Positive electrode active materials, preparation methods thereof, positive electrodes, and rechargeable lithium batteries

Patent metadata

Field	Value
Publication number	US-2025167228-A1
Application number	US-202418952931-A
Country	US
Kind code	A1
Filing date	Nov 19, 2024
Priority date	Nov 20, 2023
Publication date	May 22, 2025
Grant date	—

Abstract

A positive electrode active material includes a layered lithium nickel-based composite oxide, wherein, based on 100 mol % of a total mole of metals of the layered lithium nickel-based composite oxide excluding lithium, a nickel content is greater than or equal to about 60 mol %, an aluminum content is about 0.8 mol % to about 1.5 mol %, a zirconium content is about 0.1 mol % to about 0.3 mol %, and a ratio of the aluminum content relative to the zirconium content (Al/Zr) is greater than or equal to about 5, and the positive electrode active material is in a form of a single particle with an average particle diameter (D 50 ) of about 1 μm to about 4 μm.

First claim

What is claimed is:

1 . A positive electrode active material, comprising:
a layered lithium nickel-based composite oxide, wherein,
a nickel content is greater than or equal to about 60 mol % based on 100 mol % of a total mole of metals of the layered lithium nickel-based composite oxide excluding lithium,
an aluminum content is about 0.8 mol % to about 1.5 mol % based on the 100 mol % of the total mole of the metals of the layered lithium nickel-based composite oxide excluding lithium, and
a zirconium content is about 0.1 mol % to about 0.3 mol % based on the 100 mol % of the total mole of the metals of the layered lithium nickel-based composite oxide excluding lithium,
wherein,
a ratio of the aluminum content relative to the zirconium content (Al/Zr) is greater than or equal to about 5, and
wherein,
the positive electrode active material is in a form of a single particle with an average particle diameter (D 50 ) of about 1 μm to about 4 μm.

2 . The positive electrode active material as claimed in claim 1 , wherein: the positive electrode active material is in a form of one single particle separated from another single particle or two to nine single particles attached with each other.

3 . The positive electrode active material as claimed in claim 1 , wherein:
the layered lithium nickel-based composite oxide is represented by Chemical Formula 1:
Li a1 Ni x1 M 1 y1 Al z1 Zr w1 O 2-b1 X b1   [Chemical Formula 1]

in Chemical Formula 1, 0.9≤a1≤1.2, 0.6≤x1≤0.991, 0≤y1≤0.391, 0.008≤z1≤0.015, 0.001≤w1≤0.003, 0.9≤x1+y1+z1+w1≤1.1, and 0≤b1≤0.1, M 1 being one or more elements selected from among B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zn, and X being one or more elements selected from among F, P, and S.

4 . A positive electrode, comprising:
a positive electrode current collector, and a positive electrode active material layer located on the positive electrode current collector and comprising the positive electrode active material as claimed in claim 1 .

5 . The positive electrode as claimed in claim 4 , wherein the positive electrode active material layer comprises:
a first positive electrode active material comprising the positive electrode active material as claimed in claim 1 , and a second positive electrode active material in a form of secondary particles, wherein each of the secondary particles comprises an agglomeration of a plurality of primary particles, wherein the second positive electrode active material comprises a layered lithium nickel-based composite oxide, wherein, a nickel content is greater than or equal to about 60 mol % based on 100 mol % of a total mole of metals of the layered lithium nickel-based composite oxide excluding lithium, an aluminum content is about 0.8 mol % to about 1.5 mol % based on the 100 mol % of the total mole of the metals of the layered lithium nickel-based composite oxide excluding lithium, and a zirconium content is about 0.1 mol % to about 0.3 mol % based on the 100 mol % of the total mole of the metals of the layered lithium nickel-based composite oxide excluding lithium, wherein, a ratio of the aluminum content relative to the zirconium content (Al/Zr) is greater than or equal to about 5, and wherein, the secondary particles have a hollow structure with pores inside, and an average particle diameter (D 50 ) of the primary particles constituting the secondary particles is about 1 μm to about 4 μm.

