Claims
- 1. A positive electrode-active material comprising a composite oxide in a single phase having the general formula Lix M1y M2z M3u M4w On, where 0<x≦2, the sum of y+z+u+w is about 1 to 2, y, u and w are each greater than 0, and 2≦n≦4, where M1, M2, M3 and M4 are different and are selected from the group consisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, N, P, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, and where one of M1, M2, M3 and M4 is present in an amount of at least about 70 mol percent of the combined M1, M2, M3 and M4.
- 2. The material according to claim 1, wherein M1, M2, M3 and M4 are selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, Ga, Zr, Hf, Mg, Ca, and Sn.
- 3. The material according to claim 2, wherein Ml is manganese, M2 is nickel, M3 is cobalt and M4 is aluminum.
- 4. The material according to claim 3, wherein 0.7≦z/(y+z+u+w)<1.0.
- 5. The material according to claim 4, wherein z/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2, u/(y+z+u+w)≦0.1, and w/(y+z+u+w)≦0.1.
- 6. The material according to claim 5, wherein z/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2, u/(y+z+u+w)≦0.05, and w/(y+z+u+w)≦0.05.
- 7. The material according to claim 6, wherein the composite oxide has a general formula of Lix Mn0.2 Ni0.7 Co0.05 Al0.05 On.
- 8. A method of producing a positive electrode-active material comprising the steps:
a. mixing salts of four different metals selected from the group consisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, into solution in a liquid solvent; b. precipitating a homogeneous mixture of the four metals from the solution; c. adding lithium to the homogeneous precipitated mixture; and d. calcining the mixture of lithium and the four different metals in the presence of oxygen to form a lithiated composite oxide of the four metals.
- 9. The method according to claim 8, wherein the lithiated composite oxide comprises a single phase.
- 10. The method according to claim 9, wherein the four metals are selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, Ga, Zr, Hf, Mg, Ca, and Sn, and are supplied as salts.
- 11. The method according to claim 10, wherein the four metals are manganese, nickel, cobalt and aluminum.
- 12. The method according to claim 11, wherein one of the four metals is present in an amount of at least about 70 mol percent of the combined amount of the four metals.
- 13. The method according to claim 12, wherein the liquid solvent is water and the salts are nitrates, sulfates, phosphates, or halides and at least one of the four metal salts comprises the metal in its lowest oxidation state.
- 14. The method according to claim 13, wherein at least two of the four metal salts comprise the metals in their lowest oxidation state.
- 15. The method according to claim 14, wherein each one of the four metal salts comprises the metal in its lowest oxidation state.
- 16. The method according to claim 15, wherein the step of precipitating a homogeneous mixture of the four materials from the solution comprises the addition of a metal hydroxide to the solution.
- 17. The method according to claim 16, wherein the metal hydroxide is selected from the group consisting of lithium hydroxide and sodium hydroxide.
- 18. The method according to claim 17, wherein the step of removing lithium nitrates from the precipitated mixture is added between step b and step c.
- 19. The method according to claim 18, wherein the lithium that is added in step c comprises a material selected from the group consisting of Li2CO3, LiOH, LiNO3, LiPO4, LiF, LiCl, Lil, LiOH.H2O, Li2SO2 and LiOAc.
- 20. The method according to claim 19, wherein the amount of lithium that is added in step c is within a range of about 0.9 to about 1.1 of the combined amounts of the nickel, manganese, cobalt and aluminum on a molar basis.
- 21. The method according to claim 18, wherein the lithium is added in a water solution in step c and, prior to calcination, the precipitated mixture is intermixed with the lithium to form a suspension;
the suspension is separated into droplets; the droplets are frozen; and water is removed from the frozen droplets by sublimation to form a dry mixture of lithium hydroxide and the hydroxides of nickel, manganese, cobalt and aluminum.
- 22. The method according to claim 21, wherein the droplets are frozen by contact with liquid nitrogen.
- 23. The method according to claim 11, wherein the step of calcining the mixture comprises heating the mixture to a temperature of from about 550° C. to about 1200° C. for a time sufficient to convert the hydroxides to oxides.
- 24. The method according to claim 15, wherein following step b, and prior to step c, the precipitated homogeneous mixture is reacted with a source of oxygen under conditions designed to further oxidize at least a portion of the hydroxides.
