Positive electrode active material and lithium secondary battery comprising the same

Patent metadata

Field	Value
Publication number	US-11837725-B2
Application number	US-202318151282-A
Country	US
Kind code	B2
Filing date	Jan 6, 2023
Priority date	Nov 29, 2019
Publication date	Dec 5, 2023
Grant date	Dec 5, 2023

Abstract

The present invention relates to a positive electrode active material having improved electrical characteristics by adjusting an aspect ratio gradient of primary particles included in a secondary particle, a positive electrode including the positive electrode active material, and a lithium secondary battery using the positive electrode.

First claim

What is claimed is:

1. A positive electrode active material, comprising:
primary particles enabling lithium intercalation/deintercalation and secondary particles in which the primary particles are aggregated,
wherein the average aspect ratio of the primary particles has a gradient increasing from the center region of the secondary particle to the surface region of the secondary particle,
wherein a dopant exhibits a concentration gradient decreasing from the surface region of the secondary particle toward the center region of the secondary particle, and
wherein the primary particle is represented by Formula 1 below:
Li w Ni 1−(x+y+z+z′) Co x M1 y M2 z Nb z′ O 2   [Formula 1]

(Wherein, M1 is at least one selected from Mn and Al,
M2 is at least one selected from P, Sr, Ba, B, Ti, Zr, Mn, Al, W, Ce, Hf, Ta, Cr, F, Mg, Cr, V, Fe, Zn, Si, Y, Ga, Sn, Mo, Ge, Nd, Gd and Cu,
M1 and M2 are different elements, and
0.5≤w≤1.5, 0≤x≤0.50, 0≤y≤0.20, 0≤z≤0.20, and 0<z′≤0.20).

2. The positive electrode active material of claim 1 , as the content of a metal dopant in the primary particle increases from the center region of the secondary particle toward the surface region of the secondary particle, a difference between the average aspect ratio of all primary particles in the surface region of the secondary particle and the average aspect ratio of all primary particles in the center region of the secondary particle is reduced.

3. The positive electrode active material of claim 1 , wherein M2 and/or niobium (Nb) exhibits a concentration gradient decreasing from the surface region of the secondary particle toward the center region of the secondary particle.

4. The positive electrode active material of claim 1 , wherein a lithium ion diffusion path in the primary particle is formed in the same direction as the direction of the concentration gradient of M2 and/or niobium (Nb).

5. The positive electrode active material of claim 1 , wherein an aspect ratio of the primary particles having a relatively large sum of z and z′ in Formula 1 in the surface region of the secondary particle is smaller than an aspect ratio of the primary particles having a relatively small sum of z and z′ in Formula 1 in the surface region of the secondary particle.

6. The positive electrode active material of claim 1 , as the sum of z and z′ in Formula 1 in the primary particle increases from the center region of the secondary particle toward the surface region of the secondary particle, a difference between the average aspect ratio of all primary particles in the surface region of the secondary particle and the average aspect ratio of all primary particles in the center region of the secondary particle is reduced.

7. The positive electrode active material of claim 1 , wherein when a distance from the core to the surface region of the secondary particle is R, a region where the distance from the center region of the secondary particle is ⅘R to R is a first region (R 1 ), and a region where the distance from the center region of the secondary particle is 0 to ⅖R is a second region (R 2 ),
wherein the proportion of primary particles having a smaller aspect ratio than the average aspect ratio (W 1 ) among the primary particles in the first region is 45% or more.

8. The positive electrode active material of claim 7 , wherein a ratio (W 1 /W 2 ) of the average aspect ratio (W 1 ) of all primary particles in the first region and the average aspect ratio (W 2 ) of all primary particles in the second region is more than 1.280 and less than 2.217.

9. The positive electrode active material of claim 7 , wherein a ratio (W 3 /W 2 ) of the average aspect ratio (W 3 ) of primary particles having a smaller aspect ratio than the average aspect ratio (W 1 ) among the primary particles in the first region and the average aspect ratio (W 2 ) of all primary particles in the second region is more than 0.984 and less than 1.465.

10. The positive electrode active material of claim 7 , wherein a ratio (W 4 /W 2 ) of the average aspect ratio (W 4 ) of the primary particles having a higher aspect ratio than the average aspect ratio (W 1 ) among the primary particles in the first region and the average aspect ratio (W 2 ) of all primary particles in the second region is more than 1.793 and less than 3.076.

11. The positive electrode active material of claim 7 , wherein the average aspect ratio (W 1 ) of all primary particles in the first region is less than 4.083.

12. The positive electrode active material of claim 7 , wherein the average aspect ratio (W 2 ) of all primary particles in the second region is less than 1.842.

13. The positive electrode active material of claim 1 , further comprising:
a coating layer covering at least a part of the interface between the primary particles and the surface of the secondary particle,
wherein the coating layer comprises at least one oxide represented by Formula 2 below:
Li a M3 b O c   [Formula 2]

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

14. A positive electrode comprising the positive electrode active material of claim 1 .

15. A lithium secondary battery using the positive electrode of claim 14 .

Assignees

• Ecopro Bm Co Ltd

Inventors

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

Classifications

• 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

• C01G53/50 Primary

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

• H01B1/08

  oxides · CPC title

• H01M4/366 Primary

  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