LTO coated LRMO cathode and synthesis

• US 10,640,391 B2
• Filed: 10/16/2017
• Issued: 05/05/2020
• Est. Priority Date: 10/16/2017
• Status: Active Grant

• Current Assignee: Ford Global Technologies, LLC (Ford Motor Company)
• Original Assignee: Ford Global Technologies, LLC (Ford Motor Company)
• Inventors: Zhang, Wenkui, Huang, Hui, Xia, Yang, Zhang, Liyuang, Wang, Yishun, Liang, Chu, Yang, Xiao Guang, Kudla, Robert J., Miller, Theodore James
• Primary Examiner(s): Domone, Christopher P
• Application Number:
  US15/784,252
• Publication Number:
  US 20190115590A1
• Time in Patent Office: Days
• Field of Search: None
• CPC Class Codes: B01J 2/006 Coating of the granules without description of the process or the device by which the granules are obtained to prevent the granules sticking together B01J2/30
• CPC Class Codes: C01G 23/005 Alkali titanates
• CPC Class Codes: C01G 45/1221 Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
• CPC Class Codes: C01G 45/1257 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 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 10/0525 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 4/36 Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/366 as layered products
• 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 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

A method of forming a high energy density composite cathode material is disclosed. The method includes providing a lithium-rich manganese layered oxide (LRMO), coating the LRMO with a TiO₂ precursor, and ball-milling the TiO₂ coated LRMO with LiH to form a Li_xTiO₂ coated LRMO composite, wherein x is less than or equal to 1 and greater than zero.

Claims

1. A method of forming a composite cathode material comprising:

providing a lithium-rich manganese layered oxide (LRMO) having the formula xLi₂MnO₃.(1-x)LiMO₂, wherein M is Mn, Ni, Co, Fe, Cr, Ti, Al, Mg, V, a rare earth metal, or a combination thereof, and x is less than or equal to 1 and greater than zero;

coating the LRMO with a TiO₂ precursor; and

ball-milling the TiO₂ coated LRMO with LiH to form a Li_xTiO₂ coated LRMO composite, wherein x is less than or equal to 1 and greater than zero.

2. The method of claim 1, wherein coating the LRMO with the TiO₂ precursor includes reacting the LRMO with titanium salt, deionized water, and alcohol.

3. The method of claim 2, wherein the reacting is performed in a hydrothermal reactor.

4. The method of claim 2, wherein the reacting is performed at a temperature of about 100°

C. to about 300°

C., for about 1 to about 12 hours.

5. The method of claim 2, wherein the coating includes calcining to form the TiO₂ coated LRMO after reacting the LRMO.

6. The method of claim 5, wherein the calcining is performed at about 300°

C. to about 500°

C., for about 30 minutes to about 8 hours.

7. The method of claim 6, herein the calcining is performed at a heating rate of about 1°

C./min to about 10°

C./min.

8. The method of claim 1, wherein the TiO₂ is about 0.1 wt. % to about 9 wt. % of the TiO₂ coated LRMO.

9. The method of claim 1, wherein the ball-milling is performed at a rate of about 200 rpm to about 750 rpm, for about 6 hours to about 24 hours.

10. The method of claim 1, wherein the providing includes co-precipitating the LRMO.

11. A method of forming a composite cathode material comprising:

reacting a lithium-rich manganese layered oxide (LRMO) with a TiO₂ precursor in a hydrothermal reactor, the LRMO having the formula xLi₂MnO₃.(1-x)LiMO₂, where M is Mn, Ni, Co, Fe, Cr, Ti, Al, Mg, V, a rare earth metal, or a combination thereof, and x is less than or equal to 1 and greater than zero;

calcining a precursor coated LRMO; and

ball-milling the precursor coated LRMO with LiH to form a Li_xTiO₂ coated LRMO composite, wherein x is less than or equal to 1 and greater than zero.

12. The method of claim 11, wherein the TiO₂ precursor is about 0.1 wt. % to about 9 wt. % of the precursor coated LRMO.

13. The method of claim 11, wherein the calcining is performed at a heating rate of about 1°

C./min to about 10°

C./min.

14. The method of claim 11, wherein the ball-milling is performed at a rate of about 200 rpm to about 750 rpm, for about 6 hours to about 24 hours.

15. The method of claim 11, wherein a ratio of LiH to TiO₂ for the ball-milling is about 1:

1 to about 1.10;

1.

16. A cathode composite material comprising:

a lithium-rich manganese layered oxide (LRMO) having the formula xLi₂MnO₃.(1-x)LiMO₂; and

a ball-milled Li_xTiO₂ coating on a surface of the LRMO, the ball-milled Li_xTiO₂ coating being a ball-milled LiH and TiO₂ precursor composite coating on the LRMO,

wherein M is Mn, Ni, Co, Fe, Cr, Ti, Al, Mg, V, a rare earth metal, or a combination thereof, and x is less than or equal to 1 and greater than or equal to zero.

17. The cathode composite material of claim 16, wherein the LRMO has the formula Li[Li_(1-x-y-z)Ni_xCo_yMn_z]O₂, and x, y, and z are each independently less than or equal to 1 and greater than zero, or absent.