Nickel manganese composite hydroxide, production method for nickel manganese composite hydroxide, positive electrode active material for non-aqueous electrolyte secondary battery, production method for positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-11670765-B2
Application number	US-201716320670-A
Country	US
Kind code	B2
Filing date	Jul 28, 2017
Priority date	Jul 29, 2016
Publication date	Jun 6, 2023
Grant date	Jun 6, 2023

Abstract

Provided are a positive electrode active material that can provide a nonaqueous electrolyte secondary battery having high energy density and excellent output characteristics, a nickel-manganese composite hydroxide as a precursor thereof, and methods for producing these. A nickel-manganese composite hydroxide is represented by General Formula (1): NixMnyMz(OH)2+α and contains a secondary particle formed of a plurality of flocculated primary particles. The nickel-manganese composite hydroxide has a half width of a diffraction peak of a (001) plane of at least 0.35° and up to 0.50° and has a degree of sparsity/density represented by [(a void area within the secondary particle/a cross section of the secondary particle)×100](%) within a range of greater than 10% and up to 25%.

First claim

The invention claimed is:

1. A nickel-manganese composite hydroxide represented by General Formula (1): Ni x Mn y M z (OH) 2+α (in Formula (1), M is at least one element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; x satisfies 0.1≤x≤0.9, y satisfies 0.05≤y≤0.8, z satisfies 0≤z≤0.8, and x+y+z=1.0; and α satisfies 0≤α≤0.4) and containing a secondary particle formed of a plurality of flocculated primary particles, wherein
the nickel-manganese composite hydroxide has a half width of a diffraction peak of a (001) plane obtained by X-ray diffraction measurement of at least 0.35° and up to 0.50° and has a degree of sparsity/density represented by [(a void area within a cross section area of the secondary particle/the cross section area of the secondary particle)×100](%) within a range of greater than 10% and up to 22%.

2. The nickel-manganese composite hydroxide according to claim 1 , wherein a pore volume of the nickel-manganese composite hydroxide measured by a nitrogen adsorption method is at least 0.03 cm 3 /g and up to 0.06 cm 3 /g.

3. The nickel-manganese composite hydroxide according to claim 1 , wherein [(D90−D10)/a volume-average particle diameter MV] as an indicator indicating a spread of particle size distribution of the nickel-manganese composite hydroxide is at least 0.7, and the volume-average particle diameter MV is at least 5 μm and up to 20 μm.

4. The nickel-manganese composite hydroxide according to claim 1 , wherein a specific surface area of the nickel-manganese composite hydroxide is at least 10 m 2 /g and up to 20 m 2 /g.

5. The nickel-manganese composite hydroxide according to claim 1 , wherein a tap density of the nickel-manganese composite hydroxide is at least 1.2 g/cm 3 and up to 2.2 g/cm 3 .

6. A method for producing a nickel-manganese composite hydroxide represented by General Formula (1): Ni x Mn y M z (OH) 2+α (in Formula (1), M is at least one element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; x satisfies 0.1≤x≤0.9, y satisfies 0.05≤y≤0.8, z satisfies 0≤z≤0.8, and x+y+z=1.0; and a satisfies 0≤α≤0.4) and containing a secondary particle formed of a plurality of flocculated primary particles,
the method comprising a crystallization process of generating a nickel-manganese composite hydroxide by neutralizing a salt containing at least nickel and a salt containing at least manganese in a reaction aqueous solution, wherein
in the crystallization process, a dissolved oxygen concentration in the reaction aqueous solution is adjusted to fall within a range of greater than 4.6 mg/L and up to 6.0 mg/L, and a dissolved nickel concentration in the reaction aqueous solution is adjusted to fall within a range of at least 300 mg/L and up to 800 mg/L.

7. The method for producing the nickel-manganese composite hydroxide according to claim 6 , wherein in the crystallization process, a stirring power is adjusted to fall within a range of at least 2.0 kW/m 3 and up to 13 kW/m 3 .

