Rechargeable spinel lithium batteries with greatly improved elevated temperature cycle life

• US 6,489,060 B1
• Filed: 01/14/2000
• Issued: 12/03/2002
• Est. Priority Date: 05/26/1999
• Status: Expired due to Term

• Current Assignee: E-One Moli Energy (Canada) Limited (E-One Moli Energy Corp.)
• Original Assignee: E-One Moli Energy (Canada) Limited (E-One Moli Energy Corp.)
• Inventors: Wang, Yu, Gee, Michael, Reimers, Jan Naess, Zhang, Meijie
• Primary Examiner(s): Chaney, Carol
• Assistant Examiner(s): DOVE, TRACY MAE
• Application Number:
  US09/484,399
• Time in Patent Office: 1,054 Days
• Field of Search: 429/224, 429/231.1, 296/231
• US Class Current: 429/224
• CPC Class Codes: C01G 45/1242 of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
• CPC Class Codes: C01P 2002/32 spinel-type (AB2O4)
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2006/40 Electric properties
• 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 10/0566 Liquid materials
• CPC Class Codes: H01M 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• 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 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

Abstract

The loss in delivered capacity (capacity fade) after cycling non-aqueous rechargeable lithium manganese oxide batteries at elevated temperatures can be greatly reduced by depositing a small amount of certain foreign metal species on the surface of spinel in the cathode. In particular the foreign metal species are from compounds having either bismuth, lead, lanthanum, barium, zirconium, yttrium, strontium, zinc or magnesium. The foreign metal species are introduced to the surface of spinel by moderately heating either an aqueous treated mixture or a dry mixture of ready-made spinel and the foreign metal compound.

Claims

1. A non-aqueous rechargeable lithium manganese oxide battery having reduced capacity fade rate during cycling at elevated temperature, said battery comprising:

a lithium manganese oxide spinel structure compound cathode,

a lithium insertion compound anode,

a separator, and

a non-aqueous electrolyte including a lithium salt dissolved in a non-aqueous solvent, wherein;

the spinel structure compound is coated with the decomposition products of one or more compounds of foreign metals with atomic number greater than 11 that reduce the capacity fade rate of the battery during cycling at elevated temperature, wherein said decomposition products are formed by heating a mixture of said spinel structure compound and said foreign metal compounds at a temperature at which said foreign metal compounds decompose to coat the surface of said spinel structure compound without entering the bulk of the spinel structure or extracting lithium therefrom.

2. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein a methanol reaction of charged or de-lithiated spinel structure compound yield k/k₀<

0.9 (one minus one standard deviation of ppm amount H₂O of the untreated spinel after 40 hours at 45°

C.), where k is the ppm amount of H₂O generated per gram of charged-treated spinel structure in methanol after 40 hours at 45°

C. and k₀ is the ppm amount of H₂O generated per gram of charged-untreated spinel in methanol after 40 hours at 45°

C.

3. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the foreign metal compound is selected from one or more compounds incorporating Bi, Pb, La, Ba, Zr, Y, Sr, Zn and Mg.

4. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the foreign metal compound is selected from one or more compounds incorporating Bi, Pb, La and Y.

5. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the foreign metal compound is selected from one or more compounds incorporating La.

6. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein said mixture comprises greater than about 0.01 but less than about 5 mole % foreign metal relative to said spinel structure compound.

7. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein said mixture comprises greater than about 0.05 but less than 2 mole % foreign metal relative to said spinel structure compound.

8. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the foreign metal compound is dissolved in water, then mixed with said spinel structure compound;

and subsequently the mixture is dried then heated to coat the surface of the spinel structure with said decomposition products.

9. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 8 wherein the heating is at above the decomposition temperature of the foreign metal compound and less than or equal to 750°

C.

10. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the foreign metal compound is dry-mixed with said spinel structure compound;

and the mixture is subsequently heated to coat the surface of the spinel structure with said decomposition products.

11. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 10 wherein the heating is initially at above the decomposition temperature of the foreign metal compound, then further heated to between about 600°

C. and 750°

C.

12. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the anode comprises a carbonaceous insertion compound.

13. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 12 wherein the carbonaceous insertion compound is graphite.

14. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the lithium salt is LiPF₆.

15. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the non-aqueous solvent is an organic carbonate.

16. A non-aqueous rechargeable lithium manganese oxide battery as claimed in claim 1 wherein the non-aqueous solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, and mixtures thereof.

17. A method for reducing the capacity fade rate during cycling at elevated temperature of a non-aqueous rechargeable lithium manganese oxide battery, the battery comprising a lithium manganese oxide spinel structure compound cathode, a lithium insertion compound anode, a separator, and a non-aqueous electrolyte including a lithium salt dissolved in a non-aqueous solvent, wherein the spinel structure compound is formed by heating a mixture of said spinel structure compound and one or more compounds of foreign metals with atomic number greater than 11 at a temperature at which said foreign metal compounds decompose to coat the surface of said spinel structure compound with decomposition products without entering said compound structure, wherein said foreign metal compounds form decomposition product coatings that reduce the capacity fade rate of the battery during cycling at elevated temperature.

18. A method as claimed in claim 17 wherein a methanol reaction of the charged or de-lithiated spinel structure compound yields k/k₀<

0.9 (one minus one standard deviation of ppm amount H₂O) of the untreated spinel after 40 hours at 45°

C.), where k is the ppm amount of H₂O generated per gram of charged-treated spinel in methanol after 40 hours at 45°

C. and k₀ is the ppm amount of H₂O generated per gram of charged-untreated spinel in methanol after 40 hours at 45°

C.

19. A method as claimed in claim 17 wherein the foreign metal compound is one or more compounds containing Bi, Pb, La, Ba, Zr, Y, Sr, Zn or Mg.

20. A method as claimed in claim 17 wherein the foreign metal compound is one or more compounds containing Bi, Pb, La or Y.

21. A method as claimed in claim 17 wherein the foreign metal compound is one or more compounds containing La.

22. A method as claimed in claim 17 wherein said mixture comprises greater than about 0.01 but less than about 5 mole % foreign metal to said spinel structure compound.

23. A method as claimed in claim 17 wherein said mixture comprises greater than about 0.0.5 but less than about 2 mole % foreign metal relative to said spinel structure compound.

24. A method as claimed in claim 17 wherein the foreign metal compound is first dissolved in water then mixed with said spinet structure compound;

and subsequently the mixture is dried, then heated to coat the surface of the spinel structure with said decomposition products.

25. A method as claimed in claim 24 wherein heating is conducted at a temperature above the decomposition temperature of the foreign metal compound and less than or equal to 750°

C.

26. A method as claimed in claim 17 wherein the foreign metal compound is dry-mixed with said spinet structure compound, and the mixture is subsequently heated to coat the surface of the spinel structure compound with said decomposition products.

27. A method as claimed in claim 26 wherein heating is initially at above the decomposition temperature of the foreign metal compound, then further heated to between about 600°

C. and 750°

C.

28. A method as claimed in claim 17 wherein the anode comprises a carbonaceous insertion compound.

29. A method as claimed in claim 28 wherein the carbonaceous insertion compound is graphite.

30. A method as claimed in claim 17 wherein the lithium salt is LiPF₆.

31. A method as claimed in claim 17 wherein the non-aqueous solvent comprises an organic carbonate.

32. A method as claimed in claim 17 wherein the non-aqueous solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, and mixtures thereof.