Materials for positive electrodes of lithium ion batteries and their methods of fabrication

• US 20050130042A1
• Filed: 12/10/2004
• Published: 06/16/2005
• Est. Priority Date: 12/11/2003
• Status: Abandoned Application

• Current Assignee: BYD America Corporation (BYD Company Limited)
• Original Assignee: BYD America Corporation (BYD Company Limited)
• Inventors: Zhou, Xinying, Liu, Huiquan
• Application Number:
  US11/010,041
• Publication Number:
  US 20050130042A1
• Time in Patent Office: Days
• US Class Current: 429/231.300
• CPC Class Codes: C01G 45/1242 of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
• CPC Class Codes: C01G 51/42 containing alkali metals, e.g. LiCoO2
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/84 one phase coated with the other
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/02 Electrodes composed of, or comprising, active material
• 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 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/366 as layered products
• 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 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

This invention discloses materials for positive electrodes of secondary batteries and their methods of fabrication. Said materials comprise of granules of an active material for positive electrodes coated with an oxide layer. The active material is one or more of the following: oxides of lithium cobalt, oxides of lithium nickel cobalt, oxides of lithium nickel cobalt manganese, oxides of lithium manganese, LiCoO₂, LiNi_1-xCo_xO₂, LiNi_1/3Co_1/3Mn_1/3O₂, and LiMn₂O₄. The non-oxygen component in the oxide layer is one or more of the following: aluminum, magnesium, zinc, calcium, barium, strontium, lanthanum, cerium, vanadium, titanium, tin, silicon, boron, Al, Mg, Zn, Ca, Ba, Sr, La, Ce, V, Ti, Sn, Si, and B. Said non-oxygen component of the granules is between 0.01 wt. % to 10 wt. % of said granules of active material. The methods of fabrication for said materials includes the steps of mixing an additive and an active material for positive electrodes uniformly in water or solvent, evaporating said solvent or water, and heat treating the remaining mixture at 300° C. to 900° C. for between 1 hour to 20 hours. The additive is a compound of one or more of the following elements: aluminum, magnesium, zinc, calcium, barium, strontium, lanthanum, cerium, vanadium, titanium, tin, silicon, boron, Al, Mg, Zn, Ca, Ba, Sr, La, Ce, V, Ti, Sn, Si, and B where the element is between 0.01 wt. % to 10 wt. % of said active material. Using the materials of positive electrodes disclosed above or materials for positive electrodes fabricated in the methods disclosed above in batteries produces batteries with excellent cycling and high temperature properties.

Claims

1. A material for positive electrodes, comprising:

granules of active material for said positive electrode; and

an oxide coating for each of said granules of said active material comprising of an oxygen component and a non-oxygen component; and

wherein

said active material is at least one lithium compound selected from the group consisting of;

an oxide of lithium cobalt, an oxide of lithium nickel cobalt, an oxide of lithium nickel cobalt manganese, an oxide of lithium manganese, LiCoO₂, LiNi_1-xCo_xO₂, LiNi_1/3Co_1/3Mn_1/3O₂, and LiMn₂O₄.

2. The material for positive electrodes of claim 1 wherein said non-oxygen component of said oxide coating of one or more of said granules is between 0.1 wt. % to 10 wt. % of said respective granule of active material.

3. The material for positive electrode of claim 1 wherein each of said granules having an average granule diameter between 4 microns and 12 microns.

4. The material for positive electrode of claim 1 wherein said non-oxygen component of said oxide coating is at least one metal selected from the group consisting of:

aluminum, magnesium, zinc, calcium, barium, strontium, lanthanum, cerium, vanadium, titanium, tin, Al, Mg, Zn, Ca, Ba, Sr, La, Ce, V, Ti, and Sn.

5. The material for positive electrode of claim 1 wherein said non-oxygen component of said oxide coating is at least one non-metal element selected from the group consisting of:

silicon, boron, Si, and B.

