Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material

Patent metadata

Field	Value
Publication number	US-11670754-B2
Application number	US-202017102332-A
Country	US
Kind code	B2
Filing date	Nov 23, 2020
Priority date	Dec 4, 2017
Publication date	Jun 6, 2023
Grant date	Jun 6, 2023

Abstract

A positive active material for a rechargeable lithium battery includes a first positive active material including a secondary particle including at least two agglomerated primary particles, where at least one part of the primary particles has a radial arrangement structure, as well as a second positive active material having a monolith structure, wherein the first and second positive active materials may each include nickel-based positive active materials and the surface of the second positive active material is coated with a boron-containing compound. Further embodiments provide a method of preparing the positive active material, and a rechargeable lithium battery including a positive electrode including the positive active material.

First claim

What is claimed is:

1. A positive active material for a rechargeable lithium battery, comprising:
a first positive active material comprising a secondary particle comprising at least two agglomerated primary particles, where at least one part of the primary particles has a radial arrangement structure;
a second positive active material having a monolith structure,
wherein the first positive active material and the second positive active material each comprise a nickel-based positive active material;
a boron-containing compound coated on only a surface of the second positive active material,
wherein an amount of boron based on a total amount of the second positive active material is 0.3 mol % or less.

2. The positive active material of claim 1 , wherein the boron-containing compound is boron oxide, lithium borate, or a combination thereof.

3. The positive active material of claim 1 , wherein the boron-containing compound is B 2 O 3 , LiBO 2 , Li 3 B 7 O 12 , Li 6 B 4 O 9 , Li 3 B 11 O 18 , Li 2 B 4 O 7 , Li 3 BO 3 , or a combination thereof.

4. The positive active material of claim 1 , wherein the amount of boron based on the total amount of the second positive active material is about 0.01 mol % to about 0.3 mol %.

5. The positive active material of claim 1 , wherein an amount of the second positive active material is about 10 wt % to about 50 wt % based on a total weight of the positive active material.

6. The positive active material of claim 1 , wherein the second positive active material has an average particle diameter of about 0.05 μm to about 10 μm.

7. The positive active material of claim 1 , wherein in the first positive active material,
the secondary particle comprises a radial arrangement structure, or
the secondary particle comprises an internal part comprising an irregular porous structure and an external part comprising the radial arrangement structure.

8. The positive active material of claim 1 , wherein in the first positive active material,
the primary particles have a plate shape, and
a long-axis of the at least one part of the primary particles is arranged in a radial direction.

9. The positive active material of claim 1 , wherein in the first positive active material, an average length of the primary particles is about 0.01 μm to about 5 μm.

10. The positive active material of claim 1 , wherein in the first positive active material, an average particle diameter of the secondary particle is about 1 μm to about 20 μm.

11. The positive active material of claim 1 , wherein the first positive active material is represented by Chemical Formula 1:
Li a (Ni 1-x-y-z Co x Mn y M z )O 2 , and   Chemical Formula 1

wherein, in Chemical Formula 1, M is an element selected from boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al), and
0.95≤a≤1.3, x≤(1-x-y-z), y≤(1-x-y-z), 0<x<1, 0≤y<1, and 0≤z<1.

12. The positive active material of claim 1 , wherein the second positive active material is represented by Chemical Formula 1:
Li a (Ni 1-x-y-z Co x Mn y M z )O 2 , and   Chemical Formula 1

wherein, in Chemical Formula 1, M is an element selected from boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al), and
0.95≤a≤1.3, x≤(1-x-y-z), y≤(1-x-y-z), 0<x<1, 0≤y<1, and 0≤z<1.

13. A method of preparing a positive active material for a rechargeable lithium battery, the method comprising:
subjecting a first precursor to a first heat-treatment in a first oxidizing gas atmosphere to obtain a first nickel-based oxide;
subjecting a second precursor to a second heat-treatment in a second oxidizing gas atmosphere to obtain a second nickel-based oxide having a monolith structure;
mixing the second nickel-based oxide and a boron-containing precursor and subjecting the mixture to a third heat-treatment to obtain the second nickel-based oxide coated with a boron-containing compound; and
mixing the first nickel-based oxide and the second nickel-based oxide coated with the boron-containing compound to obtain a positive active material comprising a first positive active material and a second positive active material having a monolith structure and coated with the boron-containing compound,
wherein,
the boron-containing compound is coated on only a surface of the second positive active material, and
an amount of boron based on a total amount of the second positive active material is 0.3 mol % or less.

14. The method of claim 13 , wherein the boron-containing precursor is H 3 BO 3 , B 2 O 3 , C 6 H 5 B(OH) 2 , (C 6 H 5 O) 3 B, [CH 3 (CH 2 ) 3 O] 3 B, C 13 H 19 BO 3 , C 3 H 9 B 3 O 6 , (C 3 H 7 O) 3 B, or a combination thereof.

15. The method of claim 13 , wherein an amount of the boron- containing precursor based on 100 parts by weight of the second nickel-based oxide is about 0.01 parts by weight to about 0.35 parts by weight.

16. The method of claim 13 , wherein a temperature for the third heat-treatment for the mixture of the second nickel-based oxide and the boron-containing precursor is about 300° C. to 500° C.

17. The method of claim 13 , wherein the obtaining of the second nickel-based oxide comprises pulverizing a material obtained from subjecting the second precursor to the second heat-treatment to obtain particles having a monolith structure.

18. The method of claim 13 , wherein the second precursor is obtained by mixing a second composite metal hydroxide having a specific surface area of about 1 m 2 /g to about 30 m 2 /g, as measured utilizing a BET method, with a lithium-based material.

19. The method of claim 13 , wherein a mixing ratio of the first nickel-based oxide and the second nickel-based oxide coated with the boron-containing compound is about 9:1 to about 5:5 based on a weight ratio.

20. A rechargeable lithium battery, comprising:
a positive electrode comprising the positive active material of claim 1 ;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Yun Pilsang
• Kim Jongmin
• Kim Hyunbeom
• Park Sangin
• You Yongchan

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/364

  as mixtures · CPC title

• C01P2004/61

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