8. The method for producing the nickel-manganese composite hydroxide according to claim 6 , wherein in the crystallization process, a temperature of the reaction aqueous solution is adjusted to fall within a range of at least 35° C. and up to 60° C.

9. The method for producing the nickel-manganese composite hydroxide according to claim 6 , wherein in the crystallization process, a pH value measured with a liquid temperature of the reaction aqueous solution of 25° C. as a basis is adjusted to fall within a range of at least 10.0 and up to 13.0.

10. The method for producing the nickel-manganese composite hydroxide according to claim 6 , wherein the crystallization process includes overflowing slurry containing nickel-manganese composite hydroxide particles generated through neutralization by continuously adding a mixed aqueous solution containing nickel and manganese to a reaction tank and collecting the particles.

11. A positive electrode active material for a nonaqueous electrolyte secondary battery, the positive electrode active material comprising:
a lithium-nickel-manganese composite oxide represented by General Formula (2): Li 1+t Ni x Mn y M z O 2+β (in Formula (2), M is at least one element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; t satisfies −0.05≤t≤0.5, x satisfies 0.1≤x≤0.9, y satisfies 0.05≤y≤0.8, z satisfies 0≤z≤0.8, and x+y+z=1.0; and β satisfies 0≤β≤0.5) and containing a secondary particle formed of flocculated primary particles, wherein
the positive electrode active material for a nonaqueous electrolyte secondary battery has a degree of sparsity/density represented by [(a void area within a cross section area of the secondary particle/the cross section area of the secondary particle)×100](%) of at least 10% and up to 25% and has a DBP absorption amount measured in compliance with JIS K6217-4:2008 of greater than 20 cm 3 /100 g and up to 28 ml/100 g.

12. The positive electrode active material for the nonaqueous electrolyte secondary battery according to claim 11 , wherein the positive electrode active material has a tap density of at least 1.6 g/cm 3 and up to 2.0 g/cm 3 .

13. The positive electrode active material for the nonaqueous electrolyte secondary battery according to claim 11 , wherein a ratio I(003)/I(104) of diffraction peak intensity I(003) of a 003 plane to peak intensity I(104) of a 104 plane by X-ray diffraction measurement is at least 1.7.

14. A method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery, the positive electrode active material including a lithium-nickel-manganese composite oxide represented by General Formula (2): Li 1+t Ni x Mn y M z O 2+β (in Formula (2), M is at least one element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; t satisfies −0.05≤t≤0.5, x satisfies 0.1≤x≤0.9, y satisfies 0.05≤y≤0.8, z satisfies 0≤z≤0.8, and x+y+z=1.0; and β satisfies 0≤β≤0.5) and containing a secondary particle formed of flocculated primary particles, the method comprising:
a process of obtaining a mixture by mixing the nickel-manganese composite hydroxide according to claim 1 and a lithium compound together; and
a process of obtaining the lithium-nickel-manganese composite oxide by firing the mixture.

15. The method for producing the positive electrode active material for the nonaqueous electrolyte secondary battery according to claim 14 , wherein the nickel-manganese composite hydroxide is obtained by the method comprising a crystallization process of generating a nickel-manganese composite hydroxide by neutralizing a salt containing at least nickel and a salt containing at least manganese in a reaction aqueous solution, and
wherein in the crystallization process, a dissolved oxygen concentration in the reaction aqueous solution is adjusted to fall within a range of greater than 4.6 mg/L and up to 6.0 mg/L, and a dissolved nickel concentration in the reaction aqueous solution is adjusted to fall within a range of at least 300 mg/L and up to 800 mg/L.

16. A nonaqueous electrolyte secondary battery comprising a positive electrode which comprises the positive electrode active material according to claim 11 .

Assignees

• Sumitomo Metal Mining Co

Inventors

• KANEDA Haruki
• Koshika Yuki
• Ando Takaaki

Classifications

• C01P2004/50

  Agglomerated particles · CPC title

• C01P2006/11

  Powder tap density · CPC title

• H01M2300/0017

  Non-aqueous electrolytes · CPC title

• H01M4/131

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

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title