Cobalt-stabilized lithium metal oxide electrodes for lithium batteries

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.