Nickel composite hydroxide, positive electrode active material using nickel composite hydroxide as precursor, and methods for producing the same

Patent metadata

Field	Value
Publication number	US-12401032-B2
Application number	US-202217580746-A
Country	US
Kind code	B2
Filing date	Jan 21, 2022
Priority date	Aug 7, 2019
Publication date	Aug 26, 2025
Grant date	Aug 26, 2025

Abstract

Provided is a nickel composite hydroxide capable of reducing a calcination temperature when producing a positive electrode active material, and a positive electrode active material using the nickel composite hydroxide as a precursor. The nickel composite hydroxide for a precursor of a positive electrode active material of a non-aqueous electrolyte secondary battery, wherein when in the nickel composite hydroxide, a peak intensity of a diffraction peak on a (200) plane in powder X-ray diffraction measurement using CuKα rays is defined as α, and a peak intensity of a diffraction peak on a (013) plane in powder X-ray diffraction measurement using CuKα rays is defined as β, a value of α/β is 0.75 or more and 0.95 or less, and the nickel composite hydroxide comprises Ni, Co, Mn, and one or more additive elements M selected from the group consisting of Al, Fe, Ti and Zr.

First claim

What is claimed is:

1. A nickel composite hydroxide for a precursor of a positive electrode active material of a non-aqueous electrolyte secondary battery, wherein when in the nickel composite hydroxide, a peak intensity of a diffraction peak on a (200) plane in powder X-ray diffraction measurement using CuKα rays is defined as α, and a peak intensity of a diffraction peak on a (013) plane in powder X-ray diffraction measurement using CuKα rays is defined as β, a value of α/β is 0.75 or more and 0.95 or less, and the nickel composite hydroxide comprises Ni, Co, Mn, and one or more additive elements M selected from the group consisting of Al, Fe, Ti and Zr,
wherein a molar ratio of Ni:Co:Mn:M, of the nickel composite hydroxide is represented by 1−x−y−z:x:y:z, where 0<x≤0.15, 0<y≤0.15, 0≤z≤0.05, and M represents one or more additive elements selected from the group consisting of Al, Fe, Ti and Zr.

2. The nickel composite hydroxide according to claim 1 , wherein in the nickel composite hydroxide, the diffraction peak of the (200) plane is a diffraction peak appearing in a range of 2θ=69.2±0.1°, and the diffraction peak of the (013) plane is a diffraction peak appearing in a range of 2θ=70.4±0.1°, and when a peak intensity of the diffraction peak appearing in the range of 2θ=69.2±0.1° in powder X-ray diffraction measurement using CuKα rays is defined as α, and a peak intensity of the diffraction peak appearing in the range of 2θ=70.4±0.1° in powder X-ray diffraction measurement using CuKα rays is defined as β, a value of α/β is 0.75 or more and 0.95 or less, and the nickel composite hydroxide comprises Ni, Co, Mn, and one or more additive elements M selected from the group consisting of Al, Fe, Ti, and Zr,
wherein a molar ratio of Ni:Co:Mn:M, of the nickel composite hydroxide is represented by 1−x−y−z:x:y:z, where 0<x≤0.15, 0<y≤0.15, 0≤z≤0.05, and M represents one or more additive elements selected from the group consisting of Al, Fe, Ti and Zr.

3. The nickel composite hydroxide according to claim 1 , wherein in the nickel composite hydroxide, the diffraction peak of the (200) plane is a diffraction peak appearing in a range of 2θ=69.5±0.3°, and the diffraction peak of the (013) plane is a diffraction peak appearing in a range of 2θ=70.5±0.3°, and when a peak intensity of the diffraction peak appearing in the range of 2θ=69.5±0.3° in powder X-ray diffraction measurement using CuKα rays is defined as, and a peak intensity of the diffraction peak appearing in the range of 2θ=70.5±0.3° in powder X-ray diffraction measurement using CuKα rays is defined as β, a value of α/β is 0.75 or more and 0.95 or less, and the nickel composite hydroxide comprises Ni, Co, Mn, and one or more additive elements M selected from the group consisting of Al, Fe, Ti, and Zr,
wherein a molar ratio of Ni:Co:Mn:M, of the nickel composite hydroxide is represented by 1−x−y−z:x:y:z, where 0<x≤0.15, 0<y≤0.15, 0≤z≤0.05, and M represents one or more additive elements selected from the group consisting of Al, Fe, Ti and Zr.

4. The nickel composite hydroxide according to claim 1 , wherein a secondary particle diameter having a cumulative volume percentage of 50% by volume (D50) is 6.0 μm or more and 16.0 μm or less.

