# US 2014/0193714 A1 · Cathode active material, cathode and lithium battery including cathode active material, and method of preparing the cathode active material

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- Number: US 2014/0193714 A1
- Document ID: US20140193714A1
- Status: Published application
- Kind: A1
- Application number: 13/954,280
- Filed: 2013-07-30
- Published: 2014-07-10
- Earliest claimed: 2013-01-07
- Assignees: Samsung Fine Chemicals Co., Ltd.; Samsung SDI Co., Ltd.
- Applicants: Samsung Fine Chemicals Co., Ltd.; Samsung SDI Co., Ltd.
- Inventors: Myung-hoon KIM; Jae-gu YOON; Min-sik PARK; Jin-hwan PARK
- Web page: https://patentgrep.com/patent/US20140193714A1

## CPC

- H01M 4/364: {as mixtures}
- C01G 53/50: of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
- C01G 53/502: containing lithium and cobalt
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 45/1257: containing lithium, e.g. Li2MnO3 or Li2(MxMn1-x)O3
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/40: Electric properties
- 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 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 10/052: Li-accumulators
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. 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
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

A cathode active material including a lithium metal oxide composite having a first domain and a second domain and represented by Formula 1: x[Li2-y(M1)1-z(M2)y+zO3]-(1−x)[LiMeO2] Formula 1 wherein 0<x<1, 0≦y<1, 0≦z<1, 0<y+z<1, M1 includes at least one transition metal, M2 includes at least one metal selected from magnesium (Mg), aluminum (Al), vanadium (V), zinc (Zn), molybdenum (Mo), niobium (Nb), lanthanum (La), and ruthenium (Ru), and Me includes at least one metal selected from nickel (Ni), cobalt (Co), manganese (Mn), iron (Fe), chromium (Cr), titanium (Ti), copper (Cu), aluminum (Al), magnesium (Mg), zirconium (Zr), and boron (B).

## Claims

### Claim 1

A cathode active material comprising:
a lithium metal oxide composite comprising a first domain and a second domain and represented by Formula 1:
x[Li2-y(M1)1-z(M2)y+zO3]-(1−x)[LiMeO2] Formula 1
wherein
0<x<1,
0≦y<1,
0≦z<1,
0<y+z<1,
M1 comprises at least one transition metal,
M2 comprises at least one metal selected from magnesium (Mg), aluminum (Al), vanadium (V), zinc (Zn), molybdenum (Mo), niobium (Nb), lanthanum (La), and ruthenium (Ru), and
Me comprises at least one metal selected from nickel (Ni), cobalt (Co), manganese (Mn), iron (Fe), chromium (Cr), titanium (Ti), copper (Cu), aluminum (Al), magnesium (Mg), zirconium (Zr), and boron (B).

### Claim 2 (depends on 1)

The cathode active material of claim 1, wherein a range of y in Formula 1 is 0≦y<0.5.

### Claim 3 (depends on 1)

The cathode active material of claim 1, wherein a range of z in Formula 1 is 0≦z<0.5.

### Claim 4 (depends on 1)

The cathode active material of claim 1, wherein M1 is Mn.

### Claim 5 (depends on 1)

The cathode active material of claim 1, wherein the lithium metal oxide composite comprises a domain having a crystal structure in which a lattice constant c of a length of a c-axis is 14.24 Angstroms or greater.

### Claim 6 (depends on 1)

The cathode active material of claim 1, wherein a ratio of a peak intensity of a primary peak corresponding to a 003 plane to a peak intensity of a secondary peak corresponding to a 104 plane in an X-ray diffraction spectrum of the lithium metal oxide is 1.3 or greater.

### Claim 7 (depends on 1)

The cathode active material of claim 1, wherein a particle size of crystalline particles of the lithium metal oxide composite, when determined by analysis of a full width at half maximum of a peak corresponding to an 003 plane in an X-ray diffraction spectrum, is 80 nanometers or greater.

### Claim 8 (depends on 1)

The cathode active material of claim 1, wherein a separation distance between a peak corresponding to a 108 plane having a scattering angle of about 64.5°±0.5° two-theta and a peak corresponding to a 110 plane having a scattering angle of about 65.5°±0.5° two-theta in an X-ray diffraction spectrum of the lithium metal oxide composite is 0.8° or greater.

### Claim 9 (depends on 1)

The cathode active material of claim 1, wherein the first domain is represented by Formula 2:
Li2-y(M1)1-z(M2)y+zO3 Formula 2
and
wherein the second domain is represented by Formula 3:
LiMeO2. Formula 3

### Claim 10 (depends on 1)

A lithium battery comprising:
a cathode;
an anode; and
an electrolyte disposed between the cathode and the anode;
wherein the cathode comprises the cathode active material of claim 1.

### Claim 11 (depends on 10)

The lithium battery of claim 10, wherein an operational voltage of the cathode active material is 4.3 Volts or greater.

