Composite cathode active material, cathode and lithium battery including the same, and method of preparing the composite cathode active material

Patent metadata

Field	Value
Publication number	US-2019006669-A1
Application number	US-201815860901-A
Country	US
Kind code	A1
Filing date	Jan 3, 2018
Priority date	Jun 30, 2017
Publication date	Jan 3, 2019
Grant date	—

Abstract

A composite cathode active material and a cathode and a lithium battery including the composite cathode active material. The composite cathode active material has a core including a plurality of primary particles including a nickel-containing first lithium transition metal oxide having a layered crystal structure; a grain boundary disposed between adjacent primary particles of the plurality of primary particles; and a shell on the core, the shell including a second lithium transition metal oxide having a spinel crystal structure, wherein the grain boundary includes a first composition having a spinel crystal structure.

First claim

What is claimed is:

1 . A composite cathode active material comprising:
a core comprising
a plurality of primary particles comprising a nickel-containing first lithium transition metal oxide having a layered crystal structure, and
a grain boundary between adjacent primary particles of the plurality of primary particles; and
a shell on the core, the shell comprising a second lithium transition metal oxide having a spinel crystal structure, wherein the grain boundary comprises a first composition having a spinel crystal structure.

2 . The composite cathode active material of claim 1 , wherein the first composition comprises at least one transition metal other than nickel, and
wherein a concentration of the at least one transition metal other than nickel in the grain boundary is greater than a concentration of the at least one transition metal other than nickel within the plurality of primary particles.

3 . The composite cathode active material of claim 2 , wherein the least one transition metal other than nickel comprises Mn, Co, Fe, or a combination thereof.

4 . The composite cathode active material of claim 1 , wherein at least 50% of the grain boundaries between the adjacent primary particles of the core comprise the first composition.

5 . The composite cathode active material of claim 1 , wherein the grain boundary is substantially rectilinear in cross-section within the core.

6 . The composite cathode active material of claim 1 , wherein the grain boundary is arranged in a direction which is parallel to a surface of an adjacent primary particle of the adjacent primary particles, and
wherein the direction of the grain boundary is different from a direction of a tangent of a nearest surface of the core.

7 . The composite cathode active material of claim 1 , wherein the core comprises a first grain boundary and a second grain boundary,
wherein the first grain boundary and the second grain boundary are located directly on a same primary particle of the plurality of primary particles, and wherein the first grain boundary and the second grain boundary intersect at an angle determined by a shape of the primary particle.

8 . The composite cathode active material of claim 1 , wherein the core comprises a plurality of grain boundaries that are adjacent to the plurality of primary particles,
wherein the plurality of grain boundaries are each arranged in a direction parallel to a surface of an adjacent primary particle, and wherein grain boundaries of the plurality of grain boundaries are arranged in different directions than each other.

9 . The composite cathode active material of claim 1 , wherein a plurality of grain boundaries have an average length in a range of about 50 nanometers to about 1000 nanometers and an average thickness in a range of about 1 nanometers to about 200 nanometers,
wherein a direction of the length is parallel to a surface of an adjacent primary particle, and wherein a direction of the thickness is perpendicular to the surface of the adjacent primary particle.

10 . The composite cathode active material of claim 1 , wherein the first composition comprises about 0.1 mole to about 1.3 mole of lithium, based on 1 mole of the first composition,
about 1.7 mole to about 2.3 mole of a transition metal, based on 1 mole of the first composition, and about 3.7 mole to about 4.3 mole of oxygen, based on 1 mole of the first composition.

11 . The composite cathode active material of claim 1 , wherein the first composition is the same as the second lithium transition metal oxide.

12 . The composite cathode active material of claim 1 , wherein the spinel crystal structure has cubic symmetry.

13 . The composite cathode active material of claim 12 , wherein the spinel crystal structure belongs to an Fd 3 m space group.

14 . The composite cathode active material of claim 1 , wherein the grain boundary further comprises a second composition, and wherein the second composition comprises a lithium transition metal oxide, a lithium-free transition metal oxide, or a combination thereof.

