Cobalt-stabilized lithium metal oxide electrodes for lithium batteries

Patent metadata

Field	Value
Publication number	US-10790508-B2
Application number	US-201816020403-A
Country	US
Kind code	B2
Filing date	Jun 27, 2018
Priority date	Dec 23, 2013
Publication date	Sep 29, 2020
Grant date	Sep 29, 2020

Abstract

An electrode material comprising a composite lithium metal oxide, which in an initial state has the formula: y[xLi 2 MO 3 .(1−x)LiM′O 2 ].(1−y)Li 1+d Mn 2−z−d M″ z O 4 ; wherein 0≤x≤1; 0.75≤y<1; 0<z≤2; 0≤d≤0.2; and z−d≤2. M comprises one or more metal ions that together have an average oxidation state of +4; M′ comprises one or more metal ions that together have an average oxidation state of +3; and M″ comprises one or more metal ions that together with the Mn and any excess proportion of lithium, “d”, have a combined average oxidation state between +3.5 and +4. The Li 1+d Mn 2−z−d M″ z O 4 component comprises a spinel structure, each of the Li 2 MO 3 and the LiM′O 2 components comprise layered structures, and at least one of M, M′, and M″ comprises Co. Cells and batteries comprising the electrode material also are described.

First claim

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A three-component, structurally integrated, layered-layered-spinel composite lithium metal oxide electrode material, which in an initial state has the formula:
y [ x Li 2 MO 3 .(1 −x )LiM′O 2 ].(1 −y )Li 1+d Mn 2−z−d M″ z O 4 ;

wherein:
0<x<1;
0.75≤y<1;
0<z≤2;
0≤d≤0.2;
z−d≤2;
M comprises one or more metal ions that together have a combined average oxidation state of +4;
M′ comprises one or more metal ions that together have a combined average oxidation state of +3; and
M″ comprises one or more metal ions that together with the Mn and excess proportion, d, of lithium, have a combined average oxidation state of +3.5; and
wherein the Li 1+d Mn 2−z−d M″ z O 4 component comprises a spinel crystal lattice structure, each of the Li 2 MO 3 and the LiM′O 2 components thereof comprise layered crystal lattice structures; at least one of M, M′, and M″ comprises Co; and the layered and spinel structures are integrated together into a composite structure.

2. The electrode material of claim 1 , wherein 0.85≤y<1.

3. The electrode material of claim 1 , wherein 0.85≤y≤0.9.

4. The electrode material of claim 1 , wherein each of M and M′ independently comprises at least one metal selected from the group consisting of Mn, Ni, and Co; and M″ comprises at least one metal selected from the group consisting of Ni and Co.

5. The electrode material of claim 4 , wherein each of M and M′ independently further comprises at least one metal selected from the group consisting of Al, Mg, Li, and a first or second row transition metal other than Mn, Ni and Co; and M″ further comprises at least one metal selected from the group consisting of Al, Mg, and a first or second row transition metal other than Mn, Ni and Co.

6. The electrode material of claim 1 , wherein 0<d≤0.2; 0.2<z≤0.6; and M″ comprises Ni, Co, or a combination thereof.

7. The electrode material of claim 1 , wherein M is Mn.

8. The electrode material of claim 1 , wherein M′ comprises Mn and Ni.

9. The electrode material of claim 8 , wherein M′ further comprises Co.

10. The electrode material of claim 1 , wherein the spinel component, Li 1+d Mn 2−z−d M″ z O 4 , comprises Mn, Ni, and Co.

11. The electrode material of claim 1 , wherein M is Mn; M′ comprises Mn and Ni; and the spinel component, Li 1+d Mn 2−z−d M″ z O 4 , comprises Mn, Ni, and Co.

12. The electrode material of claim 1 , wherein M″ comprises at least one metal selected from the group consisting of Ni and Co; d>0; and 2−d−z>0.

13. The electrode material of claim 1 , wherein M″ comprises Ni and Co; Co constitutes about 1 atom percent to about 30 atom percent of transition metals in spinel component, Li 1+d Mn 2−z−d M″ z O 4 ; and the combination of Mn and Ni constitutes about 70 atom percent to about 99 atom percent of the transition metals in the spinel component.

14. The electrode material of claim 13 , wherein the combination of Mn and Ni constitutes about 80 atom percent of the transition metals in the spinel component and Co constitutes about 20 atom percent of the transition metals in the spinel component.

15. The electrode material of claim 13 , wherein the spinel component constitutes about 50 atom percent Mn, about 30 atom percent Ni, and about 20 atom percent Co of the transition metals in the spinel component.

16. The electrode material of claim 1 , wherein the Li, Mn, M, M′ and M″ cations are partially disordered over the octahedral and tetrahedral sites of the layered and spinel components of the composite lithium metal oxide structure.

17. The electrode material of claim 1 , wherein 0<x<0.5.

18. A positive electrode for a lithium electrochemical cell comprising a layer of the electrode material of claim 1 in contact with a metal current collector.

19. A lithium electrochemical cell comprising the positive electrode of claim 18 and a negative electrode in contact with a non-aqueous electrolyte comprising a lithium salt.

20. A lithium battery comprising a plurality of the electrochemical cells of claim 19 connected together in series, parallel, or both.

21. An electrode material comprising a three-component, structurally-integrated, layered-layered-spinel composite lithium metal oxide, which in an initial state has the formula:
y [ x Li 2 MO 3 .(1 −x )LiM′O 2 ].(1 −y )Li 1+d Mn 2−z−d M″ z O 4 ;

wherein:
0<x<1;
0.75≤y<1;
0<z≤2;
0≤d≤0.2;
z−d≤2;
M comprises one or more metal ions that together have a combined average oxidation state of +4;
M′ comprises one or more metal ions that together have a combined average oxidation state of +3; and
M″ comprises one or more metal ions that together with the Mn and excess proportion, d, of lithium, have a combined average oxidation state of +3.5; and
wherein the Li 1+d Mn 2−z−d M″ z O 4 component comprises a spinel crystal lattice structure, each of the Li 2 MO 3 and the LiM′O 2 components thereof comprise layered crystal lattice structures; and at least one of M, M′, and M″ comprises Co; and wherein the Co content of the three-component layered-layered-spinel composite comprises more than 50% of the combined M, M′, and M″ content thereof, or the Ni content of the three-component layered-layered-spinel composite comprises more than 50% of the combined M, M′, and M″ content thereof; and the spinel and layered structures are integrated together into a single composite structure.

22. The electrode material of claim 21 , wherein each of M and M′ comprises at least one metal selected from the group consisting of Mn, Ni, and Co; and M″ comprises at least one metal selected from the group consisting of Ni and Co.

23. The electrode material of claim 21 , wherein M′ further comprises at least one metal selected from the group consisting of Al, Mg, Li, and a first or second row transition metal other than Mn, Ni and Co; and M″ further comprises at least one metal selected from the group consisting of Al, Mg, and a first or second row transition metal other than Mn, Ni and Co.

24. A positive electrode for a lithium electrochemical cell comprising a layer of the electrode material of claim 21 in contact with a metal current collector.

25. A lithium electrochemical cell comprising the positive electrode of claim 24 and a negative electrode in contact with a non-aqueous electrolyte comprising a lithium salt.

26. A lithium battery comprising a plurality of the electrochemical cells of claim 25 connected together in series, parallel, or both.

Assignees

• Uchicago Argonne Llc

Inventors

• Thackeray Michael M
• Croy Jason R
• Long Brandon R
• Park Joong Sun
• Lee Eungje

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/505 Primary

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title