### Claim 12

A method of preparing a lithium metal oxide composite comprising a first domain and a second domain, the method comprising:
contacting a first lithium precursor, a transition metal precursor, and a metal dopant precursor to prepare a first mixture;
firstly heat treating the first mixture to prepare a first domain lithium metal oxide;
contacting the first domain lithium metal oxide with a second lithium precursor and a metal precursor to prepare a second mixture; and
secondly heat treating the second mixture to prepare a second domain lithium metal oxide to prepare the lithium metal oxide composite,
wherein the lithium metal oxide composite is represented by Formula 1:
x[Li2-y(M1)1-z(M2)y+zO3]-(1−x)[LiMeO2] Formula 1
wherein
0<x<1,
0≦y<1,
0≦z<1,
0<y+z<1,
M1 comprises at least one transition metal,
M2 comprises at least one metal selected from magnesium (Mg), aluminum (Al), vanadium (V), zinc (Zn), molybdenum (Mo), niobium (Nb), lanthanum (La), and ruthenium (Ru), and
Me comprises at least one metal selected from nickel (Ni), Cobalt (Co), manganese (Mn), iron (Fe), chromium (Cr), titanium (Ti), copper (Cu), aluminum (Al), magnesium (Mg), zirconium (Zr), and boron (B).

### Claim 13 (depends on 12)

The method of claim 12, wherein the first lithium precursor and the second lithium precursor each independently comprise at least one lithium salt selected from Li2CO3, LiOH, Li(CO2)2, LiCl, LiOCO2CH3, and LiF.

### Claim 14 (depends on 12)

The method of claim 12, wherein the transition metal precursor comprises at least one selected from MnCO3, Mn(SO4)2, Mn(NO3)2, MnCl2, MnBr2, (CH3CO2)2Mn, NiCO3, NiSO4, NiNO3, NiCl2, NiBr2, (CH3CO2)2Ni, CoCO3, CoSO4, Co(NO3)2, CoCl2, CoBr2, (CH3CO2)2Co, FeCO3, FeSO4, Fe(NO3)2, Fe(NO3)3, FeCl2, FeCl3, FeBr2, FeBr3, (CH3CO2)2Fe, CrCO3, Cr(SO4)2, Cr(NO3)2, CrCl2, CrBr2, (CH3CO2)2Cr, and a hydrate thereof.

### Claim 15 (depends on 12)

The method of claim 12, wherein the metal dopant precursor comprises at least one selected from Al2O3, MgO, V2O5, VO2, V2O3, VO, ZnO, MoO3, Nb2O3, La2O3, and RuO2.

### Claim 16 (depends on 12)

The method of claim 12, wherein an amount of the metal dopant precursor is in a range of about 0.01 mole percent to about 0.5 mole percent, based on a total moles of the first lithium precursor and the transition metal precursor.

### Claim 17 (depends on 12)

The method of claim 12, wherein the first thermal treatment is performed at a temperature of about 400° C. to about 800° C.

### Claim 18 (depends on 12)

The method of claim 12, wherein the metal precursor comprises at least one selected from NiCO3, Ni(SO4)2, Ni(NO3)2, NiCl2, NiBr2, (CH3CO2)2Ni, MnCO3, Mn(SO4)2, Mn(NO3)2, MnCl2, MnBr2, (CH3CO2)2Mn, CoCO3, Co(SO4)2, Co(NO3)2, CoCl2, CoBr2, (CH3CO2)2Co, FeCO3, FeSO4, Fe(NO3)2, Fe(NO3)3, FeCl2, FeCl3, FeBr2, FeBr3, (CH3CO2)2Fe, CrCO3, Cr(SO4)2, Cr(NO3)2, CrCl2, CrBr2, (CH3CO2)2Cr, TiCO3, Ti(SO4)2, Ti(NO3)2, TiCl2, TiBr2, CuCO3, CuSO4, Cu(NO3)2, CuCl2, CuBr2, (CH3CO2)2Cu, AlCO3, Al(SO4)3, Al(NO3)3, AlCl3, AlBr3, (CH3CO2)3Al, MgCO3, MgSO4, Mg(NO3)2, MgCl, MgBr, (CH3CO2)2Mg, Zr(CO3)2, Zr(SO4)2, Zr(NO3)2, ZrCl4, ZrBr4, B2(CO3)3, B2(SO4)3, B(NO3)3, BCl3, BBr3, and a hydrate thereof.

### Claim 19 (depends on 12)

The method of claim 12, wherein the second thermal treatment is performed at a temperature of about 700° C. to about 950° C.

### Claim 20 (depends on 12)

The method of claim 12, further comprising at least one selected from mechanically milling the first domain lithium metal oxide, and mechanically milling the lithium metal oxide composite represented by Formula 1.