# US 12,015,152 B2 · Positive electrode active material, manufacturing method thereof, and positive electrode for lithium secondary battery comprising the same

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- Number: US 12,015,152 B2
- Document ID: US12015152B2
- Status: Granted
- Kind: B2
- Application number: 18/346,301
- Filed: 2023-07-03
- Published: 2024-04-18
- Granted: 2024-06-18
- Earliest claimed: 2022-10-12
- Assignees: SK On Co., Ltd.
- Applicants: SK On Co., Ltd.
- Inventors: Sang Han Lee; Sang Wook Lee; Byoung Beom Lim; Yong Hyun Cho
- Web page: https://patentgrep.com/patent/US12015152B2

## CPC

- C01G 53/42: containing alkali metals, e.g. LiNiO2
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/502: containing lithium and cobalt
- C01G 53/504: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
- C01G 53/506: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- 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
- C01P 2002/52: containing elements as dopants
- C01P 2002/60: Compounds characterised by their crystallite size
- C01P 2002/74: by peak-intensities or a ratio thereof only
- C01P 2006/40: Electric properties
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0025: Organic electrolyte
- Y02E 60/10: Energy storage using batteries
- 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)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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

A positive electrode active material may include a lithium layer doped with a first doping element and a transition metal layer doped with a second doping element. An I(003)/I(006) peak intensity ratio in X-ray diffraction measurement is equal to or less than 23.8.

## Claims

### Claim 1

A positive electrode active material comprising a lithium layer doped with a first doping element and a transition metal layer doped with a second doping element, wherein an I(003)/I(006) peak intensity ratio in X-ray diffraction measurement is equal to or less than 23.8,
wherein the first doping element is one or more elements selected from the group consisting of Mg, V, Cr, Cu, Zn, and Ge, and wherein the second doping element is one or more elements selected from the group consisting of Ti, Fe, As, Zr, Al, Nb, Mo, Tc, Ru, Rh, Pd, V, and Te,
wherein the first doping element and the second doping element are an element having a hexacoordinate structure,
wherein the first doping element has an oxidation number of +1 to +2, and
wherein the second doping element has an oxidation number of +2 to +4 and wherein the positive electrode active material has a crystal grain size of 250 nm to 1000 nm.

### Claim 2 (depends on 1)

The positive electrode active material according to claim 1, wherein the first doping element has an effective ion radius larger than that of the second doping element.

### Claim 3 (depends on 2)

The positive electrode active material according to claim 2, wherein the first doping element has an effective ion radius of 60 pm to 80 pm.

### Claim 4 (depends on 2)

The positive electrode active material according to claim 2, wherein the second doping element has an effective ion radius of 30 pm to 70 pm.

### Claim 5 (depends on 1)

The positive electrode active material according to claim 1 is a positive electrode active material represented by Formula 1:
Lix-aM1aNi1-y-bM2yM3bO2+z [Formula 1]
wherein in Formula 1, M1 is the first doping element, M2 is the second doping element, and M3 is one or more elements selected from the group consisting of Mn, Co, and Al, and 0.9≤x-a≤1.1, y is 0≤y+b≤0.7, and z is −0.1≤z≤0.1.

### Claim 6 (depends on 5)

The positive electrode active material according to claim 5, wherein the positive electrode active material has a discharge capacity of 140+0.738×WNi or more (WNi refers to the mass percentage of nickel in a positive electrode active material).

### Claim 7 (depends on 1)

The positive electrode active material according to claim 1, wherein the positive electrode active material is a single particle.

### Claim 8

A manufacturing method of a positive electrode active material, comprising the steps of:
mixing a lithium compound, a transition metal compound, a compound comprising a first doping element doped into lithium, and a compound comprising a second doping element doped into a transition metal; and
calcining a mixture obtained in the mixing such that an I(003)/I(006) peak intensity ratio in X-ray diffraction measurement of a final product is equal to or less than 23.8,
wherein the first doping element is one or more elements selected from the group consisting of Mg, V, Cr, Cu, Zn, and Ge, and wherein the second doping element is one or more elements selected from the group consisting of Ti, Fe, As, Zr, Al, Nb, Mo, Tc, Ru, Rh, Pd, V, and Te,
wherein the first doping element and the second doping element are an element having a hexacoordinate structure,
wherein the first doping element has an oxidation number of +1 to +2, and
wherein the second doping element has an oxidation number of +2 to +4and wherein the positive electrode active material has a crystal grain size of 250 nm to 1000 nm.

### Claim 9

A positive electrode for lithium secondary batteries, comprising:
a positive electrode current collector; and
a positive electrode active material layer disposed on the positive electrode current collector,
wherein the positive electrode active material layer comprises a lithium layer doped with a first doping element and a transition metal layer doped with a second doping element; and a positive electrode active material of which an I(003)/I(006) peak intensity ratio in X-ray diffraction measurement is equal to or less than 23.8,
wherein the first doping element is one or more elements selected from the group consisting of Mg, V, Cr, Cu, Zn, and Ge, and wherein the second doping element is one or more elements selected from the group consisting of Ti, Fe, As, Zr, Al, Nb, Mo, Tc, Ru, Rh, Pd, V, and Te,
wherein the first doping element and the second doping element are an element having a hexacoordinate structure,
wherein the first doping element has an oxidation number of +1 to +2, and
wherein the second doping element has an oxidation number of +2 to +4 and wherein the positive electrode active material has a crystal grain size of 250 nm to 1000 nm.