# US 2014/0154581 A1 · Cathode active material for lithium ion secondary battery

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- Number: US 2014/0154581 A1
- Document ID: US20140154581A1
- Status: Published application
- Kind: A1
- Application number: 14/173,032
- Filed: 2014-02-05
- Published: 2014-06-05
- Earliest claimed: 2011-08-05
- Assignees: Asahi Glass Company, Limited
- Applicants: Asahi Glass Company, Limited
- Inventors: Takeshi KAWASATO; Kentaro Tsunozaki; Haisheng Zeng; Yasuyuki Takimoto; Toshio Suzuki
- Web page: https://patentgrep.com/patent/US20140154581A1

## CPC

- H01M 4/366: {as layered products}
- B05D 1/02: performed by spraying
- B05D 3/0254: {After-treatment}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01G 53/502: containing lithium and cobalt
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- 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)
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/12: Surface area
- H01M 10/052: Li-accumulators
- 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
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- 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)
- 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

To provide a cathode active material for a lithium ion secondary battery excellent in the cycle characteristics and rate characteristics even when charging is conducted at a high voltage. A cathode active material for a lithium ion secondary battery, which comprises particles (III) having a covering layer comprising a metal oxide (I) containing at least one metal element selected from the group consisting of Al, Y, Ga, In, La, Pr, Nd, Gd, Dy, Er and Yb, and a compound (II) containing Li and at least one non-metal element selected from the group consisting of S and B, on the surface of a lithium-containing composite oxide, wherein the atomic ratio (the non-metal element/the metal element) contained within 5 nm of the surface layer of the particles (III) is within a specific range.

## Claims

### Claim 1

A cathode active material for a lithium ion secondary battery, which comprises particles (III) having a covering layer comprising a metal oxide (I) containing at least one metal element selected from the group consisting of Al, Y, Ga, In, La, Pr, Nd, Gd, Dy, Er and Yb, and a compound (II) containing Li and at least one non-metal element selected from the group consisting of S and B, on the surface of a lithium-containing composite oxide comprising lithium and a transition metal element, wherein the atomic ratio of the non-metal element to the metal element (i.e. the non-metal element/the metal element) contained within 5 nm of the surface layer of the particles (III) is from 0.10 to 0.25.

### Claim 2 (depends on 1)

The cathode active material for a lithium ion secondary battery according to claim 1, wherein the specific surface area of the particles (III) is at least 0.1 m2/g and less than 3 m2/g.

### Claim 3

A cathode active material for a lithium ion secondary battery, which comprises particles (III) having a covering layer comprising a metal oxide (I) containing at least one metal element selected from the group consisting of Al, Y, Ga, In, La, Pr, Nd, Gd, Dy, Er and Yb, and a compound (II) containing Li and at least one non-metal element selected from the group consisting of S and B, on the surface of a lithium-containing composite oxide comprising lithium and a transition metal element, wherein the atomic ratio of the non-metal element to the metal element (i.e. the non-metal element/the metal element) contained within 5 nm of the surface layer of the particles (III) is from 0.01 to 0.1, and the specific surface area of the particles (III) is at least 3 m2/g and at most 10 m2/g.

### Claim 4 (depends on 1)

The cathode active material for a lithium ion secondary battery according to claim 1, wherein the metal element is at least one member selected from the group consisting of Al, Y, Ga, La, Gd and Er.

### Claim 5 (depends on 3)

The cathode active material for a lithium ion secondary battery according to claim 3, wherein the metal element is at least one member selected from the group consisting of Al, Y, Ga, La, Gd and Er.

### Claim 6 (depends on 1)

The cathode active material for a lithium ion secondary battery according to claim 1, wherein the compound (II) contains at least one member selected from the group consisting of Li2SO4 and Li2SO4.H2O.

### Claim 7 (depends on 3)

The cathode active material for a lithium ion secondary battery according to claim 3, wherein the compound (II) contains at least one member selected from the group consisting of Li2SO4 and Li2SO4.H2O.

### Claim 8 (depends on 1)

The cathode active material for a lithium ion secondary battery according to claim 1, wherein the value of the molar ratio of the metal element to the lithium-containing composite oxide is from 0.001 to 0.03.

### Claim 9 (depends on 3)

The cathode active material for a lithium ion secondary battery according to claim 3, wherein the value of the molar ratio of the metal element to the lithium-containing composite oxide is from 0.001 to 0.03.

### Claim 10 (depends on 1)

A cathode for a lithium ion secondary battery comprising the cathode active material for a lithium ion secondary battery as defined in claim 1, and a binder.

### Claim 11 (depends on 3)

A cathode for a lithium ion secondary battery comprising the cathode active material for a lithium ion secondary battery as defined in claim 3, and a binder.

### Claim 12 (depends on 10)

A lithium ion secondary battery comprising the cathode as defined in claim 10, an anode and a non-aqueous electrolyte.

### Claim 13 (depends on 11)

A lithium ion secondary battery comprising the cathode as defined in claim 11, an anode and a non-aqueous electrolyte.

### Claim 14

A process for producing a cathode active material for a lithium ion secondary battery, which comprises:
a first contact step of contacting a powder of a lithium-containing composite oxide comprising lithium and a transition metal element, and a first aqueous solution which contains a cation (p) having at least one metal element selected from the group consisting of Al, Y, Ga, In, La, Pr, Nd, Gd, Dy, Er and Yb and which does not contain an anion (n) having at least one non-metal element selected from the group consisting of S and B,
a second contact step of contacting said powder of the lithium-containing composite oxide, and a second aqueous solution which contains said anion (n) (provided that the second aqueous solution may or may not contain said cation (p)), and
a heating step of heating, after the first and second contact steps, the obtained treated powder of the lithium-containing composite oxide to a temperature of from 250 to 700° C., wherein
in the entire aqueous solution having the first and second aqueous solutions put together, |(number of moles of said anion contained in said second aqueous solution×valency of said anion)|/((number of moles of said cation contained in said first aqueous solution×valency of said cation)+(number of moles of said cation contained in said second aqueous solution×valency of said cation)) is less than 1.

### Claim 15 (depends on 14)

The process for producing a cathode active material for a lithium ion secondary battery according to claim 14, wherein the first contact step and the second contact step are the same step.

### Claim 16 (depends on 14)

The process for producing a cathode active material for a lithium ion secondary battery according to claim 14, wherein said cation (p) contains at least one member selected from the group consisting of Al3+, Y3+, Ga3+, La3+, Gd3+ and Er3+, and said anion (n) contains SO42− or BO33−.

### Claim 17 (depends on 14)

The process for producing a cathode active material for a lithium ion secondary battery according to claim 14, wherein the solvent in the aqueous solutions is water only.

### Claim 18 (depends on 14)

The process for producing a cathode active material for a lithium ion secondary battery according to claim 14, wherein in each contact step, the aqueous solution is applied by spray coating to the powder of the lithium-containing composite oxide.