Nickel-based lithium metal composite oxide, method of preparing the same, and lithium secondary battery including positive electrode including the same

Patent metadata

Field	Value
Publication number	US-2022140317-A1
Application number	US-202117514431-A
Country	US
Kind code	A1
Filing date	Oct 29, 2021
Priority date	Oct 30, 2020
Publication date	May 5, 2022
Grant date	—

Abstract

A nickel-based lithium metal composite oxide including secondary particles including aggregates of primary particles. The secondary particles include i) large secondary particles having a particle size of at least about 14 μm and including aluminum and ii) small secondary particles having a particle size of no more than about 5 μm and including manganese, and a manganese content by mole percent of each of the large secondary particles is smaller than a manganese content by mole percent of each of the small secondary particles and manganese is included on a surface of each of the large secondary particles and aluminum is included on a surface of each of the small secondary particles.

First claim

What is claimed is:

1 . A nickel-based lithium metal composite oxide comprising secondary particles including aggregates of primary particles, wherein:
the secondary particles comprise i) large secondary particles having a particle size of at least about 14 μm and including aluminum and ii) small secondary particles having a particle size of no more than about 5 μm and including manganese; and a manganese content by mole percent of each of the large secondary particles based on total moles of metal excluding lithium of the large secondary particles is smaller than a manganese content by mole percent of each of the small secondary particles based on total moles of metal excluding lithium of the small secondary particles and manganese is included on a surface of each of the large secondary particles and aluminum is included on a surface of each of the small secondary particles.

2 . The nickel-based lithium metal composite oxide of claim 1 , wherein the large secondary particles exclude manganese or at least some of the large secondary particles comprise from about 0.01 mol % to about 0.5 mol % manganese based on total moles of metal excluding lithium of the large secondary particles.

3 . The nickel-based lithium metal composite oxide of claim 1 , wherein at least some of the small secondary particles comprise from about 0.5 mol % to about 5 mol % manganese based on total moles of metal excluding lithium of the small secondary particles.

4 . The nickel-based lithium metal composite oxide of claim 1 , wherein some of the large secondary particles have a particle size of about 14 μm to about 20 μm.

5 . The nickel-based lithium metal composite oxide of claim 1 , wherein some of the small secondary particles have a particle size of about 1 μm to about 5 μm.

6 . The nickel-based lithium metal composite oxide of claim 1 , wherein a Ni content in the nickel-based lithium metal composite oxide comprises at least about 60 mol % nickel based on total moles of metal excluding lithium of the nickel-based lithium metal composite oxide.

7 . The nickel-based lithium metal composite oxide of claim 1 , wherein on a surface of at least some of the large secondary particles comprises aluminum and from about 0.01 mol % to about 0.2 mol % manganese based on total moles of metal excluding lithium of the large secondary particle.

8 . The nickel-based lithium metal composite oxide of claim 1 , wherein a surface of at least some of the small secondary particles comprises manganese and from about 0.01 mol % to about 0.2 mol % aluminum based on total moles of metal excluding lithium of the small secondary particle.

9 . The nickel-based lithium metal composite oxide of claim 1 , wherein an amount of the large secondary particles is from 30 parts by weight to 90 parts by weight based on 100 parts by weight of a total amount of the large secondary particles and the small secondary particles.

10 . The nickel-based lithium metal composite oxide of claim 1 , wherein the large secondary particles consist of a compound of Formula 1 below:
Li a (Ni 1−x−y−z Co x Al y M z )O 2±α1   Formula 1
wherein in Formula 1, M is boron, magnesium, calcium, strontium, barium, titanium, vanadium, chromium, iron, copper, or zirconium, 0.95≤a≤1.1, 0.6≤(1-x-y-z)<1, 0<x<0.4, 0<y<0.4, 0≤z<0.4, and 0≤α1≤0.1.

11 . The nickel-based lithium metal composite oxide of claim 1 , wherein the small secondary particles consist of a compound of Formula 2 below:
Li a (Ni 1−x−y−z Co x Mn y M z )O 2±α1   Formula 2
wherein in Formula 2, M is boron, magnesium, calcium, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium, or aluminum, 0.95≤a≤1.1, 0.6≤(1-x-y-z)<1, 0<x<0.4, 0<y<0.4, 0≤z<0.4, and 0≤α1≤0.1.

12 . The nickel-based lithium metal composite oxide of claim 1 , wherein at least some of the large secondary particles comprise from 0.5 mol % to 5 mol % aluminum based on total moles of metal excluding lithium of the large secondary particles.

13 . A method of preparing the nickel-based lithium metal composite oxide according to claim 1 , the method comprising the steps of:
preparing a precursor mixture by mixing a large precursor having a size of at least about 14 μm and including aluminum, a small precursor having a size of no more than about 5 μm and including manganese, and a lithium precursor; and heat-treating the precursor mixture.

14 . The method of claim 13 , wherein the heat-treating is performed at a temperature of about 600° C. to about 900° C.

15 . The method of claim 13 , wherein:
the large precursor excludes manganese or the large precursor comprises from about 0.01 mol % to about 0.5 mol % manganese based on total moles of metal of the large precursor; and the small precursor comprises from about 0.5 mol % to about 5 mol % manganese based on total moles of metal of the small precursor.

16 . The method of claim 13 , wherein the large precursor comprises from about 0.5 mol % to about 5 mol % aluminum based on total moles of metal of the large precursor.

17 . The method of claim 13 , wherein the lithium precursor comprises an anhydrous lithium hydroxide, a lithium hydroxide hydrate, a lithium fluoride, a lithium carbonate, or any mixture thereof.

18 . A positive electrode comprising the nickel-based lithium metal composite oxide of claim 1 .

19 . A lithium secondary battery comprising the positive electrode of claim 18 , a negative electrode, and an electrolyte therebetween.

20 . A metal oxide composite comprising nickel, lithium, and secondary particles including aggregates of primary particles, wherein:
the secondary particles comprise i) large secondary particles having a particle size of at least about 14 μm and including aluminum and ii) small secondary particles having a particle size of no more than about 5 μm and including manganese; and a manganese content by mole percent of at least some of the large secondary particles is smaller than a manganese content by mole percent of at least some of the small secondary particles and manganese is included on a surface of at least some of the large secondary particles and aluminum is included on a surface of at least some of the small secondary particles.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Jang Jungsue
• Song Jayhyok
• Shin Dongwook
• Shim Jaeha

Classifications

• C01G53/82

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M4/463

  Aluminium based · CPC title

• H01M4/48

  of inorganic oxides or hydroxides · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/362 Primary

  Composites · CPC title