6 . The positive electrode as claimed in claim 5 , wherein:
the layered lithium nickel-based composite oxide of the second positive electrode active material is represented by Chemical Formula 1:
Li a1 Ni x1 M 1 y1 Al z1 Zr w1 O 2-b1 X b1   [Chemical Formula 1]

in Chemical Formula 1, 0.9≤a1≤1.2, 0.6≤x1≤0.991, 0≤y1≤0.391, 0.008≤z1≤0.015, 0.001≤w1≤0.003, 0.9≤x1+y1+z1+w1≤1.1, and 0≤b1≤0.1, M 1 being one or more elements selected from among B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zn, and X being one or more elements selected from among F, P, and S.

7 . The positive electrode as claimed in claim 5 , wherein:
an average particle diameter (D 50 ) of the secondary particles of the second positive electrode active material is about 10 μm to about 20 μm.

8 . The positive electrode as claimed in claim 7 , wherein:
a size of the pores inside the secondary particles of the second positive electrode active material is about 1 μm to about 9 μm.

9 . The positive electrode as claimed in claim 5 , wherein:
based on 100 wt % of a total weight of the first positive electrode active material and the second positive electrode active material, the first positive electrode active material is included at about 5 wt % to about 60 wt %, and the second positive electrode active material is included at about 40 wt % to about 95 wt %.

10 . A method of preparing a positive electrode active material comprising
performing a co-precipitation reaction of a nickel precursor and an M 1 precursor to prepare a nickel-based composite hydroxide being in a form of particles and having micropores inside the particles, mixing the nickel-based composite hydroxide, a lithium raw material, an aluminum raw material, and a zirconium raw material and performing a heat treatment to prepare hollow secondary particles comprising layered lithium nickel-based composite oxide and having pores inside as secondary particles made by agglomerating a plurality of primary particles, pulverizing the secondary particles, and obtaining a positive electrode active material, wherein M 1 is one or more elements selected from among B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zn, and based on 100 mol % of a total mole of metals of the nickel-based composite hydroxide, aluminum in the aluminum raw material, and zirconium in the zirconium raw material, an aluminum content of the aluminum raw material is about 0.8 mol % to about 1.5 mol %, a zirconium content of the zirconium raw material is about 0.1 mol % to about 0.3 mol %, and a ratio of the aluminum content relative to the zirconium content (Al/Zr) is greater than or equal to about 5.

11 . The method as claimed in claim 10 , wherein:
the co-precipitation reaction comprises a first reacting at a pH ranging from about 11 to about 12, and a second reacting at a pH lower than that of the first reacting.

12 . The method as claimed in claim 10 , wherein:
the nickel-based composite hydroxide is represented by Chemical Formula 11:
Ni x11 M 1 y11 (OH) 2   [Chemical Formula 11]

in Chemical Formula 11, 0.6≤x11≤1, 0≤y11≤0.4, and 0.9≤x11+y11≤1.1, and M 1 being one or more elements selected from among B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zn; and wherein the nickel-based composite hydroxide is amorphous, and the nickel-based composite hydroxide is in a form of a particle, and the particle comprises an inner portion comprising a plurality of micropores and an outer portion that surrounds the inner portion and has a dense structure.

13 . The method as claimed in claim 10 , wherein:
a lithium content of the lithium raw material is about 0.9 parts by mole to about 1.2 parts by mole based on the total metals of 1 part by mole of metals of the nickel-based composite hydroxide, aluminum of the aluminum raw material, and zirconium of the zirconium raw material, the aluminum raw material is aluminum oxide, and the zirconium raw material is zirconium oxide.

14 . The method as claimed in claim 10 , wherein:
the heat treatment is performed at about 700° C. to about 900° C. in an oxidizing gas atm

Assignees

• Samsung Sdi Co Ltd

Inventors

• Choi Seungyeon
• Kim Soohyeon
• Shin Dongwook
• Hong Soonkie
• Choi Aram
• Ha Jeuk
• Cha Minah
• Kim Minhan

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/052

  Li-accumulators · 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

• 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

• H01M4/366

  as layered products · CPC title