Composite positive electrode active material, positive electrode including the same, and lithium battery including the positive electrode

Patent metadata

Field	Value
Publication number	US-10862106-B2
Application number	US-201615335781-A
Country	US
Kind code	B2
Filing date	Oct 27, 2016
Priority date	Oct 28, 2015
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

A composite positive electrode active material includes: a first metal oxide that has a layered structure and is represented by Formula 1; and a second metal oxide that has a spinel structure and is represented by Formula 2, wherein the composite positive electrode active material includes a composite of the first metal oxide and the second metal oxide:

LiMO 2   Formula 1

LiMe 2 O 4   Formula 2
wherein, in Formulas 1 and 2, M and Me are each independently at least one element selected from Groups 2 to 14 of the periodic table, and a molar ratio of Li/(M+Me) in the composite is less than 1.

First claim

What is claimed is:

1. A composite positive electrode active material comprising:
an integrated crystal structure formed of a lithium compound and a co-precipitation product of a Co precursor, a Mn precursor, and a Ni precursor, wherein the lithium compound and the co-precipitation product form a lithium layer disposed between layers of a first lithium oxide,
wherein the first lithium oxide has the formula LiCoO 2 and has a layered structure;
wherein the lithium layer comprises a second lithium oxide of the formula Li(Ni 1-c Mn c ) 2 O 4 , wherein 0.2<c<1 and having a spinel structure,
wherein the first metal oxide and the second metal oxide form the integrated crystal structure,
wherein a content of Mn and Ni in the lithium layer is greater than 0 and less than about 10%, based a total content of a lithium site in the lithium layer of the composite positive electrode active material,
wherein the composite positive electrode active material has a molar ratio of Li/(Co+(Ni+Mn)) of 0.8 to less than 1, and
wherein the composite positive electrode active material has a structure in which the second lithium oxide of the formula Li(Ni 1-c Mn c ) 2 O 4 having the spinel structure is disposed between layers of the first lithium oxide of the formula LiCoO 2 having the layered structure.

2. The composite positive electrode active material of claim 1 , wherein the composite positive electrode active material comprises a compound represented by Formula 3:
x LiMO 2 .y LiMe 2 O 4   Formula 3

wherein, in Formula 3 x+y=1, 0<x<1, 0<y<1, and 0.2<c<1, and
a molar ratio of Li/(Co+(Ni+Mn)) in the composite is less than 1.

3. The composite positive electrode active material of claim 2 , wherein, in Formula 3, x is in a range of about 0.75 to about 0.99; and y is in a range of about 0.01 to about 0.25.

4. The composite positive electrode active material of claim 2 , wherein the compound represented by Formula 3 is xLiCoO 2 .yLiNi 0.5 Mn 1.5 O 4 .

5. The composite positive electrode active material of claim 2 , wherein the compound represented by Formula 3 is 0.8LiCoO 2 .0.2LiNi 0.5 Mn 1.5 O 4 , 0.9LiCoO 2 .0.1LiNi 0.5 Mn 1.5 O 4 , 0.95LiCoO 2 .0.05LiNi 0.5 Mn 1.5 O 4 , 0.85LiCoO 2 .0.15LiNi 0.5 Mn 1.5 O 4 , or 0.6LiCoO 2 .0.4LiNi 0.5 Mn 1.5 O 4 .

6. The composite positive electrode active material of claim 1 , wherein, in Formula 1, a molar ratio of Li/(Co+(Ni+Mn)) is in a range of about 0.8 to about 0.95.

7. The composite positive electrode active material of claim 1 , wherein the second metal oxide is LiNi 0.5 Mn 1.5 O 4 .

8. The composite positive electrode active material of claim 1 , wherein the content of the Mn, Ni, or a combination thereof in the lithium layer is determined by Equation 1:
Cation mixing ratio={ I (003) /I (104) }×100  Equation 1

wherein, I (003) is an intensity of an X-ray diffraction peak of the (003) face of the composite and I (104) is an intensity of an X-ray diffraction peak of the (104) face of the composite, when determined using Cu-kα radiation.

9. The composite positive electrode active material of claim 1 , wherein a full width at half maximum of an X-ray diffraction peak within a 2θ range of about 18° to about 19° is in a range of about 0.2° to about 0.28°, when determined using Cu-kα radiation.

10. The composite positive electrode active material of claim 1 , wherein an average discharge voltage of a half-cell during a 50 th cycle is about 97.5% to about 99.95% of an average discharge voltage during a first cycle, when determined using a positive electrode comprising the composite positive electrode active material and lithium as a counter electrode.

11. The composite positive electrode active material of claim 1 , wherein the composite positive electrode active material further comprises a coating layer comprising at least one selected from a conductive material, a metal oxide, and an inorganic fluoride.

12. The composite positive electrode active material of claim 11 , wherein the conductive material is at least one selected from a carbon-containing material, indium tin oxide, RuO 2 , and ZnO.

13. The composite positive electrode active material of claim 11 , wherein the metal oxide is at least one selected from silica, alumina, a zirconium oxide, a titanium oxide, and a mixture thereof.

14. The composite positive electrode active material of claim 11 , wherein the inorganic fluoride is at least one selected from AlF 3 , CsF, KF, LiF, NaF, RbF, TiF 4 , AgF, AgF 2 , BaF 2 , CaF 2 , CuF 2 , CdF 2 , FeF 2 , HgF 2 , Hg 2 F 2 , MnF 2 , MgF 2 , NiF 2 , PbF 2 , SnF 2 , SrF 2 , XeF 2 , ZnF 2 , BF 3 , BiF 3 , CeF 3 , CrF 3 , DyF 3 , EuF 3 , GaF 3 , GdF 3 , Fe F3 , HoF 3 , InF 3 , LaF 3 , LuF 3 , MnF 3 , NdF 3 , VOF 3 , PrF 3 , SbF 3 , ScF 3 , SmF 3 , TbF 3 , TiF 3 , TmF 3 , YF 3 , YbF 3 , TIF 3 , CeF4, GeF 4 , HfF 4 , SiF 4 , SnF 4 , TiF 4 , VF 4 , ZrF 4 , NbF 5 , SbF 5 , TaF 5 , BiF 5 , MoF 6 , ReF 6 , SF 6 , and WF 6 .

15. A positive electrode comprising the composite positive electrode active material of claim 1 .

16. A lithium battery comprising the positive electrode of claim 15 .

17. The lithium battery of claim 16 , wherein a working voltage of the lithium battery is between about 2.5 volts to about 4.5 volts.

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Kim Donghan
• Kim Ryounghee
• Park Jinhwan
• Song Jayhyok
• Yu Byongyong
• Choi Byungjin

Classifications

• H01M10/052

  Li-accumulators · 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

• H01M10/0525

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

• H01M4/131 Primary

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

• H01M4/505

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