15 . The composite cathode active material of claim 14 , wherein the second composition has an amorphous structure, a layered structure, a spinel structure, a polyvalent anion crystal structure, or a combination thereof.

16 . The composite cathode active material of claim 1 , wherein the first lithium transition metal oxide comprises about 0.1 mole to about 1.3 mole of lithium, about 0.7 mole to about 0.99 mole of nickel, about 0.01 mole to about 0.3 mole of a transition metal other than nickel, and about 1.7 mole to about 2.3 mole of oxygen, based on 1 mole of the first lithium transition metal oxide.

17 . The composite cathode active material of claim 1 , wherein the first lithium transition metal oxide is represented by Formula 1:
Li a MO 2   Formula 1
wherein, in Formula 1, M comprises nickel and at least one non-nickel Group 4 to Group 13 element, an amount of nickel is in a range of about 70 mole percent to less than about 100 mol percent, based on a total content of M, and
0.9≤ a≤ 1.1.

18 . The composite cathode active material of claim 1 , wherein the first lithium transition metal oxide is represented by Formula 2:
Li a Ni b M1 c M2 d M3 e O 2   Formula 2
wherein, in Formula 2, M1, M2, and M3 are different and each independently comprises manganese, vanadium, chromium, iron, cobalt, zirconium, rhenium, aluminum, boron, germanium, ruthenium, tin, titanium, niobium, molybdenum, or platinum; and
0.9≤ a≤ 1.1,0.7< b< 1.0,0< c< 0.3,0< d< 0.3,0≤ e< 0.1, and b+c+d+e= 1.

19 . The composite cathode active material of claim 1 , wherein the first lithium transition metal oxide is represented by Formula 3:
Li a Ni b CO c Mn d M3′ e O 2   Formula 3
wherein, in Formula 3, M3′ comprises vanadium, chromium, iron, zirconium, rhenium, aluminum, boron, germanium, ruthenium, tin, titanium, niobium, molybdenum, or platinum,
0.9≤ a≤ 1.1,0.7< b< 1.0,0< c< 0.3,0< d< 0.3,0≤ e< 0.1, and b+c+d+e= 1.

20 . The composite cathode active material of claim 1 , wherein the first lithium transition metal oxide is represented by Formula 4c:
a Li 2 MnO 3- (1 −a )LiM″O 2   Formula 4c
wherein, in Formula 4c, M″ comprises nickel and cobalt, manganese, vanadium, chromium, iron, zirconium, rhenium, aluminum, boron, germanium, ruthenium, tin, titanium, niobium, molybdenum, platinum, or a combination thereof, and
0< a< 1.

21 . The composite cathode active material of claim 1 , wherein the second lithium transition metal oxide is represented by Formula 5:
Li b M′ 2 O 4   Formula 5
wherein, in Formula 5, M comprises manganese and at least one non-manganese Group 4 to Group 13 element, and
1.0≤ b≤ 1.1.

22 . The composite cathode active material of claim 1 , wherein the second lithium transition metal oxide is represented by Formula 6:
Li a Mn b M4 c M5 d O 4   Formula 6
wherein, in Formula 6, M4 and M5 are different and each independently comprises cobalt, nickel, vanadium, chromium, iron, zirconium, rhenium, aluminum, boron, germanium, ruthenium, tin, titanium, niobium, molybdenum, or platinum,
0.9≤ a ≤1.1,0< b≤ 2.0,0≤ c< 2.0,0≤ d< 0.1, and b+c+d= 2.

23 . The composite cathode active material of claim 1 , wherein the second lithium transition metal oxide is represented by Formula 7:
Li a Mn b Co c M5′ d O 4   Formula 7
wherein, in Formula 7, M5′ compris

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Park Kwangjin
• Ko Dongsu
• Min Kyoungmin
• Jung Changhoon
• Choi Byungjin

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M4/505

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

• H01M4/525 Primary

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title