Composite positive active material, method of preparing the same, and positive electrode and lithium battery containing the material

Patent metadata

Field	Value
Publication number	US-9570739-B2
Application number	US-201313957351-A
Country	US
Kind code	B2
Filing date	Aug 1, 2013
Priority date	Feb 28, 2013
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

A composite positive active material including an over-lithiated lithium transition metal oxide, the over-lithiated transition metal oxide including a compound represented by Formula 1 or Formula 3: [Formula 1] xLi 2-y M″ y MO 3 -(1-x)LiM′O 2 , [Formula 3] xLi 2-y M″ y MO 3 -x′LiM′O 2 -x″Li 1+d M′″ 2-d O 4 , x+x′+x″=1, 0<x<1, 0<x′<1, 0<x″<1, 0<y≦1, and 0≦d≦0.33, is disclosed. A positive electrode and a lithium battery containing the composite positive active material, and a method of preparing the composite positive active material are also disclosed.

First claim

What is claimed is:

1. A composite positive active material comprising an over-lithiated lithium transition metal oxide, the over-lithiated lithium transition metal oxide comprising a compound represented by Formula 1 or Formula 3:
x Li 2-y M″ y MO 3 -(1- x )LiM′O 2   [Formula 1]

in Formula 1, M being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number of +4,
M′ being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number of +3,
M″ being different from M and being at least one metal cation selected from Period 2 to Period 7 elements,
0<x<1, and 0<y≦1;
x Li 2-y M″ y MO 3 - x ′LiM′O 2 - x ″Li 1+d M′″ 2-d O 4   [Formula 3]

in Formula 3, M being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number of +4,
M′ being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number of +3,
M′″ being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number from +3 to +4, and
M″ being different from M, M′ and M′″ and being at least one metal cation selected from Period 2 to Period 7 elements,
x+x′+x″=1, 0<x<1, 0<x′<1, 0<x″<1, 0<y≦1, and 0≦d≦0.33,
wherein the over-lithiated lithium transition metal oxide has more than one phase.

2. The composite positive active material of claim 1 , wherein, in Formula 1, M″ is doped in a Li ion layer of Li 2-y M″ y MO 3 .

3. The composite positive active material of claim 1 , wherein 0<x<0.6 and 0<y<0.1.

4. The composite positive active material of claim 1 , wherein the over-lithiated lithium transition metal oxide further comprises fluorine.

5. The composite positive active material of claim 1 , wherein M is at least one metal selected from Mn, Ti, Zr, Sn, and Mo.

6. The composite positive active material of claim 1 , wherein M′ is at least one metal selected from Ni, Co, Mn, Fe, Al, Mg, Zn, Cu, Cr, V, and Nb.

7. The composite positive active material of claim 1 , wherein M″ is at least one metal cation selected from Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, and In.

8. The composite positive active material of claim 7 , wherein M″ is at least one metal cation selected from Al, Mn, Cr, Zn, Ga, Mg, V, and Zr.

9. The composite positive active material of claim 1 , wherein the over-lithiated lithium transition metal oxide comprises a compound represented by Formula 2:
x Li 2-y M″ y MnO 3 -(1- x )LiNi a Co b Mn c O 2   [Formula 2]

wherein 0<x<1, 0<y≦1, 0<a<1, 0<b<1, 0<c<1, a+b+c=1, and M″ is different from Mn and is at least one metal cation selected from Period 2 to Period 7 elements.

10. The composite positive active material of claim 1 , wherein the over-lithiated lithium transition metal oxide is included in particles having an average particle size from about 10 nm to about 500 μm.

11. A lithium battery comprising:
a positive electrode comprising the composite positive active material of claim 1 ;
a negative electrode facing the positive electrode; and
an electrolyte between the positive electrode and the negative electrode.

12. A composite positive active material comprising an over-lithiated lithium transition metal oxide, the over-lithiated lithium transition metal oxide comprising a compound represented by Formula 9:
x Li 2 MO 3 -(1- x )LiM′O 2   [Formula 9]

M being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number of +4,
M′ being at least one metal selected from Period 4 transition metals and Period 5 transition metals and having an average oxidation number of +3,
a portion y, wherein 0<y≦1, of Li in a Li ion layer of the over-lithiated lithium transition metal oxide being replaced with at least one metal cation selected from Period 2 to Period 7 elements, and
0<x<1,
wherein the over-lithiated lithium transition metal oxide has more than one phase.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Song Jay-Hyok
• Park Jun-Seok
• Matulevich Evgeniya
• Kim Chang-Wook
• You Yong-Chan
• Kang Sun-Ho

Classifications

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• H01M4/1391

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

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• H01M4/485 Primary

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

• 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