Cathode active material precursor, cathode active material formed therefrom, method of preparing the cathode active material, and cathode and lithium battery each including the cathode active material

Patent metadata

Field	Value
Publication number	US-2019074513-A1
Application number	US-201816119170-A
Country	US
Kind code	A1
Filing date	Aug 31, 2018
Priority date	Sep 4, 2017
Publication date	Mar 7, 2019
Grant date	—

Abstract

A cathode active material includes a secondary particle including an aggregate of a plurality of primary particles, wherein the secondary particle includes a nickel-containing lithium transition metal oxide having a layered crystal structure, wherein the plurality of primary particles includes a first primary particle having a size greater than about 400 nanometers, a second primary particle having a size less than about 150 nanometers, and a third primary particle having a size of about 150 nanometers to about 400 nanometers, wherein the third primary particle has a area of greater than or equal to about 80% of a total area of the plurality of primary particles, and wherein the secondary particle has a porosity of less than or equal to about 10% of a total area of the cathode active material.

First claim

What is claimed is:

1 . A cathode active material comprising:
a secondary particle comprising an aggregate of a plurality of primary particles, wherein the secondary particle comprises a nickel-containing lithium transition metal oxide having a layered crystal structure, wherein the plurality of primary particles comprises
a first primary particle having a size greater than about 400 nanometers,
a second primary particle having a size less than about 150 nanometers, and
a third primary particle having a size of about 150 nanometers to about 400 nanometers,
wherein the third primary particle has an area of greater than or equal to about 80% of a total area of the plurality of primary particles, and
wherein the secondary particle has a porosity of less than or equal to about 10% of a total area of the cathode active material.

2 . The cathode active material of claim 1 ,
wherein the first primary particle has an area of less than or equal to about 20% of the total area of the plurality of primary particles, wherein an area of the second primary particle is less than or equal to about 9% of the total area of the plurality of primary particles, and wherein the secondary particle has a porosity of about 1% to about 10% of the total area of the cathode active material.

3 . The cathode active material of claim 1 ,
wherein the plurality of primary particles has a particle uniformity of greater than or equal to about 90%, wherein the first primary particle has an area of about 2.1% to about 19.2% of the total area of the plurality of primary particles, wherein the second primary particle has an area of about 0.1% to about 8.6% of the total area of the plurality of primary particles, and wherein the secondary particle has a porosity of about 1.5% to about 7% of the total area of the cathode active material.

4 . The cathode active material of claim 1 , wherein the secondary particle comprising the nickel-containing lithium transition metal oxide having a layered crystal structure has an average particle diameter of about 15 μm to about 30 μm.

5 . The cathode active material of claim 1 , wherein the third primary particle has an area of about 80% to about 95% of the total area of the plurality of primary particles.

6 . The cathode active material of claim 1 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure has a layered rock-salt structure and belongs to space group R-3m.

7 . The cathode active material of claim 1 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure is a compound represented by Formulae 1 to 4:
Li x Ni 1−y−z−α Co y Mn z Me α O 2   Formula 1
wherein, in Formula 1,
1≤x≤1.1, 0≤y≤0.2, 0≤z≤0.2, 0≤α≤0.05,
Me may be Zr, Al, Mg, Ti, Cu, W, B, or a combination thereof, and
y+z+α≤0.3,
Li x Co 1−y M y O 2−α X α   Formula 2

Li x Ni 1−y Me y O 2−α X α   Formula 3

Li x Ni 1−y−z Mn y Ma z O 2−α X α   Formula 4

wherein, in Formulae 2 to 4,
1≤x≤1.1, 0≤y≤0.9, 0≤z≤0.2, 0≤α≤2,
M may be Ni, Mn, Zr, Al, Mg, Ag, Mo, Ti, V, Cr, Fe, Cu, B, or a combination thereof,
Me may be Co, Zr, Al, Mg, Ag, Mo, Ti, V, Cr, Mn, Fe, Cu, B, or a combination thereof,
Ma may be Co, Zr, Al, Mg, Ag, Mo, Ti, V, Cr, Fe, Cu, B, or a combination thereof, and
X may be F, S, P or a combination thereof, and
wherein x, y, z, α, and Me are independently selected for each of Formulae 1 to 4.

8 . The cathode active material of claim 1 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure is a compound represented by Formulae 5 to 7:
Li[Li 1−a Me a ]O 2+d   Formula 5
wherein, in Formula 5, 0.8≤a<1, 0≤d≤0.1, and
Me may be Ni, Co, Mn, Al, V, Cr, Fe, Zr, Re, B, Ge, Ru, Sn, Ti, Nb, Mo, Pt or a combination thereof,
Li[Li 1−x−y−z Ma x Mb y Mc z ]O 2+d   Formula 6

wherein, in Formula 6, 0.8≤x+y+z<1, 0<x<1, 0<y<1, 0<z<1, 0≤d≤0.1, and
Ma, Mb, and Mc are each independently Mn, Co, Ni, Al, or a combination thereof
Li[Li 1−x−y−z Ni x Co y Mn z ]O 2+d   Formula 7

wherein, in Formula 7, 0.8≤x+y+z<1; 0<x<1, 0<y<1, 0<z<1, and 0≤d≤0.1, and wherein x, y, z, d, Me, and Ma are independently selected for each of Formulae 5 to 7.

