# US 9,437,874 B2 · Active material for a lithium secondary battery, method of manufacturing the same, electrode including the active material, and lithium secondary battery including the electrode

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- Number: US 9,437,874 B2
- Document ID: US9437874B2
- Status: Granted
- Kind: B2
- Application number: 14/037,572
- Filed: 2013-09-26
- Published: 2014-12-18
- Granted: 2016-09-06
- Earliest claimed: 2013-06-18
- Assignees: Samsung SDI Co., Ltd.
- Applicants: Samsung SDI Co., Ltd.
- Inventors: Andrei Kapylou; Jay-Hyok Song; Evgeniya Matulevich; Chang-Wook Kim; Yong-Chan You; Sun-Ho Kang
- Web page: https://patentgrep.com/patent/US9437874B2

## CPC

- 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
- 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
- C01P 2002/50: Solid solutions
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2004/03: obtained by SEM
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/12: Surface area
- H01M 4/1315: containing halogen atoms, e.g. LiCoOxFy
- 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)
- 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

An active material for a lithium secondary battery, a method of manufacturing the same, an electrode including the active material, and a lithium secondary battery including the electrode, the active material including a lithium composite oxide represented by the following Formula 1: Li[LixNiaCobMnc]O2-yFy. [Formula 1]

## Claims

### Claim 1

An active material for a lithium secondary battery, the active material comprising a lithium composite oxide represented by the following Formula 1:
Li[LixNiaCobMnc]O2-yFy, [Formula 1]
wherein:
in Formula 1, x, a, b, c, and y satisfy the following relations: 0.05≦x≦0.3, 0.12≦a≦0.25, 0.00≦b≦0.25, 0.45≦c≦0.60, x+a+b+c=1.0, 1.25≦(1+x)/(a+b+c)≦1.6, and 0<y≦0.1, and
the lithium composite oxide has a full width at half maximum of a diffraction angle at a (003) surface of about 0.216° to about 0.219° in a powder X-ray diffraction spectrum obtained by using CuKα ray.

### Claim 2 (depends on 1)

The active material as claimed in claim 1, wherein the lithium composite oxide represented by Formula 1 is represented by the following Formula 1a:
Li[Li1/6Ni1/6Co1/6Mn1/2]O2-yFy, in which 0<y≦0.1. [Formula 1a]

### Claim 3 (depends on 1)

The active material as claimed in claim 1, wherein, in Formula 1, 0.02≦y≦0.06.

### Claim 4 (depends on 1)

The active material as claimed in claim 1, wherein the lithium composite oxide represented by Formula 1 is one of Li[Li1/6Ni1/6Co1/6Mn1/2]O1.96F0.04, Li[Li1/6Ni1/6Co1/6Mn1/2]O1.94F0.06, or Li[Li1/6Ni1/6Co1/6Mn1/2]O1.98F0.02.

### Claim 5 (depends on 1)

The active material as claimed in claim 1, wherein, in Formula 1, x, a, b, c, and y satisfy the following relations: 0.1≦x≦0.2, 0.17≦a≦0.21, 0.05≦b≦0.17, 0.50≦c≦0.55, 0.01≦y≦0.1.

### Claim 6

A method of manufacturing an active material for a lithium secondary battery, the method comprising:
mixing a fluorine-containing compound, a lithium compound, and a metal hydroxide represented by the following Formula 2:
NiaCobMnc(OH)2 [Formula 2]
wherein, in Formula 2, a, b, and c satisfy the following relations: 0.15≦a≦0.30, 0.0≦b≦0.30, 0.55≦c≦0.70, and a+b+c=1.0;
heat treating the mixture under an oxidizing atmosphere at a temperature of about 650° C. to about 850° C.; and
cooling the heat treated mixture at a cooling rate of about 0.1° C./min to about 2° C./min such that the active material includes a lithium composite oxide having a full width at half maximum of a diffraction angle at a (003) surface of about 0.216° to about 0.219° in a powder X-ray diffraction spectrum obtained by using CuKα ray.

### Claim 7 (depends on 6)

The method as claimed in claim 6, wherein the lithium composite oxide is represented by the following Formula 1:
Li[LixNiaCobMnc]O2-yFy, [Formula 1]
wherein, in Formula 1, x, a, b, c, and y satisfy the following relations: 0.05≦x≦0.3, 0.12≦a≦0.25, 0.00≦b≦0.25, 0.45≦c≦0.60, x+a+b+c=1.0, 1.25≦(1+x)/(a+b+c)≦1.6, and 0<y≦0.1.

### Claim 8 (depends on 6)

The method as claimed in claim 6, wherein the fluorine-containing compound includes LiF or NH4F.

### Claim 9 (depends on 6)

The method as claimed in claim 6, wherein the cooling is performed for about 350 to about 7,000 minutes.

### Claim 10 (depends on 6)

The method as claimed in claim 6, wherein the heat treating is performed at about 675° C. to about 750° C.

### Claim 11 (depends on 6)

The method as claimed in claim 6, wherein the heat treating is performed for about 1 to about 10 hours.

### Claim 12 (depends on 6)

The method as claimed in claim 6, wherein the oxidizing atmosphere includes:
about 10 to about 20 vol % of oxygen or air, and
about 80 to about 90 vol % of inert gas.

### Claim 13 (depends on 6)

The method as claimed in claim 6, wherein the metal hydroxide represented by Formula 2 includes one of Ni1/6Co1/6Mn1/2(OH)2 or Ni0.2Co0.2Mn0.6(OH)2.

### Claim 14 (depends on 7)

The method as claimed in claim 7, wherein the active material represented by Formula 1 is one of Li[Li1/6Ni1/6Co1/6Mn1/2]O1.96F0.04, Li[Li1/6Ni1/6Co1/6Mn1/2]O1.94F0.06, or Li[Li1/6Ni1/6Co1/6Mn1/2]O1.98F0.02.

### Claim 15 (depends on 1)

An electrode for a lithium secondary battery, the electrode comprising the active material as claimed in claim 1.

### Claim 16 (depends on 15)

A lithium secondary battery including the electrode as claimed in claim 15.

### Claim 17 (depends on 1)

The active material as claimed in claim 1, wherein the lithium composite oxide is prepared by:
mixing a fluorine-containing compound, a lithium compound, and a metal hydroxide represented by the following Formula 2:
NiaCobMnc(OH)2 [Formula 2]
wherein, in Formula 2, a, b, and c satisfy the following relations: 0.15≦a≦0.30, 0.0≦b≦0.30, 0.55≦c≦0.70, and a+b+c=1.0;
heat treating the mixture under an oxidizing atmosphere at a temperature of about 650° C. to about 850° C.; and
cooling the heat treated mixture at a cooling rate of about 0.1° C./min to about 2° C./min.