- 25. The method according to claim 24, wherein the precipitated homogeneous mixture is contacted with a source of oxygen selected from the group consisting of air, oxygen gas, and hydroperoxides.
- 26. The method according to claim 25, wherein the precipitated homogeneous mixture is separated from the liquid prior to contact with a source of oxygen; and then the precipitated mixture is heated to a temperature of between about 40° C. and about 120° C. in the presence of air for a period sufficient for at least some of the hydroxides to react to form oxides.
- 27. The method according to claim 25 wherein the material that has been contacted with oxygen is then mixed in step c with an amount of lithium that is within a range of about 0.9 to about 1.1 of the combined amounts of the nickel, manganese, cobalt and aluminum on a molar basis.
- 28. An electrochemical cell produced by the method of claim 8, wherein 0.7≦z/(y+z+u+w)<1.0.
- 29. An electrochemical cell comprising a positive electrode, a negative electrode and an electrolyte which electrochemically interconnects the positive electrode and the negative electrode, wherein the positive electrode comprises a composite oxide in a single phase having the general formula Lix M1y M2z M3u M4w On, where 0<x≦2, the sum of y+z+u+w is about 1 to 2, and 2<n<4, where M1, M2, M3 and M4 are different and are selected from the group consisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, and where one of M1, M2, M3 and M4 is present in an amount of at least about 70 mol percent of the combined M1, M2, M3 and M4.
- 30. The electrochemical cell according to claim 29, wherein Ml is Mn, M2 is N1, M3 is Co, M4 is Al, and 0.7≦z/(y+z+u+w)<1.0.
- 31. The electrochemical cell according to claim 30, wherein z/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2, u/(y+z+u+w)≦0.1, and w/(y+z+u+w)≦0.1.
- 32. The electrochemical cell according to claim 31, wherein z/(y+z+u+w)≧0.7, y/(y+z+u+w)≦0.2, u/(y+z+u+w)≦0.05, and w/(y+z+u+w)≦0.05.
- 33. A lithium-ion battery comprising a sealable cell container, a positive electrode, a negative electrode, an electrolyte solution, a separator, a positive electrode current collector, and a negative electrode current collector, where the positive electrode comprises a composite oxide in a single phase having the general formula Lix Mny Niz Cou Alw On, where 0<x≦2, the sum of y+z+u+w is about 1 to 2, and 2≦n≦4, and 0.7<z/(y+z+u+w)<1.0.
- 34. The battery according to claim 33, wherein the positive electrode, the negative electrode, and the separator comprise flexible polymeric materials.
- 35. A method of producing a positive electrode-active material that is a composite oxide of at least two metals, the method comprising the steps:
(a) forming a mixture of the hydroxides of at least two metals selected from the group consisting of Ba, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Al, B, Si, Ga, Ge, As, Zr, Hf, Mo, W, Re, Ru, Rh, Pt, Ag, Os, Ir, Au, Sn, and lanthanides, where at least one of the metals is in its lowest oxidation state; (b) contacting the mixture with oxygen under conditions suitable for the further oxidation of at least some of the metal hydroxides; (c) adding lithium to the mixture; and (d) calcining the mixture in the presence of oxygen to form a lithiated composite oxide of the at least two metals.
- 36. The method according to claim 35, wherein step (a) comprises:
providing the at least two metals as metal salts, where at least one of the metals is in its lowest oxidation state; forming a homogeneous solution of the salts in a solvent; and adding a base to the solution to convert the metal salts to metal hydroxides which form a precipitated homogeneous mixture of the metal hydroxides.
CROSS REFERENCE TO RELATED PATENTS AND PATENT APPLICATIONS
[0001] This application is a divisional of and claims priority to application Ser. No. 09/742,754, filed Dec. 21, 2000; which claimed the benefit of priority from U.S. Provisional Patent Application Serial No. 60/173,911, filed on Dec. 29, 1999; both of which are incorporated by reference herein in their entireties. The subject matter of the present invention is related to the co-pending and commonly assigned U.S. patent application Ser. No. 09/742,738, which was filed on the same date as the present application and which has issued as U.S. Pat. No. 6,350,543.
Provisional Applications (1)
|
Number |
Date |
Country |
|
60173911 |
Dec 1999 |
US |
Divisions (1)
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Number |
Date |
Country |
Parent |
09742754 |
Dec 2000 |
US |
Child |
10456106 |
Jun 2003 |
US |