# US 12,015,151 B2 · Composite positive electrode active material, method of preparing the same, positive electrode including composite positive electrode active material,and lithium battery including positive electrode

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- Number: US 12,015,151 B2
- Document ID: US12015151B2
- Status: Granted
- Kind: B2
- Application number: 17/748,307
- Filed: 2022-05-19
- Published: 2022-09-01
- Granted: 2024-06-18
- Earliest claimed: 2018-11-23
- Assignees: Samsung Electronics Co., Ltd.; Postech Academy-Industry Foundation
- Applicants: Samsung Electronics Co., Ltd.; Postech Academy-Industry Foundation
- Inventors: Donghee Yeon; Byoungwoo Kang; Junghwa Lee; Byungjin Choi; Sukgi Hong; Jinsu Ha
- Web page: https://patentgrep.com/patent/US12015151B2

## CPC

- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/362: {Composites}
- 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
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- 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
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A composite positive active material represented by Formula 1, LiaNibCOcMndMeO2 Formula 1 wherein, in Formula 1, M is zirconium (Zr), aluminum (Al), rhenium (Re), vanadium (V), chromium (Cr), iron (Fe), gallium (Ga), silicon (Si), boron (B), ruthenium (Ru), titanium (Ti), niobium (Nb), molybdenum (Mo), magnesium (Mg), or platinum (Pt), 1.1≤a≤1.3, b+c+d+e≤1, 0≤b≤0.3, 0≤c≤0.3, 0<d≤0.6, and 0≤e≤0.1, wherein, through atomic interdiffusion of lithium and the metal, the composite positive active material has a uniform distribution of lithium excess regions and a uniform degree of disorder of metal cations, and the metal cations have a disordered, irregular arrangement at an atomic scale. Also a method of preparing the composite positive active material, a positive electrode including the composite positive active material, and a lithium battery including the positive electrode.

## Claims

### Claim 1

A composite positive active material represented by Formula 1,
LiaNibCOcMndMeO2 Formula 1
wherein, in Formula 1,
M is zirconium, aluminum, rhenium, vanadium, chromium, iron, gallium, silicon, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum,
1.1≤a≤1.3, b+c+d+e≤1, 0≤b≤0.3, 0≤c≤0.3, 0<d≤0.6, and 0≤e≤0.1, and
wherein, through atomic interdiffusion of lithium and the metal, the composite positive active material has
a uniform distribution of lithium excess regions, and a uniform degree of disorder of metal cations, and
the metal cations have a disordered, irregular arrangement at an atomic scale and a mixed disordered cation structure,
wherein a ratio of an intensity of a (003) peak to an intensity of a (104) peak is about 0.87 to about 1.11, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation, and
wherein a full width at half-maximum of a diffraction peak between 43º and 45° 2θ of the composite positive active material is about 0.2° to about 0.32°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 2 (depends on 1)

The composite positive active material of claim 1, wherein the composite positive active material comprises
a layered phase structure in which a metal layer and a lithium layer are not distinguishable from one another, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 3 (depends on 2)

The composite positive active material of claim 2, wherein a ratio of I(44.x°)/I(44.y°) is 0.2 or less, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 4 (depends on 1)

The composite positive active material of claim 1, wherein a full width at half-maximum of a diffraction peak between 43° and 45° 2θ of the composite positive active material is from 0.24° to less than 0.31°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 5 (depends on 1)

The composite positive active material of claim 1, wherein ordering of lithium excess regions is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

### Claim 6 (depends on 1)

The composite positive active material of claim 1, wherein ordering of Li, Ni, Co, Mn, and M cations is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

### Claim 7 (depends on 1)

The composite positive active material of claim 1, wherein the composite positive active material is a composite represented by Formula 2:
aLi1+xNi0.5−xMn0.5O2·bLi2−yNiyMnO3 Formula 2
wherein, in Formula 2, 0≤x<0.2, 0≤y<0.2, 0<a<1, 0<b<1, a+b=1, and ax=by.

### Claim 8 (depends on 1)

The composite positive active material of claim 1, wherein the composite positive active material is Li1.2Ni0.2Mn0.6O2, Li1.2Ni0.3Mn0.3O2, Li1.1Ni0.3Mn0.6O2, or a combination thereof.

### Claim 9 (depends on 1)

The composite positive active material of claim 1, wherein the composite positive active material has a capacity of about 275 milliampere-hours per gram or greater.

### Claim 10 (depends on 1)

A positive electrode comprising the composite positive active material according to claim 1.

