Stabilized electrodes for lithium batteries

Patent metadata

Field	Value
Publication number	US-2017047587-A1
Application number	US-201615232188-A
Country	US
Kind code	A1
Filing date	Aug 9, 2016
Priority date	Aug 11, 2015
Publication date	Feb 16, 2017
Grant date	—

Abstract

A structurally inhomogeneous lithium metal oxide material having the Formula (I): Y[xLi 2 MO 3 •(1-x)LiM′O 2 ]•(1-y)Li 1+d M″ 2−d O 4 ; wherein 0≦x≦1; 0<y<1; 0≦d≦0.33; and wherein the Li 1+d M″ 2−d O 4 component comprises a spinel structure, and each of the Li 2 MO 3 and the LiM′ 2 components thereof comprise layered structures. Each of M, M′, and M″ independently comprises one or more metal ions. The composition of the material of Formula (I) varies across the electrode particles by changing at least one of x, y, d, M, M′ and M″. Electrodes, cells and batteries comprising the lithium metal oxide material are also described.

First claim

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

1 : A structurally inhomogeneous lithium metal oxide material of Formula (I):
y[x Li 2 MO 3 •(1- x )LiM′O 2 ]•(1- y )Li 1+d M″ 2-d O 4 ;   (I)

wherein:
0 ≦x≦ 1;
0 <y <1;
0 ≦d ≦0.33;

M, M′, and M″ each independently comprises one or more multivalent metal ions; and
wherein the Li 1−d M″ 2−d O 4 component comprises a spinel structure, and each of the Li 2 MO 3 and the LiM′O 2 components thereof comprise layered structures; and wherein the chemical composition of particles of the material differs by at least one of x, y, d, M, M′ and M″ from the surface to the interior across the particles.

2 . The material of claim 1 , wherein
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.

3 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which 0.75≦y<1.

4 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which 0.85≦y<1.

5 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which 0.85≦y≦0.9.

6 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which 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.

7 . The material of claim 6 , wherein particles of the material comprise a composition of Formula (I) in which 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.

8 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which 0<d≦0.2; and M″ comprises Mn and at least one of Ni and Co.

9 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M is Mn.

10 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M′ comprises Mn and Ni.

11 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M′ comprises Mn, Ni, and Co.

12 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M″ comprises Mn, Ni, and Co.

13 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M is Mn; M′ comprises Mn and Ni; and M″ comprises Mn, Ni, and Co.

14 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M″ comprises Mn and at least one metal selected from the group consisting of Ni and Co; and d>0.

15 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which M″ comprises Mn, Ni and Co; Co constitutes about 1 atom percent to about 30 atom percent of transition metals in spinel component, Li 1+d M″ 2−d 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.

16 . The material of claim 15 , wherein particles of the material comprise a composition of Formula (I) in which 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, or wherein particles of the material comprise a composition of Formula (I) in which 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 material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which the Li, 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.

18 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) in which 0≦x≦0.5.

19 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) wherein x is 0.

20 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) with intermediate layered- and spinel-type character, in which the Li, M, M′ and M″ cations of the spinel and layered electrode components are partially disordered over the octahedral and tetrahedral sites of the layered and spinel components.

21 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) with deviations from ideal layered and spinel compositions and structures, by inclusion of cation and anion vacancies, stacking faults, structural and/or compositional disorder, particularly at domain or grain boundaries.

22 . The material of claim 1 , wherein particles of the material comprise a composition of Formula (I) that includes localized rocksalt, defect rocksalt, defect spinel, and/or defect layered configurations of the transition metal ions and/or oxygen ions within the structure thereof.

23 . The material of claim 1 , wherein particles of the material are contacted with an acidic solution remove a portion of lithium ions from the surface of the particles to vary the lithium concentration from the surface to the interior across the particles.

24 . A positive electrode for a lithium electrochemical cell comprising a layer of the electrode material of claim 1 in contact with a 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
• Amine Khalil
• Yonemoto Bryan T
• Park Joong Sun

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · 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

• H01M2004/028

  Positive electrodes · CPC title

• H01M2/1077

  Electricity · mapped topic

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title