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

Patent metadata

Field	Value
Publication number	US-12009517-B2
Application number	US-202318134130-A
Country	US
Kind code	B2
Filing date	Apr 13, 2023
Priority date	Jul 29, 2016
Publication date	Jun 11, 2024
Grant date	Jun 11, 2024

Abstract

Provided are a positive electrode active material with which a nonaqueous electrolyte secondary battery having a high energy density can be obtained, a nickel-manganese composite hydroxide suitable as a precursor of the positive electrode active material, and production methods capable of easily producing these in an industrial scale. Provided is a nickel-manganese composite hydroxide represented by General Formula (1): Ni x Mn y M z (OH) 2+α and containing 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 obtained by X-ray diffraction measurement of at least 0.10° and up to 0.40° and has a degree of sparsity/density represented by [(void area within secondary particle/cross section of secondary particle)×100](%) of at least 0.5% and up to 10%. Also provided is a production method of the nickel-manganese composite hydroxide.

First claim

The invention claimed is:

1. 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; and x, y, z, and a satisfy 0.1≤x≤0.9, 0.05≤y≤0.8, 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 the 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
in the reaction aqueous solution in the crystallization process, a dissolved oxygen concentration is adjusted to fall within a range of at least 0.2 mg/L and up to 4.6 mg/L, and a dissolved nickel concentration is adjusted to fall within a range of at least 700 mg/L and up to 1,500 mg/L.

2. The method for producing a nickel-manganese composite hydroxide according to claim 1 , wherein a stirring power loaded to the reaction aqueous solution in the crystallization process is adjusted to fall within a range of at least 3 kW/m 3 and up to 15 kW/m 3 .

3. The method for producing a nickel-manganese composite hydroxide according to claim 1 , wherein a temperature of the reaction aqueous solution in the crystallization process is adjusted to fall within a range of at least 35° C. and up to 60° C.

4. The method for producing a nickel-manganese composite hydroxide according to claim 1 , wherein a pH value in the crystallization process measured based on a temperature of the reaction aqueous solution at 25° C. is adjusted to fall within a range of at least 10.0 and up to 13.0.

5. The method for producing a nickel-manganese composite hydroxide according to claim 1 , 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 secondary particle.

6. A method for producing 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 additional element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and t, x, y, z, and β satisfy −0.05≤t≤0.5, 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤β≤0.5 and contains a secondary particle formed of a plurality of flocculated primary particles,
the method comprising:
a process of providing 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; and x, y, z, and a satisfy 0.1≤x≤0.9, 0.05≤y≤0.8, 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 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 0.10° and up to 0.40° and has a degree of sparsity/density represented by [(void area within secondary particle/cross section of secondary particle)×100](%) of at least 0.5% and up to 10%;
a process of mixing the nickel-manganese composite hydroxide with a lithium compound to obtain a mixture; and
a process of firing the mixture to obtain the lithium-nickel-manganese composite oxide.

7. The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 6 , wherein the nickel-manganese composite hydroxide is obtained by the method comprising a crystallization process of forming the 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
in the reaction aqueous solution in the crystallization process, a dissolved oxygen concentration is adjusted to fall within a range of at least 0.2 mg/L and up to 4.6 mg/L, and a dissolved nickel concentration is adjusted to fall within a range of at least 700 mg/L and up to 1,500 mg/L.

Assignees

• Sumitomo Metal Mining Co

Inventors

• KANEDA Haruki
• Koshika Yuki
• Ando Takaaki

Classifications

• C01G53/82 Primary

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M2004/8689

  Positive electrodes · CPC title

• H01M10/0525

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

• C01P2006/40

  Electric properties · CPC title

• C01P2006/14

  Pore volume · CPC title