Active material for a lithium secondary battery, method of manufacturing the same, electrode including the active material, and lithium secondary battery including the electrode

Patent metadata

Field	Value
Publication number	US-9437874-B2
Application number	US-201314037572-A
Country	US
Kind code	B2
Filing date	Sep 26, 2013
Priority date	Jun 18, 2013
Publication date	Sep 6, 2016
Grant date	Sep 6, 2016

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[Li x Ni a Co b Mn c ]O 2-y F y .  [Formula 1]

First claim

What is claimed is:

1. An active material for a lithium secondary battery, the active material comprising a lithium composite oxide represented by the following Formula 1:
Li[Li x Ni a Co b Mn c ]O 2-y F y ,  [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.

2. 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[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 2-y F y , in which 0<y≦0.1.  [Formula 1a]

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

4. The active material as claimed in claim 1 , wherein the lithium composite oxide represented by Formula 1 is one of Li[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 1.96 F 0.04 , Li[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 1.94 F 0.06 , or Li[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 1.98 F 0.02 .

5. 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.

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:
Ni a Co b Mn c (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.

7. The method as claimed in claim 6 , wherein the lithium composite oxide is represented by the following Formula 1:
Li[Li x Ni a Co b Mn c ]O 2-y F y ,  [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.

8. The method as claimed in claim 6 , wherein the fluorine-containing compound includes LiF or NH 4 F.

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

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

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

12. 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.

13. The method as claimed in claim 6 , wherein the metal hydroxide represented by Formula 2 includes one of Ni 1/6 Co 1/6 Mn 1/2 (OH) 2 or Ni 0.2 Co 0.2 Mn 0.6 (OH) 2 .

14. The method as claimed in claim 7 , wherein the active material represented by Formula 1 is one of Li[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 1.96 F 0.04 , Li[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 1.94 F 0.06 , or Li[Li 1/6 Ni 1/6 Co 1/6 Mn 1/2 ]O 1.98 F 0.02 .

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

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

17. 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:
Ni a Co b Mn c (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.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Kapylou Andrei
• Song Jay-Hyok
• Matulevich Evgeniya
• Kim Chang-Wook
• You Yong-Chan
• Kang Sun-Ho

Classifications

• H01M4/505 Primary

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

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• C01P2002/54

  one element only · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2002/50

  Solid solutions · CPC title