# US 11,909,030 B2 · Lithium secondary battery

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- Number: US 11,909,030 B2
- Document ID: US11909030B2
- Status: Granted
- Kind: B2
- Application number: 17/540,052
- Filed: 2021-12-01
- Published: 2022-03-24
- Granted: 2024-02-20
- Earliest claimed: 2018-07-06
- Assignees: SK On Co., Ltd.
- Applicants: SK Innovation Co., Ltd.
- Inventors: Min Gu Kang; Soo Ho Kim; Young Hoon Do; Yong Hyun Cho
- Web page: https://patentgrep.com/patent/US11909030B2

## CPC

- 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 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- 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 4/621: {Binders}
- H01M 4/66: Selection of materials
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- H01M 10/052: Li-accumulators
- H01M 50/489: Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- 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 lithium secondary battery includes a cathode formed from a cathode active material including a first cathode active material particle and a second cathode active material particle, an anode and a separation layer interposed between the cathode and the anode. The first cathode active material particle includes a lithium metal oxide in which at least one metal forms a concentration gradient. The second cathode active material particle includes primary particles having different shapes or crystalline structures from each other.

## Claims

### Claim 1

A cathode active material for a lithium secondary battery, comprising:
a first cathode active material particle represented by the following Chemical Formula 1;
LixM1aM2bM3cOy [Chemical Formula 1]
wherein in Chemical Formula 1, M1, M2 and M3 independently include at least one element selected from a group consisting of Ni, Co, Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga and B,
0<x≤1.1, 1.98≤y≤2.02, 0.6≤a≤0.95 and 0.05≤b+c≤0.4, and
a second cathode active material particle represented by the following Chemical Formula 2 or Formula 3;
LixNiaCobMncM4dM5eOy [Chemical Formula 2]
wherein in Chemical Formula 2, M4 includes at least one element selected from a group consisting of Ti, Zr, Al, Mg, and Cr; and M5 includes at least one element selected from a group consisting of Sr, Y, W, and Mo; and
0<x<1.5, 1.98≤y≤2.02, 0.313≤a≤0.353, 0.313≤b≤0.353, 0.313≤c≤0.353, 0≤d≤0.03, 0≤e≤0.03, and 0.98≤a+b+c≤1.02,
LixNiαCoβMnγM4δM5εOy [Chemical Formula 3]
wherein in Chemical Formula 3, M4 includes at least one element selected from a group consisting of Ti, Zr, Al, Mg, and Cr; and M5 includes at least one element selected from a group consisting of Sr, Y, W, and Mo; and
0<x<1.1, 1.98≤y≤2.02, 0.48≤α≤0.52 0.18<β≤0.27, 0.24≤γ≤0.32, 0≤δ≤0.03, 0≤ε≤0.03, and 0.98≤α+β+γ≤1.02,
wherein metal elements except for lithium included in the second cathode active material particle do not have a concentration gradient region between a central portion of the second cathode active material particle and a surface of second cathode active material particle,
wherein the second cathode active material particle includes primary particles being aggregated with each other, the primary particles having different shapes or crystalline structures from each other,
wherein the different shapes include a first shape including a granular shape or a spherical shape and a second shape including a rod shape or a needle shape,
wherein the second cathode active material particle includes a first particle arranged in a central region and a second particle arranged in a peripheral region, and the first particle and the second particle have the different shapes or crystalline structures from each other.

### Claim 2 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1,
wherein the first particle has the granular shape or the spherical shape, and the second particle has the rod shape or the needle shape.

### Claim 3 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein the central region of the second cathode active material particle includes an area within a region corresponding to 20% to 80% of a radius from a center of the second cathode active material particle.

### Claim 4 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein the first cathode active material particle includes a core portion, a shell portion, and a concentration gradient region between the core portion and the shell portion.

### Claim 5 (depends on 4)

The cathode active material for a lithium secondary battery according to claim 4, wherein the core portion and the shell portion each includes a fixed composition.

### Claim 6 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein the first cathode active material particle includes a continuous concentration gradient region formed from a center of the first cathode active material particle to a surface of the first cathode active material particle.

### Claim 7 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein 0.7≤a≤0.9 and 0.1≤b+c≤0.3 in the Chemical Formula 1.

### Claim 8 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1,
wherein M1 is nickel (Ni), M2 is manganese (Mn), and M3 is cobalt (Co).

### Claim 9 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein 0.49≤α≤0.51 0.18≤β≤0.22, and 0.28≤γ≤0.32 in the Chemical Formula 3.

### Claim 10 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein a blending weight ratio of the first cathode active material particle and the second cathode active material particle is in a range from 9:1 to 1:9.

### Claim 11 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein an exothermic peak of the second cathode active material particle is 40 J/g or less at 200° C. or more in a Differential Scanning Calorimetry (DSC) measurement.

### Claim 12 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein the first cathode active material particle or the second cathode active material particle further includes a coating on a surface thereof, and the coating includes at least one selected from a group consisting of Al, Ti, Ba, Zr, Si, B, Mg, P, an alloy thereof and an oxide thereof.

### Claim 13 (depends on 1)

The cathode active material for a lithium secondary battery according to claim 1, wherein the first cathode active material particle or the second cathode active material particle further includes a dopant including at least one selected from a group consisting of Al, Ti, Ba, Zr, Si, B, Mg, P, an alloy thereof and an oxide thereof.