# US 10,483,540 B2 · Lithium complex oxide for lithium secondary battery positive active material and method of preparing the same

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- Number: US 10,483,540 B2
- Document ID: US10483540B2
- Status: Granted
- Kind: B2
- Application number: 15/471,317
- Filed: 2017-03-28
- Published: 2018-02-08
- Granted: 2019-11-19
- Earliest claimed: 2016-08-02
- Assignees: Ecopro Bm Co., Ltd.
- Applicants: Ecopro Bm Co., Ltd.
- Inventors: Moon Ho Choi; Jong Seung Shin; Dong Hee Kim; Suk Yong Jeon; Hyun Jong Yu; Kyoung Jun Lee; Young Nam Park
- Web page: https://patentgrep.com/patent/US10483540B2

## CPC

- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- C01G 53/42: containing alkali metals, e.g. LiNiO2
- H01B 1/08: oxides
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/364: {as mixtures}
- H01M 4/366: {as layered products}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/48: of inorganic oxides or hydroxides
- H01M 4/50: of manganese
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2004/50: Agglomerated particles
- C01P 2006/40: Electric properties
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## 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.

## Claims

### Claim 1

A lithium complex oxide secondary particle formed by coagulation of a plurality of primary particles, wherein Co concentration at a boundary of the primary particle is higher than Co concentration in an internal part of the primary particle,
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,
wherein the P1 and the P2 are ranged respectively in 779 eV≤P1≤780 eV and 794 eV≤P2≤795 eV, and
wherein a primary particle located at a surface part of the secondary particle has a Co concentration gradient reduced by 0.05 to 0.07 mol % per nm toward a center of the primary particle from a surface of the primary particle.

### Claim 2 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein the Co concentration of the primary particle located at the surface part of the secondary particle, at a part which is in contact with the surface of the secondary particle, is higher than at a part that is in noncontact with the surface of the secondary particle.

### Claim 3 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein Co ion concentration is graded, in the primary particle located at the surface of the secondary particle, toward a center of the particle from the surface of the particle.

### Claim 4 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein the primary particle located at the surface part of the secondary particle is configured to satisfy that dc/dh is 2 to 10, where the dc is a length toward the center and the dh is a length vertical to the center.

### Claim 5 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein the secondary particle has at least one peak at positions (104), (110), (113), (101), (102), and (003) during XRD analysis.

### Claim 6 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein the secondary particle has a ratio of peak intensity (I531) around 531 eV and peak intensity (I528) around 528.5 eV during an O 1s core-level spectrometry that is obtained through XPS measurement, and
wherein the ratio is I531/I528≤2.

### Claim 7 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein the secondary particle has a ratio between peak intensity (I289) around 289 eV and peak intensity (I284) around 284.5 eV during a C 1s core-level spectrometry that is obtained through XPS measurement, and
wherein the ratio is I289/I284≤0.9.

### Claim 8 (depends on 1)

The lithium complex oxide secondary particle of claim 1, wherein the secondary particle is given by the following Formula 1,
LixNi1-(a1+b1+c1)Coa1M1b1M2c1M3dOy, [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≤x≤1.05, 1.50≤y≤2.1, 0.02≤a1≤0.25, 0.01≤b1≤0.20, 0≤c1≤0.20, and 0≤d≤0.20.

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 9)

The lithium secondary battery of claim 9, wherein the lithium secondary battery is configured to have residual lithium equal to or smaller than 6,000 ppm.

### Claim 11 (depends on 1)

A method of preparing a lithium complex oxide secondary particle by claim 1, the method comprising:
manufacturing precursors of lithium secondary battery positive active materials given by the following Formula 2,
Ni1−(x2+y2+z2)Cox2M1y2M2z2(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≤2≤0.25, 0≤y2≤0.20, and 0≤z2≤0.20;
reacting precursors of lithium secondary battery positive active materials with a lithium compound and manufacturing a positive active material by first thermal 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 M2 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;
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.

### Claim 12 (depends on 11)

The method of claim 11, wherein the reactively coating comprises:
reactively coating the washed positive active material with the solution containing Co.

### Claim 13 (depends on 11)

The method of claim 11, wherein, in the reactively coating, the solution containing Co ion has concentration of 1 to 10 mol %.