Metal composite hydroxide and method for producing same, positive electrode active material for non-aqueous electrolyte secondary battery and method for producing same, and non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-12580179-B2
Application number	US-201916975304-A
Country	US
Kind code	B2
Filing date	Feb 20, 2019
Priority date	Feb 22, 2018
Publication date	Mar 17, 2026
Grant date	Mar 17, 2026

Abstract

A metal composite hydroxide represented by a general formula (1): Ni 1-x-y Co x Mn y M z (OH) 2+α (where 0.02≤x≤0.3, 0.02≤y≤0.3, 0≤z≤0.05, and −0.5≤α≤0.5 are satisfied and M is at least one element selected from the group consisting of Mg, Ca, Al, Si, Fe, Cr, V, Mo, W, Nb, Ti, and Zr), in which the metal composite hydroxide contains a first particle having a core portion inside the particle and a shell portion formed around the core portion and [(D90−D10)/MV] is 0.80 or more.

First claim

The invention claimed is:

1 . A positive electrode active material for non-aqueous electrolyte secondary battery comprising a lithium-metal composite oxide represented by a general formula (4): Li 1+α Ni 1-x-y Co x Mn y M z O 2+β (where −0.05≤a≤0.50, 0.02≤x≤0.3, 0.02≤y≤0.3, 0≤z≤0.05, −0.5≤β≤0.5, and M is at least one element selected from the group consisting of Mg, Ca, Al, Si, Fe, Cr, V, Mo, W, Nb, Ti, and Zr), wherein
[(D90−D10)/MV] of the positive electrode active material that indicates a dispersion of a particle size in particle size distribution calculated by D90, D10 and the volume average particle diameter (MV) by a laser diffraction scattering method is 0.80 or more,
the lithium-metal composite oxide contains a secondary particle formed of primary particles and having a core portion formed of the primary particles which are aggregated inside the secondary particle and a shell portion formed around the core portion,
a composition of the core portion in the secondary particle is represented by a general formula (5): Li 1+a1 Ni 1-x1-y1 Co x1 Mn y1 M z1 O 2+β1 (where −0.05≤a1≤0.50, 0.7≤(1−x 1 −y 1 )≤0.96, 0≤z 1 ≤0.05, and −0.5≤β 1 ≤0.5 are satisfied),
a composition of the shell portion in the secondary particle is represented by a general formula (6): Li 1+a2 Ni 1-x2-y2 Co x2 Mn y2 M z2 O 2+β2 (where −0.05≤a2≤0.50, (1−x 1 −y 1 )/(1−x 2 −y 2 )>1.0, 0<(1−x 2 −y 2 )<0.6, 0≤z 2 ≤0.05, −0.5≤β 2 ≤0.5 are satisfied), and
the shell portion has a thickness to be 10% or more and 40% or less of a radius of the secondary particle in a direction from a surface to a center of the secondary particle in the secondary particle having a particle size that is in a range of ±10% of the volume average particle diameter (MV) of the positive electrode active material, and
the core portion has a radius to be 60% or more and 90% or less of the radius of the secondary particle in a direction from the center thereof in the secondary particle having the particle size that is in the range of ±10% of the volume average particle diameter (MV) of the positive electrode active material.

2 . The positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , which has a tap density of 2.0 g/cm 3 or more and the volume average particle diameter (MV) of 5 μm or more 20 μm or less in the particle size distribution by the laser diffraction scattering method.

3 . The positive electrode active material for non-aqueous electrolyte secondary battery according to claim 2 , wherein the element M is uniformly distributed inside the lithium-metal composite oxide and/or covers at least a part of a surface of the lithium-metal composite oxide.

