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

Patent metadata

Field	Value
Publication number	US-12015151-B2
Application number	US-202217748307-A
Country	US
Kind code	B2
Filing date	May 19, 2022
Priority date	Nov 23, 2018
Publication date	Jun 18, 2024
Grant date	Jun 18, 2024

Abstract

A composite positive active material represented by Formula 1,

Li a Ni b CO c Mn d M e O 2   Formula 1

wherein, in Formula 1, M is zirconium (Zr), aluminum (Al), rhenium (Re), vanadium (V), chromium (Cr), iron (Fe), gallium (Ga), silicon (Si), boron (B), ruthenium (Ru), titanium (Ti), niobium (Nb), molybdenum (Mo), magnesium (Mg), or platinum (Pt), 1.1≤a≤1.3, b+c+d+e≤1, 0≤b≤0.3, 0≤c≤0.3, 0<d≤0.6, and 0≤e≤0.1, wherein, through atomic interdiffusion of lithium and the metal, the composite positive active material has a uniform distribution of lithium excess regions and a uniform degree of disorder of metal cations, and the metal cations have a disordered, irregular arrangement at an atomic scale. Also a method of preparing the composite positive active material, a positive electrode including the composite positive active material, and a lithium battery including the positive electrode.

First claim

What is claimed is:

1. A composite positive active material represented by Formula 1,
Li a Ni b CO c Mn d M e O 2   Formula 1

wherein, in Formula 1,
M is zirconium, aluminum, rhenium, vanadium, chromium, iron, gallium, silicon, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum,
1.1≤a≤1.3, b+c+d+e≤1, 0≤b≤0.3, 0≤c≤0.3, 0<d≤0.6, and 0≤e≤0.1, and
wherein, through atomic interdiffusion of lithium and the metal, the composite positive active material has
a uniform distribution of lithium excess regions, and a uniform degree of disorder of metal cations, and
the metal cations have a disordered, irregular arrangement at an atomic scale and a mixed disordered cation structure,
wherein a ratio of an intensity of a (003) peak to an intensity of a (104) peak is about 0.87 to about 1.11, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation, and
wherein a full width at half-maximum of a diffraction peak between 43º and 45° 2θ of the composite positive active material is about 0.2° to about 0.32°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

2. The composite positive active material of claim 1 , wherein the composite positive active material comprises
a layered phase structure in which a metal layer and a lithium layer are not distinguishable from one another, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

3. The composite positive active material of claim 2 , wherein a ratio of I(44.x°)/I(44.y°) is 0.2 or less, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

4. The composite positive active material of claim 1 , wherein a full width at half-maximum of a diffraction peak between 43° and 45° 2θ of the composite positive active material is from 0.24° to less than 0.31°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

5. The composite positive active material of claim 1 , wherein ordering of lithium excess regions is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

6. The composite positive active material of claim 1 , wherein ordering of Li, Ni, Co, Mn, and M cations is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

7. The composite positive active material of claim 1 , wherein the composite positive active material is a composite represented by Formula 2:
a Li 1+x Ni 0.5−x Mn 0.5 O 2 ·b Li 2−y Ni y MnO 3   Formula 2

wherein, in Formula 2, 0≤x<0.2, 0≤y<0.2, 0<a<1, 0<b<1, a+b=1, and ax=by.

8. The composite positive active material of claim 1 , wherein the composite positive active material is Li 1.2 Ni 0.2 Mn 0.6 O 2 , Li 1.2 Ni 0.3 Mn 0.3 O 2 , Li 1.1 Ni 0.3 Mn 0.6 O 2 , or a combination thereof.

9. The composite positive active material of claim 1 , wherein the composite positive active material has a capacity of about 275 milliampere-hours per gram or greater.

10. A positive electrode comprising the composite positive active material according to claim 1 .

11. The positive electrode of claim 10 , wherein a ratio of I(44.x°)/I(44.y°) is 0.2 or less, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

12. The positive electrode of claim 10 , wherein a full width at half-maximum of a diffraction peak between 43° and 45° 2θ of the composite positive active material is about 0.2° to about 0.32°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

13. The positive electrode of claim 10 , wherein ordering of lithium excess regions is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

14. The positive electrode of claim 10 , wherein ordering of Li, Ni, Co, Mn, and M cations is not observed when the composite positive active material is analyzed by high-angle annular dark-field/annular bright-field imaging-scanning transmission electron microscopy.

15. The positive electrode of claim 10 , wherein the composite positive active material is a composite represented by Formula 2:
a Li 1+x Ni 0.5−x Mn 0.5 O 2 ·b Li 2−y Ni y MnO 3   Formula 2

wherein, in Formula 2, 0≤x<0.2, 0≤y<0.2, 0<a<1, 0<b<1, a+b=1, and ax=by.

16. The positive electrode of claim 10 , wherein the composite positive active material is Li 1.2 Ni 0.2 Mn 0.6 O 2 , Li 1.2 Ni 0.3 Mn 0.3 O 2 , Li 1.1 Ni 0.3 Mn 0.6 O 2 , or a combination thereof.

17. The positive electrode of claim 10 , wherein the composite positive active material has a capacity of about 275 milliampere-hours per gram or greater.

18. A lithium battery comprising:
the positive electrode of claim 10 ;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode.

19. A method of preparing a composite positive active material, the method comprising:
mixing a precursor for forming a composite positive active material represented by Formula 1 to obtain a precursor mixture;
pulverizing the precursor mixture to obtain a pulverized product;
first thermally treating the pulverized product to obtain a first thermal treatment product; and
cooling the first thermal treatment product, wherein the cooling comprises cooling at a cooling rate of about 500° C. per minute to about 900° C. per minute,
Li a Ni b CO c Mn d M e O 2   Formula 1

wherein, in Formula 1, M is zirconium, aluminum, rhenium, vanadium, chromium, iron, gallium, silicon, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum,
1.1≤a≤1.3, b+c+d+e≤1, 0≤b≤0.3, 0≤c≤0.3, 0<d≤0.6, and 0≤e≤0.1, and
wherein, through atomic interdiffusion of lithium and the metal, the composite positive active material has
a uniform distribution of lithium excess regions, and a uniform degree of disorder of metal cations, and
the metal cations have a mixed disordered, irregular arrangement at an atomic scale and a disordered cation structure,
a ratio of an intensity of a (003) peak to an intensity of a (104) peak is about 0.87 to about 1.11, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation, and
wherein a full width at half-maximum of a diffraction peak between 43º and 45° 2θ of the composite positive active material is about 0.2° to about 0.32°, when the composite positive active material is analyzed by X-ray diffraction using Cu Kα radiation.

20. The method of claim 19 , wherein the first thermally treating comprises contacting with an oxidizing gas at a temperature of about 900° C. or greater.

21. The method of claim 20 , further comprising second thermally treating the precursor mixture before the pulverizing of the precursor mixture.

22. The method of claim 21 , wherein the second thermally treating comprises contacting with an oxidizing gas at a temperature of about 700° C. or greater.

23. The method of claim 19 , wherein the first thermally treating comprises contacting with an oxidizing gas at a temperature of about 900° ° C. to about 1100° C.

24. The method of claim 19 , wherein the cooling comprises coolin

Assignees

• Samsung Electronics Co Ltd
• Postech Acad Ind Found

Inventors

• Yeon Donghee
• Kang Byoungwoo
• Lee Junghwa
• Choi Byungjin
• Hong Sukgi
• Ha Jinsu

Classifications

• H01M4/362

  Composites · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · 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

• H01M10/0525

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