5. The nickel composite hydroxide according to claim 2 , wherein a secondary particle diameter having a cumulative volume percentage of 50% by volume (D50) is 6.0 μm or more and 16.0 μm or less.

6. The nickel composite hydroxide according to claim 3 , wherein a secondary particle diameter having a cumulative volume percentage of 50% by volume (D50) is 6.0 μm or more and 16.0 μm or less.

7. The nickel composite hydroxide according to claim 1 , wherein a value of [a secondary particle diameter having a cumulative volume percentage of 90% by volume (D90)−a secondary particle diameter having a cumulative volume percentage of 10% by volume (D10)]/a secondary particle diameter having a cumulative volume percentage of 50% by volume (D50), is 0.80 or more and 1.2 or less.

8. The nickel composite hydroxide according to claim 2 , wherein a value of [a secondary particle diameter having a cumulative volume percentage of 90% by volume (D90)−a secondary particle diameter having a cumulative volume percentage of 10% by volume (D10)]/a secondary particle diameter having a cumulative volume percentage of 50% by volume (D50), is 0.80 or more and 1.2 or less.

9. The nickel composite hydroxide according to claim 3 , wherein a value of [a secondary particle diameter having a cumulative volume percentage of 90% by volume (D90)−a secondary particle diameter having a cumulative volume percentage of 10% by volume (D10)]/a secondary particle diameter having a cumulative volume percentage of 50% by volume (D50), is 0.80 or more and 1.2 or less.

10. A positive electrode active material of a non-aqueous electrolyte secondary battery, wherein the nickel composite hydroxide according to claim 1 is calcined with a lithium compound.

11. A positive electrode active material of a non-aqueous electrolyte secondary battery, wherein the nickel composite hydroxide according to claim 2 is calcined with a lithium compound.

12. A positive electrode active material of a non-aqueous electrolyte secondary battery, wherein the nickel composite hydroxide according to claim 3 is calcined with a lithium compound.

13. A method for producing a nickel composite hydroxide, comprising:
a crystallization step of mixing an aqueous solution containing a nickel salt, a cobalt salt, and a manganese salt with a pH adjuster in a reaction vessel and performing coprecipitation reaction in the mixed liquid to obtain a crude nickel composite hydroxide; and
a solid-liquid separation step of washing the crude nickel composite hydroxide obtained in the crystallization step with an alkaline aqueous solution and then subjecting the resultant to solid-liquid separation,
wherein an ammonia concentration of the mixed liquid in the crystallization step is 0.0 g/L or more and 3.5 g/L or less, and a pH of the mixed liquid based on a liquid temperature of 40° C. is 10.4 or more and 11.5 or less, and
wherein in the nickel composite hydroxide, a peak intensity of a diffraction peak on a (200) plane in powder X-ray diffraction measurement using CuKα rays is defined as α, and a peak intensity of a diffraction peak on a (013) plane in powder X-ray diffraction measurement using CuKα rays is defined as β, a value of α/β is 0.75 or more and 0.95 or less, and the nickel composite hydroxide comprises Ni, Co, Mn, and one or more additive elements M selected from the group consisting of Al, Fe, Ti and Zr, and
wherein a molar ratio of Ni:Co:Mn:M, of the nickel composite hydroxide is represented by 1−x−y−z:x:y:z, where 0<x≤0.15, 0<y≤0.15, 0≤z≤0.05, and M represents one or more additive elements selected from the group consisting of Al, Fe, Ti and Zr.

14. The method for producing a nickel composite hydroxide according to claim 13 , wherein the aqueous solution containing a nickel salt, a cobalt salt, and a manganese salt is mixed with an ammonium ion donor and the pH adjuster in the reaction vessel.

15. A method for producing a positive electrode active material of a non-aqueous electrolyte secondary battery, comprising:
a crystallization step of mixing an aqueous solution containing a nickel salt, a cobalt salt, and a manganese salt with a pH adjuster in a reaction vessel and performing coprecipitation reaction in the mixed liquid to obtain a crude nickel composite hydroxide; and
a solid-liquid separation step of washing the crude nickel composite hydroxide obtained in the crystallization step with an alkaline aqueous solution and then su

Assignees

• Tanaka Chemical Corp

Inventors

• SATOMI Naotoshi
• Iida Yasutaka
• Hata Mikio

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M2004/021

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

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/0416

  involving impregnation with a solution, dispersion, paste or dry powder (H01M4/0438 takes precedence) · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title