IP Library Granted Patent US 10,069,143
Granted Patent B2
US 10,069,143 · App. 14/733,512 · Granted Sep 4, 2018

Cobalt-stabilized lithium metal oxide electrodes for lithium batteries

Inventors: Michael M. Thackeray (Naperville, IL); Jason R. Croy (Plainfield, IL); Brandon R. Long (Plainfield, IL); Joong Sun Park (Woodridge, IL); Eungje Lee (Naperville, IL)
Assignee: UCHICAGO ARGONNE, LLC
H01M4/505H01M4/131H01M4/485H01M4/525H01M4/0471H01M10/052H01M2220/20H01M2220/30Y02E60/122
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Quick Facts
Patent No.
US 10,069,143
App. No.
14/733,512
Granted
Sep 4, 2018
Kind
B2
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.

Claims (29)

1. An electrode material comprising a two-component, structurally integrated layered-spinel composite lithium metal oxide, which in an initial state has the formula:

y LiM′O 2 .(1 −y )Li 1+d Mn 2-z-d M″ z O 4 ;

wherein:

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 +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; the LiM′O 2 component thereof comprises a layered crystal lattice structure; at least one of M′ and M″ comprises Co; and the spinel and layered structures are integrated together into a single composite structure.

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

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

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

5. The electrode material of claim 1 , wherein 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.

6. The electrode material of claim 5 , 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.

7. 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.

8. The electrode material of claim 1 , wherein M″ comprises at least one metal selected from Ni and Co.

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

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

11. 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.

12. The electrode material of claim 1 , wherein 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.

13. 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.

14. 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.

15. The electrode material of claim 14 , 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.

16. The electrode material of claim 14 , 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.

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

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.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 23, 2017
From: THACKERAY, MICHAEL M.; CROY, JASON R.; LONG, BRANDON R.; PARK, JOONG SUN; LEE, EUNGJE
To: UCHICAGO ARGONNE, LLC
Reel/Frame 042794/0159 →
CONFIRMATORY LICENSE Recorded Oct 7, 2015
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 036815/0322 →
Continuity (3)
Continuation In Part 14554762 · Nov 26, 2014
Provisional Application 61920283 · Dec 23, 2013
Related Publication 20150318546A1 · Nov 5, 2015