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

Patent metadata

Field	Value
Publication number	US-2024063382-A1
Application number	US-202318205366-A
Country	US
Kind code	A1
Filing date	Jun 2, 2023
Priority date	Aug 2, 2016
Publication date	Feb 22, 2024
Grant date	—

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 a 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

1 - 20 . (canceled)

21 . A lithium complex oxide secondary particle formed by coagulation of a plurality of primary particles,
wherein the primary particle locating on the surface part of the secondary particle has a Co concentration at a boundary between the primary particle and another primary particle that is higher than a Co concentration of an internal part of each of the primary particles, and wherein the secondary particle has at least one peak at positions (104), (110), (113), (101), (102), and (003) during XRD analysis.

22 . The lithium complex oxide secondary particle of claim 21 , wherein the lithium complex oxide secondary particle is configured to satisfy the following Relation 1,
d 1> d 2,  [Relation 1]
where the d1 is an interplanar distance of a crystalline structure in a primary particle, among the plurality of primary particles, locating in the internal part of the secondary particle and the d2 is an interplanar distance of a crystalline structure in the primary particle locating on the surface part of the secondary particle.

23 . The lithium complex oxide secondary particle of claim 21 , wherein the primary particle locating on the surface part of the secondary particle has the Co concentration gradient in 0.05 to 0.07 mol % per one nm toward the center part of the particle.

24 . The lithium complex oxide secondary particle of claim 22 , wherein the lithium complex oxide secondary particle is configured to satisfy the following Relation 2 with the d1, the d2, and d3,
d 1> d 3> d 2,  [Relation 2]
where the d3 is an interplanar distance of a crystalline structure at a boundary of the Co-coated layer in the primary particle locating on the surface part of the secondary particle.

25 . The lithium complex oxide secondary particle of claim 22 , wherein the d1, which is the interplanar distance of the crystalline structure in the primary particle locating in the internal part of the secondary particle, is configured to be equal to or larger than 4.8 nm.

26 . The lithium complex oxide secondary particle of claim 22 , wherein the d2, which is the interplanar distance of the crystalline structure in the primary particle locating on the surface part of the secondary particle, is configured to be equal to or smaller than 4.7 nm.

27 . The lithium complex oxide secondary particle of claim 21 , wherein the secondary particle has a bound energy (P1) of spin-orbit-spit 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.

28 . A method of preparing a lithium complex oxide secondary particle by claim 21 , the method comprising:
manufacturing precursors of lithium secondary battery positive active material given by the following Formula 2
Ni 1−(x2+y2+z2) Co x2 M1 y2 M2 z2 (OH) 2 ,  [Formula 2]

wherein, in Formula 2, M1 is Mn or Al, and M2 is a metal selected from a group of Al, Ba, B, Co, Ce, Cr, F, Li, Mg, Mn, Mo, P, Sr, Ti, and Zr, and wherein 0≤x2≤0.20, 0≤y2≤0.20, and 0≤z2≤0.20; reacting the precursors of lithium secondary battery positive active material with a lithium compound and manufacturing a positive active material by first thermally treating the reactant; washing the positive active material with distilled water or an alkaline solution; reactively coating the washed positive active material with a solution containing Co; drying particles of the positive active material; and mixing the dried positive active material with M3 that is a metal selected from the group of Al, Ba, B, Co, Ce, Cr, F, Li, Mg, Mn, Mo, P, Sr, Ti, and Zr and doping the metal M3 into the particles by second thermal treating the mixture.

29 . The method of claim 28 , wherein, in the reactively coating, the solution including Co ion has concentration of 1 to 10 mol %.

30 . A lithium complex oxide secondary particle prepared by the method of claim 28 .

31 . A lithium secondary battery comprising a lithium complex oxide secondary particle of claim 30 .

32 . The lithium secondary battery of claim 31 , wherein the lithium secondary battery is configured to have residual lithium equal to or smaller than 6,000 ppm.

33 . The lithium complex oxide secondary particle of claim 21 , wherein the secondary particle is given by the following Formula 1
Li X1 Ni 1−(x1+y1+z1) Co x1 M1 y1 M2 z1 M3 r1 O a ,  [Formula 1]
wherein, in the Formula 1, M1 is Mn or Al, and M2 and M3 are metals selected from a group 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, 0.02x1≤0.25, 0.01≤y1≤0.20, 0≤z1≤0.20, and 0≤r1≤0.20.

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

• H01M4/525 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

• 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

• Y02T10/70

  Energy storage systems for electromobility, e.g. batteries · CPC title

• H01M2004/028

  Positive electrodes · CPC title