### Claim 11 (depends on 10)

The positive electrode of claim 10, wherein a ratio of I(44.x°)/I(44.y°) is 0.2 or less, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 12 (depends on 10)

The positive electrode of claim 10, wherein a full width at half-maximum of a diffraction peak between 43° and 45° 2θ of the composite positive active material is about 0.2° to about 0.32°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 13 (depends on 10)

The positive electrode of claim 10, wherein ordering of lithium excess regions is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

### Claim 14 (depends on 10)

The positive electrode of claim 10, wherein ordering of Li, Ni, Co, Mn, and M cations is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

### Claim 15 (depends on 10)

The positive electrode of claim 10, wherein the composite positive active material is a composite represented by Formula 2:
aLi1+xNi0.5−xMn0.5O2·bLi2−yNiyMnO3 Formula 2
wherein, in Formula 2, 0≤x<0.2, 0≤y<0.2, 0<a<1, 0<b<1, a+b=1, and ax=by.

### Claim 16 (depends on 10)

The positive electrode of claim 10, wherein the composite positive active material is Li1.2Ni0.2Mn0.6O2, Li1.2Ni0.3Mn0.3O2, Li1.1Ni0.3Mn0.6O2, or a combination thereof.

### Claim 17 (depends on 10)

The positive electrode of claim 10, wherein the composite positive active material has a capacity of about 275 milliampere-hours per gram or greater.

### Claim 18 (depends on 10)

A lithium battery comprising:
the positive electrode of claim 10;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode.

### Claim 19

A method of preparing a composite positive active material, the method comprising:
mixing a precursor for forming a composite positive active material represented by Formula 1 to obtain a precursor mixture;
pulverizing the precursor mixture to obtain a pulverized product;
first thermally treating the pulverized product to obtain a first thermal treatment product; and
cooling the first thermal treatment product, wherein the cooling comprises cooling at a cooling rate of about 500° C. per minute to about 900° C. per minute,
LiaNibCOcMndMeO2 Formula 1
wherein, in Formula 1, M is zirconium, aluminum, rhenium, vanadium, chromium, iron, gallium, silicon, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum,
1.1≤a≤1.3, b+c+d+e≤1, 0≤b≤0.3, 0≤c≤0.3, 0<d≤0.6, and 0≤e≤0.1, and
wherein, through atomic interdiffusion of lithium and the metal, the composite positive active material has
a uniform distribution of lithium excess regions, and a uniform degree of disorder of metal cations, and
the metal cations have a mixed disordered, irregular arrangement at an atomic scale and a disordered cation structure,
a ratio of an intensity of a (003) peak to an intensity of a (104) peak is about 0.87 to about 1.11, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation, and
wherein a full width at half-maximum of a diffraction peak between 43º and 45° 2θ of the composite positive active material is about 0.2° to about 0.32°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

### Claim 20 (depends on 19)

The method of claim 19, wherein the first thermally treating comprises contacting with an oxidizing gas at a temperature of about 900° C. or greater.

### Claim 21 (depends on 20)

The method of claim 20, further comprising second thermally treating the precursor mixture before the pulverizing of the precursor mixture.

### Claim 22 (depends on 21)

The method of claim 21, wherein the second thermally treating comprises contacting with an oxidizing gas at a temperature of about 700° C. or greater.

### Claim 23 (depends on 19)

The method of claim 19, wherein the first thermally treating comprises contacting with an oxidizing gas at a temperature of about 900° ° C. to about 1100° C.

### Claim 24 (depends on 19)

The method of claim 19, wherein the cooling comprises cooling from a temperature of about 900° C. or greater.

### Claim 25 (depends on 19)

The method of claim 19, wherein the pulverizing comprises ball milling, water milling, air-jet milling, or roller milling.

### Claim 26 (depends on 19)

The method of claim 19, wherein the pulverized product has a D50 particle size of about 1 micrometer or less, when determined by light scattering.

### Claim 27 (depends on 19)

The method of claim 19, wherein the precursor mixture comprises a lithium precursor, a nickel precursor, and a manganese precursor, and
the mixing of the precursors comprises adding the lithium precursor to a mixture of the nickel precursor and the manganese precursor to obtain the precursor mixture.

### Claim 28 (depends on 19)

The method of claim 19, wherein the precursor mixture comprises a lithium precursor, a nickel precursor, and a manganese precursor, and
the mixing of the precursors comprises simultaneously adding and mixing the lithium precursor, the nickel precursor, and the manganese precursor to obtain the precursor mixture.

### Claim 29 (depends on 19)

The method of claim 19, wherein the mixing of the precursors comprises mechanical milling.

### Claim 30 (depends on 19)

The method of claim 19, further comprising, before the first thermally treating of the pulverized product, the method comprises drying the pulverized product at a temperature of about 100° C. or less to obtain a dried product, and
pelletizing the dried product.