9 . The cathode active material of claim 1 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure is a compound represented by Formula 8:
aLi 2 MnO 3− (1−a)LiMO 2   Formula 8
wherein, in Formula 8, 0<a<1, and
M comprises nickel, cobalt, manganese, vanadium, chromium, iron, zirconium, rhenium, aluminum, boron, germanium, ruthenium, tin, titanium, niobium, molybdenum, platinum, or a combination thereof.

10 . The cathode active material of claim 1 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure is a compound represented by Formula 9:
Li x Ni 1−y−z M y Co z O 2   Formula 9
wherein, in Formula 9, 0.90≤x≤1.1, 0≤y≤0.2, 0<z≤0.2, 0.7≤1−y−z≤0.99, and
M is manganese, aluminum, titanium, calcium, or a combination thereof.

11 . The cathode active material of claim 1 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure is a compound represented by Formula 9a:
Li x Ni 1−y−z M x Co y O 2   Formula 9a
wherein, in Formula 9a, 0.80≤x≤1.1, 0≤y≤0.2, 0<z≤0.2, and 0.8≤1−y−z≤0.99.

12 . The cathode active material of claim 11 , wherein the nickel-containing lithium transition metal oxide having a layered crystal structure is Li 1.03 [Ni 0.91 Co 0.06 Mn 0.03 ]O 2 , Li 1.03 [Ni 0.88 Co 0.08 Mn 0.04 ]O 2 , Li 1.03 [Ni 0.8 Co 0.15 Mn 0.05 ]O 2 , Li 1.03 [Ni 0.85 Co 0.10 Mn 0.05 ]O 2 , Li 1.03 [Ni 0.91 Co 0.05 Mn 0.04 ]O 2 , Li 1.05 [Ni 0.91 Co 0.06 Mn 0.03 ]O 2 , Li 1.05 [Ni 0.88 Co 0.08 Mn 0.04 ]O 2 , Li 1.05 [Ni 0.8 Co 0.15 Mn 0.05 ]O 2 , Li 1.05 [Ni 0.85 Co 0.10 Mn 0.05 ]O 2 , Li 1.05 [Ni 0.91 Co 0.05 Mn 0.04 ]O 2 , Li 1.06 [Ni 0.91 Co 0.06 Mn 0.03 ]O 2 , Li 1.06 [Ni 0.88 Co 0.08 Mn 0.04 ]O 2 , Li 1.06 [Ni 0.8 Co 0.15 Mn 0.05 ]O 2 , Li 1.06 [Ni 0.85 Co 0.10 Mn 0.05 ]O 2 , Li 1.06 [Ni 0.91 Co 0.05 Mn 0.04 ]O 2 ; Li 1.09 [Ni 0.91 Co 0.06 Mn 0.03 ]O 2 , Li 1.09 [Ni 0.88 Co 0.08 Mn 0.04 ]O 2 , Li 1.09 [Ni 0.8 Co 0.15 Mn 0.05 ]O 2 , Li 1.09 [Ni 0.85 Co 0.10 Mn 0.05 ]O 2 , or Li 1.09 [Ni 0.91 Co 0.05 Mn 0.04 ]O 2 .

13 . The cathode active material of claim 1 , wherein the cathode active material further includes a small-particle-size cathode active material, and a mixture of the cathode active material and small-particle-size cathode active material has a pressed density of about 3.3 grams per cubic centimeter or greater.

14 . A cathode comprising the cathode active material of claim 1 .

15 . A lithium battery comprising:
the cathode of claim 14 , an anode, and an electrolyte disposed between the cathode and the anode.

16 . The lithium battery of claim 15 , wherein the lithium battery has an initial efficiency of about 93% or greater, and
the cathode has a pressed density of greater than or equal to about 2.8 grams per cubic centimeter.

17 . The lithium battery of claim 15 , wherein, after discharging to 3.5 volts, the cathode active material has
an a-axis crystal lattice constant that is about 0.1% to about 0.5% less than an a-axis crystal lattice constant before the discharging, and a c-axis crystal lattice constant that is about 0.1% to about 0.5% greater than a c-axis crystal lattice constant before the discharging.

18 . A cathode active material precursor comprising:
a vertical plate network-structure

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Ham Dongjin
• Song Jayhyok
• Kapylou Andrei
• Park Jinhwan
• Son Youhwan
• Moon San
• Ahn Sungjin
• Yeon Donghee
• Ha Jinsu
• Park Kwangjin
• Choi Byungjin

Classifications

• 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

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · 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

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title