IMPROVED LITHIUM METAL OXIDE CATHODE MATERIALS AND METHOD TO MAKE THEM

• US 20160315315A1
• Filed: 12/10/2014
• Published: 10/27/2016
• Est. Priority Date: 12/17/2013
• Status: Abandoned Application

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Inventors: Klann, John J., Olken, Michael M.
• Application Number:
  US15/102,729
• Publication Number:
  US 20160315315A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C01G 45/1228 of the type [MnO2]n- , e.g. LiMnO2, Li[MxMn1-x]O2
• 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 2002/02 Amorphous compounds
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2004/84 one phase coated with the other
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C23C 16/40 Oxides
• 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 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 2220/30 : Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 4/0404 : by coating on electrode collectors
• CPC Class Codes: H01M 4/0435 : Rolling or calendering
• 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 4/382 : Lithium H01M4/405 takes precedence
• 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 4/582 : Halogenides
• CPC Class Codes: H01M 4/623 : fluorinated polymers
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: H01M 4/661 : Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• 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

Abstract

A coated cathode material comprises a lithium metal oxide particulate having a surface at least partially coated with a coating comprised of a complex metal oxide of aluminum and a second metal that is lanthanum, yttria or combination thereof. The coated cathode material may be made by providing a lithium metal oxide particulate which is then contacted with a precursor compound that forms a complex metal oxide upon heating. The coated lithium metal oxide is then heated to a temperature sufficient to form the complex metal oxide, wherein the complex metal oxide is amorphous and contains aluminum and a second metal that is lanthanum, yttria or combination thereof and the complex metal oxide is bonded to the lithium metal oxide.

Claims

1. A composition useful as a cathode material comprising a lithium metal oxide particulate having a surface at least partially coated with a coating comprised of a complex metal oxide containing aluminum and a second metal that is lanthanum, yttria or combination thereof.

2. The composition of claim 1, wherein the complex metal oxide is amorphous.

3. The composition of claim 1, wherein the molar ratio of the aluminum/second metal is 0.5 to 2.

4. The composition of claim 1, wherein the molar ratio of the aluminum/second metal is essentially 1.

5. The composition of claim 1, wherein the metal of the lithium metal oxide is comprised of Mn, Ni, and Co.

6. The composition of claim 1, wherein the lithium metal oxide is a lithium rich layered metal oxide represented by a formula:

Li_xM_yO₂

Where 1<

x<

2, y is 1 and the metal may be any metal that has an oxidation state from 2 to 4.

7. The composition of claim 1, wherein the lithium metal oxide particulate is comprised of primary particles aggregated into a secondary particle such that the secondary particle has core primary particles that are enveloped by surface primary particles.

8. The composition of claim 7, wherein the coating is unevenly distributed on the surface and core primary particles such that there is more coating on the surface primary particles than the core primary particles.

9. The composition of claim 1, wherein the volume of the coating is 0.2% to 10% by volume of the composition.

10. The composition of claim 1, wherein the coating is comprised of a crystalline structure.

11. The composition of claim 10, wherein the crystalline structure is a perovskite crystalline structure.

17. A lithium ion battery comprising a cathode comprised of the composition of claim 1.

12. A method of making a lithium metal oxide coated with a complex metal oxide comprising

(i) providing a lithium metal oxide particulate,

(ii) contacting the lithium metal oxide with a precursor compound that forms a complex metal oxide upon heating, and

(iii) heating to a temperature sufficient to form the complex metal oxide, wherein the complex metal oxide is amorphous and contains aluminum and a second metal that is lanthanum, yttria or combination thereof and the complex metal oxide is bonded to the lithium metal oxide.

13. The method of claim 12, wherein the heating is to a temperature from 350°

C. to 450°

C.

14. The method of claim 12, wherein the precursor dissolved in a liquid and the liquid is contacted with the lithium metal oxide and the precursor is precipitated onto the surface of the lithium metal oxide.

15. The method of claim 14, wherein at least two precursors are dissolved in the liquid and upon precipitation forms a complex precursor compound having aluminum and a second metal that is lanthanum, yttria or combination thereof.

16. The method of claim 12, wherein the precursor is an aluminum compound that is a nitrate hydrate and at least one yttrium or lanthanum compound that is nitrate hydrate.

18. The method of claim 14, wherein the lithium metal oxide is first wetted with a liquid not having precursors dissolved therein to form a slurry and then, the liquid having precursors dissolved therein is added to the slurry and the precursor is precipitated onto the lithium metal oxide.

19. The method claim 18, wherein the precipitation is caused by a change in condition of the slurry containing the liquid having precursors dissolved therein.

20. The method of claim 19, wherein the change in condition is a combination of heating and change in pH.