Nickel manganese composite hydroxide and method for producing same, positive electrode active material for nonaqueous electrolyte secondary battery and method for producing same, and nonaqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-2019260024-A1
Application number	US-201716320748-A
Country	US
Kind code	A1
Filing date	Jun 6, 2017
Priority date	Jul 29, 2016
Publication date	Aug 22, 2019
Grant date	—

Abstract

Provided are a nickel-manganese composite hydroxide capable of producing a secondary battery having a high particle fillability and excellent battery characteristics when used as a precursor of a positive electrode active material and a method for producing the same. A nickel-manganese composite hydroxide is represented by General Formula: NixMnyMz(OH)2+α and contains a secondary particle formed of a plurality of flocculated primary particles. The primary particles have an aspect ratio of at least 3, and at least some of the primary particles are disposed radially from a central part of the secondary particle toward an outer circumference thereof. The secondary particle has a ratio I(101)/I(001) of a diffraction peak intensity I(101) of a 101 plane to a peak intensity I(001) of a 001 plane, measured by an X-ray diffraction measurement, of up to 0.15.

First claim

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 additional element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and x, y, z, and α satisfy 0.1≤x≤0.8, 0.1≤y≤0.6, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4) and containing a secondary particle formed of a plurality of flocculated primary particles, wherein
the primary particles have an aspect ratio of at least 3, and at least some of the primary particles are disposed radially in a direction from a central part of the secondary particle to an outer circumference thereof, and
the secondary particle has a ratio (I(101)/I(001)) of a diffraction peak intensity I(101) of a 101 plane to a diffraction peak intensity I(001) of a 001 plane, measured by an X-ray diffraction measurement, of up to 0.15.

2 . The nickel-manganese composite hydroxide according to claim 1 , wherein in an area within 50% of a radius of the secondary particle from the outer circumference of the secondary particle toward the central part thereof, at least 50% of the primary particles in number relative to a total number of the primary particles present within this area are disposed radially.

3 . The nickel-manganese composite hydroxide according to claim 1 , wherein a total pore volume in a pore volume distribution is at least 0.015 cm 3 /g and up to 0.03 cm 3 /g.

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

5 . 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 additional element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf Ta, Fe, and W; and x, y, z, and α satisfy 0.1≤x≤0.8, 0.1≤y≤0.6, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4) and containing a secondary particle formed of a plurality of flocculated primary particles,
the method comprising a crystallization process of forming a nickel-manganese composite hydroxide by neutralizing a salt containing at least nickel and a salt containing at least manganese in an aqueous reaction solution, wherein
in the crystallization process, a dissolved nickel concentration in the aqueous reaction solution is controlled in a range of at least 300 mg/L and up to 1,500 mg/L, a dissolved oxygen concentration is controlled in a range of at least 0.5 mg/L and up to 3.5 mg/L, and a stirring power applied to the aqueous reaction solution is controlled in a range of at least 4 kW/m 3 and up to 8 kW/m 3 .

6 . The method for producing a nickel-manganese composite hydroxide according to claim 5 , wherein the crystallization process includes continuously adding a mixed aqueous solution including nickel and manganese into a reaction vessel and overflowing slurry including nickel-manganese composite hydroxide particles formed by neutralization to recover the particles.

7 . The method for producing a nickel-manganese composite hydroxide according to claim 6 , wherein in the crystallization process, a residence time of the mixed aqueous solution in the reaction vessel is at least 3 hours and up to 15 hours.

8 . A method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery, the method comprising:
a process of mixing the nickel-manganese composite hydroxide according to claim 1 and a lithium compound to obtain a mixture; and a process of firing the mixture to obtain a lithium-nickel-manganese composite oxide.

9 . The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 8 , wherein the nickel-manganese composite hydroxide is obtained by the method comprising a crystallization Process of forming a nickel-manganese composite hydroxide by neutralizing a salt containing at least nickel and a salt containing at least manganese in an aqueous reaction solution,
Wherein, in the crystallization process, a dissolved nickel concentration in the aqueous reaction solution is controlled in a range of at least 300 me/L and up to 1,500 mg/L, a dissolved oxygen concentration is controlled in a range of at least 0.5 m/L and up to 3.5 mg/L, and a stirring power applied to the aqueous reaction solution is controlled in a range of at least 4 kW/m 3 and up to 8 kW/m 3 .

10 . A positive electrode active material for a nonaqueous electrolyte secondary battery, the positive electrode active material comprising:
a lithium-nickel-manganese composite oxide containing a secondary particle formed of a plurality of flocculated primary particles and represented by General Formula (2): Li 1+u Ni x Mn y M z O Z+β (in Formula (2), M is at least one additional element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and u, x, y, z, and β satisfy −0.05≤u≤0.5, 0.1≤x≤0.8, 0.1≤y≤0.6, 0≤z≤0.8, x+y+z=1.0, and 0≤β≤0.5), wherein when an arbitrary radial direction from a center of a cross section of the secondary particle toward an outside thereof is regarded as an x-axis direction and a direction perpendicular to the x-axis direction is regarded as a y-axis direction, an orientation rate of a crystal ab plane measured by an electron backscatter diffraction method is at least 55% in each of the x-axis direction and the y-axis direction.

11 . A positive electrode active material for a nonaqueous electrolyte secondary battery, the positive electrode active material comprising:
a lithium-nickel-manganese composite oxide containing a secondary particle formed of a plurality of flocculated primary particles and represented by General Formula (2): Li 1+u Ni x Mn y M z O 2−β (in Formula (2), M is at least one additional element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and u, x, y, z, and β satisfy −0.05≤u≤0.5, 0.1≤x≤0.8, 0.1≤y≤0.6, 0≤z≤0.8, x+y+z=1.0, and 0≤β≤0.5), wherein the primary particles have an aspect ratio of at least 2, and at least some of the primary particles are disposed radially in a direction from a central part of the particle to an outer circumference thereof, a sparse density obtained from an image analysis result of a SEM image of a cross section of the secondary particle is at least 0.5% and up to 25%, and a particle strength is at least 70 MPa and up to 100 MPa.

12 . The positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 11 , wherein in an area within 50% of a radius of the secondary particle from the outer circumference of the secondary particle toward the central part thereof, at least 50% of the primary particles in number relative to a total number of the primary particles present within this area are disposed radially.

13 . The positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 10 , wherein a volume-average particle diameter MV is at least 5 μm and up to 20 μm, and [(D90−D10)/average particle diameter] that is an indicator to represent a spread of particle size distribution is at least 0.7.

14 . A nonaqueous electrolyte secondary battery comprising:
a positive electrode that comprises the positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 10 .

Assignees

• Sumitomo Metal Mining Co

Inventors

• Nakamura Takuma
• KANEDA Haruki
• Honma Takehide
• Ando Takaaki
• Yamaji Koji

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• C01P2006/40

  Electric properties · CPC title

• H01M4/505

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

• C01P2004/54

  Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title