Nickel manganese composite hydroxide particles and manufacturing method thereof, cathode active material for a non-aqueous electrolyte secondary battery and manufacturing method thereof, and a non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-10044025-B2
Application number	US-201514692213-A
Country	US
Kind code	B2
Filing date	Apr 21, 2015
Priority date	Jun 7, 2011
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Provided are nickel manganese composite hydroxide particles that are a precursor for forming cathode active material comprising lithium nickel manganese composite oxide having hollow structure of particles having a small and uniform particle size for obtaining a non-aqueous electrolyte secondary battery having high capacity, high output and good cyclability. When obtaining the nickel manganese composite hydroxide particles from a crystallization reaction, an aqueous solution for nucleation, which includes at least a metallic compound that contains nickel and a metallic compound that contains manganese, and does not include a complex ion formation agent that forms complex ions with nickel, manganese and cobalt, is controlled so that the temperature of the solution is 60° C. or greater, and so that the pH value that is measured at a standard solution temperature of 25° C. is 11.5 to 13.5, and after nucleation is performed, an aqueous solution for particle growth, which includes the nuclei that were formed in the nucleation step and does not substantially include a complex ion formation agent that forms complex ions with nickel, manganese and cobalt, is controlled so that the temperature of the solution is 60° C. or greater, and so that the pH value that is measured at a standard solution temperature of 25° C. is 9.5 to 11.5, and is less than the pH value in the nucleation step.

First claim

What is claimed is:

1. A cathode active material for a non-aqueous electrolyte secondary battery, the cathode active material comprising:
spherical secondary particles formed with aggregated primary particles of a lithium nickel manganese composite oxide, the lithium nickel manganese composite oxide expressed by the general formula Li 1+u Ni x Mn y Co z M t O 2
wherein
−0.05≤u≤0.50,
x+y+z+t=1,
0.3≤x≤0.7,
0.1≤y≤0.55,
0≤z≤0.4,
0≤t≤0.1,
M is an added element selected from one or more elements from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo and W;

wherein the secondary particles comprise
a layered hexagonal crystal structure,
an average particle size of 3 to 6.5 μm,
a value of 0.55 or less of index ((d90−d10)/average particle size) indicating an extent of a particle size distribution,
a specific surface area of 1 to 1.8 m 2 /g, and
a hollow structure comprising a hollow section formed in a center section of the secondary particles and an outer shell section on the outside of the hollow section, the thickness of the outer shell section being 0.5 to 2 μm; and
a ratio of the thickness of the outer shell section with respect to the particle size of the lithium nickel manganese composite oxide particles is 0.05 to 0.38.

2. A non-aqueous electrolyte secondary battery, the battery comprising:
a cathode comprising a cathode active material,
the cathode active material comprising
spherical secondary particles formed with aggregated primary particles of a lithium nickel manganese composite oxide, the lithium nickel manganese composite oxide expressed by the general formula Li 1+u Ni x Mn y Co 2 M t O 2

wherein
−0.05≤u≤0.50,
x+y+z+t=1,
0.3≤x≤0.7,
0.1≤y≤0.55,
0≤z≤0.4,
0≤t≤0.1,
M is an added element selected from one or more elements from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo and W;

wherein the secondary particles comprise
a layered hexagonal crystal structure,
an average particle size of 3 to 6.5 μm,
a value of 0.55 or less of index ((d90−d10)/average particle size) indicating an extent of a particle size distribution,
a specific surface area of 1 to 1.8 m 2 /g, and
a hollow structure comprising a hollow section formed in a center section of the secondary particles and an outer shell section on the outside of the hollow section, the thickness of the outer shell section being 0.5 to 2 μm; and
a ratio of the thickness of the outer shell section with respect to the particle size of the lithium nickel manganese composite oxide particles is 0.05 to 0.38.

Assignees

• Sumitomo Metal Mining Co

Inventors

• Toya Hiroyuki
• Ryoshi Kazuomi
• Osako Toshiyuki

Classifications

• H01M4/1391

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

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• C01P2004/50

  Agglomerated particles · CPC title

• H01M4/131 Primary

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