6. The material for positive electrode of claim 1 wherein said non-oxygen component of said oxide coating is at least one element selected from the group consisting of:

aluminum, magnesium, zinc, calcium, barium, strontium, lanthanum, cerium, vanadium, titanium, tin, silicon, boron, Al, Mg, Zn, Ca, Ba, Sr, La, Ce, V, Ti, Sn, Si, and B.

7. The material for positive electrode of claim 4 wherein said non-oxygen component of said oxide coating of one or more of said granules is between 0.1 wt. % to 10 wt. % of said respective granule of active material.

8. The material for positive electrode of claim 5 wherein said non-oxygen component of said oxide coating of one or more of said granules is between 0.1 wt. % to 10 wt. % of said respective granule of active material.

9. The material for positive electrode of claim 6 wherein said non-oxygen component of said oxide coating of one or more of said granules is between 0.1 wt. % to 10 wt. % of said respective granule of active material.

10. The material for positive electrode of claim 6 wherein each of said granules having an average granule diameter between 4 microns and 12.

11. The material for positive electrode of claim 9 wherein each of said granules having an average granule diameter between 4 microns and 12

12. A method for fabricating a material for positive electrodes, comprising the steps of:

mixing granules of an active material and an additive in a solution;

evaporating said solution to obtain a composite of said granules of active material and additive;

heating said composite at between 300°

C. to 900°

C. for between 1 hour to 20 hours to obtain said material for said positive electrode; and

wherein

said active material is at least one lithium compound selected from the group consisting of;

an oxide of lithium cobalt, an oxide of lithium nickel cobalt, an oxide of lithium nickel cobalt manganese, an oxide of lithium manganese, LiCoO₂, LiNi_1-xCo_xO₂, LiNi_1/3Co_1/3Mn_1/3O₂, and LiMn₂O₄.

13. The method for fabricating a material for positive electrodes in claim 12 wherein each of said granules having an average granule diameter between 4 microns and 12 microns.

14. The method for fabricating a material for positive electrodes in claim 12 wherein each of said granules having an average granule diameter between 10 microns and 12 microns.

19. The method for fabricating a material for positive electrodes of claim 12 wherein said solution is water or an organic solvent.

15. The method for fabricating a material for positive electrodes of 12 wherein said additive is a compound of one or more element selected from the group consisting of:

aluminum, magnesium, zinc, calcium, barium, strontium, lanthanum, cerium, vanadium, titanium, tin, silicon, boron, Al, Mg, Zn, Ca, Ba, Sr, La, Ce, V, Ti, Sn, Si, and B.

16. The method for fabricating a material for positive electrodes of claim 15 wherein said elements in said additive is between 0.1 wt. % to 10 wt. % of said active material.

17. The method for fabricating a material for positive electrodes in claim 15 wherein each of said granules having an average granule diameter between 4 microns and 12 microns.

18. The method for fabricating a material for positive electrodes in claim 16 wherein each of said granules having an average granule diameter between 4 microns and 12 microns.

20. A material for positive electrodes, comprising:

granules of active material for said positive electrode; and

an oxide coating for each of said granules comprising of an oxygen component and a non-oxygen component; and

wherein

said active material is at least one lithium compound selected from the group consisting of;

an oxide of lithium cobalt, an oxide of lithium nickel cobalt, an oxide of lithium nickel cobalt manganese, an oxide of lithium manganese, LiCoO₂, LiNi_1-xCo_xO₂, LiNi_1/3Co_1/3Mn_1/3O₂, and LiMn₂O₄;

said non-oxygen component of said oxide coating of one or more of said granules is between 0.1 wt. % to 10 wt. % of said respective granule of active material;

each of said granules having an average granule diameter between 4 microns and 12 microns; and

said non-oxygen component of said oxide coating is at least one element selected from the group consisting of;

aluminum, magnesium, zinc, calcium, barium, strontium, lanthanum, cerium, vanadium, titanium, tin, silicon, boron, Al, Mg, Zn, Ca, Ba, Sr, La, Ce, V, Ti, Sn, Si, and B.