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

Patent metadata

Field	Value
Publication number	US-11764352-B2
Application number	US-202017078269-A
Country	US
Kind code	B2
Filing date	Oct 23, 2020
Priority date	Oct 28, 2015
Publication date	Sep 19, 2023
Grant date	Sep 19, 2023

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:
a first metal oxide having a layered crystal structure, wherein the first metal oxide is represented by Formula 8, Formula 9, or Formula 10:
LiNi d Co 1-d-e-f Mn e M f O 2   Formula 8

wherein, in Formula 8, 0<d<1, 0<e<1, 0≤f<1, and 0<d+e+f<1, and M is at least one metal of V, Mg, Ga, Si, W, Mo, Fe, Cr, Cu, Zn, Ti, Al, or B,
Li[Co 1-d M d ]O 2   Formula 9

wherein, in Formula 9, 0≤d≤0.5, and M is at least one metal of Mg, Al, Ni, Mn, Zn, Fe, Cr, Ga, Mo, or W, or
Li[Ni 1-d M d ]O 2   Formula 10

wherein, in Formula 10, 0.01≤d≤0.5, and M is at least one metal of Mg, Al, Co, Mn, Zn, Fe, Cr, Ga, Mo, or W; and
a second metal oxide having a spinel structure, wherein the second metal oxide is a compound represented by the formula Li(Ni 1-c Mn c ) 2 O 4 , wherein 0.2<c<1, and
wherein
the first metal oxide and the second metal oxide form an integrated crystal structure such that the second metal oxide having the spinel structure is integrated within the crystal structure of the first metal oxide, and
the composite positive electrode active material has a crystal structure in which the second metal oxide having the spinel structure is disposed between crystallographic layers of the first metal oxide in the crystal structure of the composite.

2. The composite positive electrode active material of claim 1 , wherein the composite positive electrode active material comprises a compound comprising the first metal oxide represented by Formula 8 and the second metal oxide, the compound represented by the formula
xLiNi d Co 1-d-e-f Mn e M f O 2 ·yLi(Ni 1-c Mn c ) 2 O 4

wherein x+y=1, 0<x<1, and 0<y<1, and
a molar ratio of Li/(M+(Ni+Mn)) in the composite is in a range of about 0.8 to about 0.95, wherein a molar content of Li is based on a total Li content in the composite.

3. The composite positive electrode active material of claim 2 , wherein in the formula xLiNi d Co 1-d-e-f Mn e M f O 2 ·yLi(Ni 1-c Mn c ) 2 O 4 , M is at least one metal of Ga, Mo, Fe, Cr, or Al.

4. The composite positive electrode active material of claim 2 , wherein, 0.75≤x≤0.99 and 0.01≤y≤0.25.

5. The composite positive electrode active material of claim 2 , wherein, the molar ratio of Li/(M+(Ni+Mn)) is in a range of about 0.8 to about 0.9, wherein the molar content of Li is based on the total Li content in the composite.

6. The composite positive electrode active material of claim 2 , wherein
0.5≤d<1, and f=0.

7. The composite positive electrode active material of claim 1 , wherein the first metal oxide is a compound represented by Formula 9 or Formula 10, comprising LiNi 0.5 Co 0.5 O 2 .

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

9. The composite positive electrode active material of claim 1 , wherein a cation mixing ratio in the composite positive electrode active material is greater than 0 and less than about 10%, based on a total amount of lithium sites in crystallographic lithium layers between transition metal layers in a crystal structure of the composite positive electrode active material.

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

11. The composite positive electrode active material of claim 1 , having an average discharge voltage versus lithium during a 50 th cycle of about 97.5% to about 99.95% of an average discharge voltage versus lithium during a first cycle of a positive electrode comprising the composite positive electrode active material and lithium as a counter electrode.

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

13. A lithium battery comprising the positive electrode of claim 12 .

14. The lithium battery of claim 13 , wherein a working voltage of the lithium battery is 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

• H01M4/131 Primary

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

• H01M4/364 Primary

  as mixtures · CPC title

• H01M4/366

  as layered products · CPC title

• H01M10/0525

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