Cathode active material, cathode and lithium battery including cathode active material, and method of preparing the cathode active material

Patent metadata

Field	Value
Publication number	US-9620771-B2
Application number	US-201313954280-A
Country	US
Kind code	B2
Filing date	Jul 30, 2013
Priority date	Jan 7, 2013
Publication date	Apr 11, 2017
Grant date	Apr 11, 2017

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 [Li 2-y (M1) 1-z (M2) y+z O 3 ]-(1− x )[LiMeO 2 ]  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).

First claim

What is claimed is:

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 [Li 2-y (M1) 1-z (M2) y+z O 3 ]-(1 −x )[LiMeO 2 ]  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).

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

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

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

5. 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.

6. 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.

7. 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.

8. 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.

9. The cathode active material of claim 1 , wherein the first domain is represented by Formula 2:
Li 2-y (M1) 1-z (M2) y+z O 3   Formula 2

wherein the second domain is represented by Formula 3:
LiMeO 2 .  Formula 3

10. 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 .

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

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 [Li 2-y (M1) 1-z (M2) y+z O 3 ]-(1 −x )[LiMeO 2 ]  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).

13. 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 Li 2 CO 3 , LiOH, Li(CO 2 ) 2 , LiCl, LiOCO 2 CH 3 , and LiF.

14. The method of claim 12 , wherein the transition metal precursor comprises at least one selected from MnCO 3 , Mn(SO 4 ) 2 , Mn(NO 3 ) 2 , MnCl 2 , MnBr 2 , (CH 3 CO 2 ) 2 Mn, NiCO 3 , NiSO 4 , NiNO 3 , NiCl 2 , NiBr 2 , (CH 3 CO 2 ) 2 Ni, CoCO 3 , CoSO 4 , Co(NO 3 ) 2 , CoCl 2 , CoBr 2 , (CH 3 CO 2 ) 2 Co, FeCO 3 , FeSO 4 , Fe(NO 3 ) 2 , Fe(NO 3 ) 3 , FeCl 2 , FeCl 3 , FeBr 2 , FeBr 3 , (CH 3 CO 2 ) 2 Fe, CrCO 3 , Cr(SO 4 ) 2 , Cr(NO 3 ) 2 , CrCl 2 , CrBr 2 , (CH 3 CO 2 ) 2 Cr, and a hydrate thereof.

15. The method of claim 12 , wherein the metal dopant precursor comprises at least one selected from Al 2 O 3 , MgO, V 2 O 5 , VO 2 , V 2 O 3 , VO, ZnO, MoO 3 , Nb 2 O 3 , La 2 O 3 , and RuO 2 .

16. 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.

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

18. The method of claim 12 , wherein the metal precursor comprises at least one selected from NiCO 3 , Ni(SO 4 ) 2 , Ni(NO 3 ) 2 , NiCl 2 , NiBr 2 , (CH 3 CO 2 ) 2 Ni, MnCO 3 , Mn(SO 4 ) 2 , Mn(NO 3 ) 2 , MnCl 2 , MnBr 2 , (CH 3 CO 2 ) 2 Mn, CoCO 3 , Co(SO 4 ) 2 , Co(NO 3 ) 2 , CoCl 2 , CoBr 2 , (CH 3 CO 2 ) 2 Co, FeCO 3 , FeSO 4 , Fe(NO 3 ) 2 , Fe(NO 3 ) 3 , FeCl 2 , FeCl 3 , FeBr 2 , FeBr 3 , (CH 3 CO 2 ) 2 Fe, CrCO 3 , Cr(SO 4 ) 2 , Cr(NO 3 ) 2 , CrCl 2 , CrBr 2 , (CH 3 CO 2 ) 2 Cr, TiCO 3 , Ti(SO 4 ) 2 , Ti(NO 3 ) 2 , TiCl 2 , TiBr 2 , CuCO 3 , CuSO 4 , Cu(NO 3 ) 2 , CuCl 2 , CuBr 2 , (CH 3 CO 2 ) 2 Cu, AICO 3 , Al(SO 4 ) 3 , Al(NO 3 ) 3 , AlCl 3 , AlBr 3 , (CH 3 CO 2 ) 3 Al, MgCO 3 , MgSO 4 , Mg(NO 3 ) 2 , MgCl, MgBr, (CH 3 CO 2 ) 2 Mg, Zr(CO 3 ) 2 , Zr(SO 4 ) 2 , Zr(NO 3 ) 2 , ZrCl 4 , ZrBr 4 , B 2 (CO 3 ) 3 , B 2 (SO 4 ) 3 , B(NO 3 ) 3 , BCl 3 , BBr 3 , and a hydrate thereof.

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

20. 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.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Kim Myung-Hoon
• Yoon Jae-Gu
• Park Min-Sik
• Park Jin-Hwan

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/364 Primary

  as mixtures · CPC title

• C01P2004/80

  Particles consisting of a mixture of two or more inorganic phases · CPC title

• H01M4/505 Primary

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• C01P2006/40

  Electric properties · CPC title