. The invention provides a rechargeable lithium battery which comprises an electrode formed from the novel lithium-mixed metal materials. Methods for making the novel lithium-mixed metal materials and methods for using such lithium-mixed metal materials in electrochemical cells are also provided. The lithium-mixed metal materials comprise lithium and at least one other metal besides lithium. Preferred materials are lithium-mixed metal phosphates which contain lithium and two other metals besides lithium.

Claims

1. A single phase compound represented by the nominal general formula LiFe₁₋

yM_yPO₄ where 0<

y<

0.5 and M is at least one metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof.

2. The single phase compound of claim 1 where 0<

y≦

0.2.

3. The single phase compound of claim 1 having the nominal formula LiFe₁₋

yMg_yPO₄.

4. The single phase compound of claim 1 having the nominal formula LiFe_0.9Mg_0.1PO₄.

5. The single phase compound of claim 1 having the nominal formula LiFe₁₋

yCa_yPO₄.

6. The single phase compound of claim 1 having the nominal formula LiFe_0.9Ca_0.1PO₄.

7. The single phase compound of claim 1 having the nominal formula LiFe₁₋

yZn_yPO₄.

8. The single phase compound of claim 1 having the nominal formula LiFe_0.9Zn_0.1PO₄.

9. The single phase compound of claim 1 which has an olivine structure.

10. A single phase compound having the nominal general formula LiMI₁₋

yMII_yPO₄ where MI is selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Sn, Ti, Cr, and mixtures thereof, and MII is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof, and where y is greater than zero and less than one.

11. An olivine compound having the nominal general formula LiM₁₋

yM_yPO₄where MI is at least one transition metal selected from Groups 4 to 11 inclusive of the Periodic Table and has a +2 valence state, MII is at least one metallic element which is selected from Groups 2, 12, and 14 of the Periodic Table and has a +2 valence state, and where 0<

y<

1.

12. The compound of claim 11 wherein MI is selected from the group consisting of V, Cr, Mn, Fe, Co, Cu, and mixtures thereof.

13. The compound of claim 11 wherein MII is selected from the group consisting of Mg, Ca, Ba, Zn, and mixtures thereof.

14. An electrode comprising a binder, an electrically conductive carbonaceous material, and an active material represented by the nominal general formula LiFe₁₋

yM_yPO₄ where 0<

y<

0.5 and M is at least one metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof.

15. The electrode of claim 14 wherein said active material is a single phase compound where 0<

y≦

0.2.

16. The electrode of claim 14 wherein said active material is a single phase compound having the nominal formula LiFe₁₋

yMg_yPO₄.

17. The electrode of claim 14 wherein said active material is a single phase compound having the nominal formula LiFe_0.9Mg_0.1PO₄.

18. The electrode of claim 14 wherein said active material is a single phase compound having the nominal formula LiFe₁₋

yCa_yPO₄.

19. The electrode of claim 14 wherein said active material is a single phase compound having the nominal formula LiFe_0.9Ca_0.1PO₄.

20. The electrode of claim 14 wherein said active material is a single phase compound having the nominal formula LiFe₁₋

yZn_yPO₄.

21. The electrode of claim 14 wherein said active material is a single phase compound having the nominal formula LiFe_0.9Zn_0.1PO₄.

22. The electrode of claim 14 wherein said active material has an olivine structure.

23. An electrode comprising a binder, an electrically conductive carbonaceous material and an active material which is an olivine compound represented by the nominal general formula LiM₁₋

yM_yPO₄ where MI is at least one transition metal selected from Groups 4 to 11 inclusive of the Periodic Table and has a +2 valence state, MII is at least one metallic element which is selected from Groups 2, 12, and 14 of the Periodic Table and has a +2 valence state, and where 0<

y<

1.

24. The electrode of claim 23 wherein MI is selected from the group consisting of V, Cr, Mn, Fe, Co, Cu, and mixtures thereof.

25. The electrode of claim 23 wherein MII is selected from the group consisting of Mg, Ca, Ba, Zn, and mixtures thereof.

26. A lithium ion battery comprising:

a first electrode having an active material represented by the general formula LiFe<sub>1−

y</sub>M_yPO₄ where 0<

y<

0.5 and M is at least one metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof;

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

an electrolyte between said electrodes.

27. The battery of claim 26 wherein said active material is a single phase compound where 0<

y≦

0.2.

28. The battery of claim 26 wherein said active material is a single phase compound having the nominal formula LiFe₁₋

yMg_yPO₄.

29. The battery of claim 26 wherein said active material is a single phase compound having the nominal formula LiFe_0.9Mg_0.1PO₄.

30. The battery of claim 26 wherein said active material is a single phase compound having the nominal formula LiFe₁₋

yCa_yPO₄.

31. The battery of claim 26 wherein said active material is a single phase compound having the nominal formula LiFe_0.9Ca_0.1PO₄.

32. The battery of claim 26 wherein said active material is a single phase compound having the nominal formula LiFe₁₋

yZn_yPO₄.

33. The battery of claim 26 wherein said active material is a single phase compound having the nominal formula LiFe_0.9Zn_0.1PO₄.

34. The battery of claim 26 wherein said active material has an olivine structure.

35. A lithium ion battery comprising:

a first electrode having an active material which is an olivine compound represented by the nominal general formula LiM<sub>1−

y</sub>M_yPO₄ where MI is at least one transition metal selected from Groups 4 to 11 inclusive of the Periodic Table and has a +2 valence state, MII is at least one metallic element which is selected from Groups 2, 12, and 14 of the Periodic Table and has a +2 valence state, and where 0<

y<

1;

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

an electrolyte between said electrodes.

36. The battery of claim 35 wherein MI is selected from the group consisting of V, Cr, Mn, Fe, Co, Cu, and mixtures thereof.

37. The battery of claim 35 wherein MII is selected from the group consisting of Mg, Ca, Ba, Zn, and mixtures thereof.

38. A single phase compound represented by the nominal formula LiV₂O₅ and having an orthorhombic crystal structure with a=9.7±

0.2 Å

, =3.6±

0.2 Å and

c=10.6±

0.2 Å

.

39. The compound of claim 38 which is prepared by reacting vanadium pentoxide and lithium compound in the presence of carbon at an elevated temperature sufficient to form said single phase compound.

40. An electrode comprising a binder, an electrically conductive carbonaceous material and an active material which is a single phase compound represented by the nominal general formula LiV₂O₅ and having an orthorhombic crystal structure with a=9.7±

0.2 Å

, b=3.6±

0.2 Å and

c=10.6±

0.2 Å

.

41. A lithium ion battery comprising:

a first electrode having an active material which is a single phase compound represented by the nominal formula LiV₂O₅ and having orthorhombic crystal structure which a=9.7±

0.2 Å

, b=3.6±

0.2 Å and

c=10.6±

0.2 Å

;

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

an electrolyte between said electrodes.