4 . A method for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 3 , the method comprising:
a mixing process of mixing a metal composite hydroxide with a lithium compound to obtain a lithium mixture; and a firing process of firing the lithium mixture in an oxidizing atmosphere at 650° C. or more and 900° C. or less, wherein the metal composite hydroxide is represented by a general formula (1): Ni 1-x-y Co x Mn y M z (OH) 2+α (where 0.02≤x≤0.3, 0.02≤y≤0.3, 0≤z≤0.05, and −0.5≤α≤0.5 are satisfied and M is at least one element selected from the group consisting of Mg, Ca, Al, Si, Fe, Cr, V, Mo, W, Nb, Ti, and Zr), wherein [(D90−D10)/MV] that indicates a dispersion of a particle size in particle size distribution calculated by D90, D10 and a volume average particle diameter (MV) by a laser diffraction scattering method is 0.80 or more, the metal composite hydroxide comprises a secondary particle formed of primary particles and having a core portion formed of the primary particles which are aggregated inside the secondary particle and a shell portion formed around the core portion, a composition of the core portion is represented by a general formula (2): Ni 1-x1-y1 Co x1 Mn y1 M z (OH) 2+α1 (where 0.7≤(1−x 1 −y 1 )≤0.96, 0≤z 1 ≤0.05, and −0.5≤α 1 ≤0.5 are satisfied), a composition of the shell portion is represented by a general formula (3): Ni 1-x2-y2 Co x2 Mn y2 M z2 (OH) 2+α2 (where (1−x 1 −y 1 )/(1−x 2 −y 2 )>1.0, 0<(1−x 2 −y 2 )<0.6, 0≤z 2 ≤0.05, and −0.5≤a2≤0.5 are satisfied), and the shell portion has a thickness to be 10% or more and 40% or less of a radius of the particle in a direction from a surface to a center of the secondary particle in the secondary particle having a particle size that is in a range of ±10% of the volume average particle diameter (MV).

5 . The method according to claim 4 , wherein the metal composite hydroxide has the volume average particle diameter (MV) of 5 μm or more and 20 μm or less.

6 . The method according to claim 4 , wherein the element M of the metal composite hydroxide is uniformly present inside the secondary particle and/or on a surface of the secondary particle.

7 . A method for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 5 , the method comprising:
a heat treatment process of subjecting a metal composite hydroxide to a heat treatment; a mixing process of mixing a lithium compound with at least either of a metal composite hydroxide or a metal composite oxide obtained after the heat treatment to obtain a lithium mixture; and a firing process of firing the lithium mixture in an oxidizing atmosphere at 650° C. or more and 900° C. or less, wherein the metal composite hydroxide is represented by a general formula (1): Ni 1-x-y Co x Mn y M z (OH) 2+α (where 0.02≤x≤0.3, 0.02≤y≤0.3, 0≤z≤0.05, and −0.5≤α≤0.5 are satisfied and M is at least one element selected from the group consisting of Mg, Ca, Al, Si, Fe, Cr, V, Mo, W, Nb, Ti, and Zr), wherein [(D90−D10)/MV] that indicates a dispersion of a particle size in particle size distribution calculated by D90, D10 and a volume average particle diameter (MV) by a laser diffraction scattering method is 0.80 or more, the metal composite hydroxide comprises a secondary particle formed of primary particles and having a core portion formed of the primary particles which are aggregated inside the secondary particle and a shell portion formed around the core portion, a composition of the core portion is represented by a general formula (2): Ni 1-x1-y1 Co x1 Mn y1 M z1 (OH) 2+α1 (where 0.7≤(1−x 1 −y 1 )≤0.96, 0≤z 1 ≤0.05, and −0.5≤a 1 ≤0.5 are satisfied), a composition of the shell portion is represented by a general formula (3): Ni 1-x2-y2 Co x2 Mn y2 M z2 (OH) 2+α2 (where (1−x 1 −y 1 )/( 1 −x 2 −y 2 )>1.0, 0<(1−x 2 −y 2 )<0.6, 0≤z 2 ≤0.05, and −0.5≤a2≤0.5 are satisfied), and the shell portion has a thickness to be 10% or more and 40% or less of a radius of the secondary particle in a direction from a surface to a center of the secondary particle in the particle having a particle size that is in a range of +10% of the volume average particle diameter (MV).

8 . The method according to claim 7 , wherein the metal composite hydroxide has the volume average particle diameter (MV) of 5 μm or more and 20 μm or less.

9 . The method according to claim 7 , wherein the element M of the metal composite hydroxide is uniformly present inside the secondary particle and/or on a surface of the secondary particle.

10 . A non-aqueous electrolyte secondary battery comprising a positive electrode containing the positive electrode active material according to claim 1 , a negative electrode, and a non-aqueous electrolyte.

11 . The positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , wherein a thickness of the shell portion is 0.2 μm or more and 1.6 μm or less in the direction from t

Assignees

• Sumitomo Metal Mining Co

Inventors

• Toma Takahiro
• KANEDA Haruki
• Koshika Yuki

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M2004/021

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

• H01M4/505

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