Lithium complex oxide for lithium secondary battery positive active material and method of preparing the same

Patent metadata

Field	Value
Publication number	US-11502297-B2
Application number	US-202017124480-A
Country	US
Kind code	B2
Filing date	Dec 16, 2020
Priority date	Aug 2, 2016
Publication date	Nov 15, 2022
Grant date	Nov 15, 2022

Abstract

Disclosed is a lithium complex oxide and method of manufacturing the same, more particularly, a lithium complex oxide effective in improving the characteristics of capacity, resistance, and lifetime with reduced residual lithium and with different interplanar distances of crystalline structure between a primary particle locating in an internal part of secondary particle and a primary particle locating on the surface part of the secondary particle, and a method of preparing the same.

First claim

The invention claimed is:

1. A lithium complex oxide secondary particle formed by coagulation of a plurality of primary particles,
wherein an interplanar distance of a crystalline structure in said primary particles decreases toward a surface from a center of the secondary particle, and
wherein the secondary particle has a ratio between a highest peak intensity (I 289 ) between 288 eV and 290 eV and a highest peak intensity (I 284 ) between 283.5 eV and 285.5 eV during a C 1s core-level spectrometry that is obtained through XPS measurement, and wherein the ratio is I 289 /I 284 ≤0.9.

2. The lithium complex oxide secondary particle of claim 1 , wherein an interplanar distance of the crystalline structure in said primary particles at the center of the secondary particle, d1, is configured to be equal to or larger than 4.8 nm.

3. The lithium complex oxide secondary particle of claim 1 , wherein an interplanar distance of the crystalline structure in said primary particles on the surface of the secondary particle, d2, is configured to be equal to or smaller than 4.7 nm.

4. The lithium complex oxide secondary particle of claim 1 , wherein the lithium complex oxide secondary particle is configured in a hexagonal structure, and
wherein a lithium ion pathway in said primary particles is formed toward the center from the surface of the secondary particle.

5. The lithium complex oxide secondary particle of claim 1 ,
wherein the secondary particle comprises a Co-coated layer on the surface.

6. The lithium complex oxide secondary particle of claim 1 , wherein the secondary particle has a bound energy (P1) of spin-orbit splitting 2p3/2 peak and a bound energy (P2) of 2p1/2 peak in a Co 2p core-level spectrometry obtained through XPS measurement, and
wherein the P1 and the P2 are ranged respectively in 779 eV≤P1≤780 eV and 794 eV≤P2≤795 eV.

7. The lithium complex oxide secondary particle of claim 1 , wherein the secondary particle has a ratio of a highest peak intensity (I 531 ) between 530 eV and 532 eV and a highest peak intensity (I 528 ) between 527.5 eV and 529.5 eV during an O 1s core-level spectrometry that is obtained through XPS measurement, and wherein the ratio is I 531 /I 528 ≤2.

8. The lithium complex oxide secondary particle of claim 1 , wherein the secondary particle is given by the following Formula 1
Li X1 Ni 1−(x1+y1+z1+r1) Co x1 M1 y1 M2 z1 M3 r1 O a ,  [Formula 1]

wherein, in the Formula 1, M1 is Mn or Al, and M2 is Co, and M3 is selected from the group consisting of Al, Ba, B, Co, Ce, Cr, F, Li, Mg, Mn, Mo, P, Sr, Ti, and Zr, and
wherein 0.95≤X1≤1.05, 1.50≤a≤2.1, 0.02≤x1≤0.25, 0.01≤y1≤0.20, 0<z1≤0.20, and 0≤r1≤0.20.

9. A method of preparing a lithium complex oxide secondary particle of claim 1 , the method comprising:
manufacturing precursors of lithium secondary battery positive active material;
reacting the precursors of lithium secondary battery positive active material with a lithium compound and manufacturing a positive active material by a first thermal treatment;
washing the positive active material with distilled water or an alkaline solution;
reactively coating the washed positive active material with a solution containing Co with distilled water or an alkaline solution;
drying particles of the positive active material; and
mixing the dried positive active material with one or more elements selected from the group consisting of Al, Ba, B, Co, Ce, Cr, F, Mg, Mn, Mo, P, Sr, Ti, and Zr and doping the one or more elements into the particles by a second thermal treatment.

10. A lithium secondary battery comprising a lithium complex oxide secondary particle of claim 1 .

11. The lithium secondary battery of claim 10 , wherein the lithium secondary battery is configured to have residual lithium equal to or smaller than 6,000 ppm.

Assignees

• Ecopro Bm Co Ltd

Inventors

• Choi Moon Ho
• Shin Jong Seung
• Kim Dong Hee
• Jeon Suk Yong
• Yu Hyun Jong
• Lee Kyoung Jun
• Park Young Nam

Classifications

• 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

• H01M4/505

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

• C01P2004/84

  one phase coated with the other · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title