Positive electrode active material and lithium secondary battery comprising the same

Patent metadata

Field	Value
Publication number	US-12087946-B2
Application number	US-202117382667-A
Country	US
Kind code	B2
Filing date	Jul 22, 2021
Priority date	Oct 27, 2020
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

The present invention relates to a positive electrode active material which makes it possible to improve the electrochemical properties and stability of a positive electrode active material including a lithium composite oxide by adjusting the direction of a concentration gradient of a metal element of the lithium composite oxide, and a lithium secondary battery using a positive electrode including the positive electrode active material.

First claim

What is claimed is:

1. A positive electrode active material, comprising:
a lithium composite oxide enabling lithium intercalation/deintercalation,
wherein at least one metal element of the lithium composite oxide exhibits a concentration gradient including a first concentration gradient section having a (+) slope and a second concentration gradient section having a (−) slope from the outermost surface toward the center of the lithium composite oxide,
the first concentration gradient section is present from the outermost surface of the lithium composite oxide to a predetermined depth, and the second concentration gradient section is present at an inner side of the first concentration gradient section,
in the first concentration gradient section, a nickel concentration of the lithium composite oxide is decreased, and a cobalt concentration of the lithium composite oxide is increased from the surface toward the center of the lithium composite oxide, and
in the second concentration gradient section, a nickel concentration of the lithium composite oxide is increased, and a cobalt concentration of the lithium composite oxide is decreased from the surface toward the center of the lithium composite oxide,
wherein:
in the first concentration gradient section, a concentration of at least one selected from manganese and aluminum thereof is increased from the surface toward the center of the lithium composite oxide;
in the second concentration gradient section, a concentration of at least one selected from manganese and aluminum thereof is decreased from the surface toward the center of the lithium composite oxide;
there is a concentration maintenance section which is located at an inner side of the second concentration gradient section, and in which the concentration of at least one metal element of the lithium composite oxide is maintained from the surface toward the center of the lithium composite oxide; and
a nickel concentration of the lithium composite oxide in the concentration maintenance section is higher than those in the first concentration gradient section and the second concentration gradient section.

2. The positive electrode active material of claim 1 , wherein the first concentration gradient section and the second concentration gradient section are continuously present from the outermost surface of the lithium composite oxide.

3. The positive electrode active material of claim 2 , wherein, when the average diameter of the lithium composite oxide is indicated as d, the first concentration gradient section and the second concentration gradient section are present in a depth range of 0.05d to 0.33d from the outermost surface of the lithium composite oxide.

4. The positive electrode active material of claim 3 , wherein the first concentration gradient section and the second concentration gradient section are present to a depth of 1 μm from the outermost surface of the lithium composite oxide.

5. The positive electrode active material of claim 1 , wherein the absolute value of the rate of change in concentration of at least one metal element in the concentration maintenance section is 5 mol % or less.

6. The positive electrode active material of claim 1 , wherein the concentrations of at least one selected from cobalt, manganese and aluminum of the lithium composite oxide in the first concentration gradient section and second concentration gradient section are higher than that in the concentration maintenance section.

7. The positive electrode active material of claim 1 , wherein the lithium composite oxide is represented by Formula 1 below:
Li w Ni 1−(x+y+z) Co x M1 y M2 z O 2+δ
(Wherein,
M1 is at least one selected from Mn or Al,
M2 is at least one selected from P, Sr, Ba, B, Ti, Zr, Mn, Al, W, Ce, Hf, Ta, F, Mg, Cr, V, Fe, Zn, Si, Y, Ga, Sn, Mo, Ge, Nd, Gd and Cu,
M1 and M2 are different elements,
0.5≤w≤1.5, 0≤x≤0.50,0≤y≤0.20, 0≤z≤0.20, and 0≤8≤0.02.).

8. The positive electrode active material of claim 7 , wherein the Ni, Co, M1 and M2 concentrations (mol %) of the lithium composite oxide satisfy the following Equation 1:

Ni
/

(

Ni
+
Co
+

M
⁢
1

+

M
⁢
2

)

≥

8
⁢

0.
.

[

Equation
⁢

1

]

9. The positive electrode active material of claim 1 , wherein the lithium composite oxide comprises a primary particle having a layered crystal structure, and a secondary particle formed by aggregating primary particles.

10. The positive electrode active material of claim 9 , wherein the secondary particle has an average particle diameter of 3 to 20 μm.

11. The positive electrode active material of claim 9 , wherein the positive electrode active material comprises a coating layer which covers at least a part of a region selected from the interface between the primary particles and the surface of the secondary particle, and comprises at least one lithium alloy oxide represented by Formula 2 below:
Li a M3 b O c   [Formula 2]

(Wherein,
M3 is at least one selected from the group consisting of Ni, Mn, Co, Fe, Cu, Nb, Mo, Ti, Al, Cr, Zr, Zn, Na, K, Ca, Mg, Pt, Au, B, P, Eu, Sm, W, V, Ba, Ta, Sn, Hf, Ce, Gd and Nd,
0≤a≤10, 0<b≤8, and 2≤c≤13.).

12. A positive electrode including the positive electrode active material of claim 1 .

13. A lithium secondary battery using the positive electrode of claim 12 .

Assignees

• Ecopro Bm Co Ltd

Inventors

• Choi Gwang Seok
• Choi Moon Ho
• Suh Jun Won
• Yun Jin Kyeong
• Lee Jung Han
• Choi Seung Woo
• Bae Joong Ho
• Kim Du Yeol

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

• H01M4/505

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

• H01M4/525 Primary

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

• C01G53/82

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title