Nickel composite hydroxide and production method thereof, cathode active material for a non-aqueous electrolyte secondary battery and production method thereof, and a nonaqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-9685656-B2
Application number	US-201615389387-A
Country	US
Kind code	B2
Filing date	Dec 22, 2016
Priority date	Feb 23, 2012
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

Provided is a cathode active material for a non-aqueous electrolyte secondary battery that has a uniform particle size and high packing density, and that is capable of increased battery capacity and improved coulomb efficiency.
When producing a nickel composite hydroxide that is a precursor to the cathode active material by supplying an aqueous solution that includes at least a nickel salt, a neutralizing agent and a complexing agent into a reaction vessel while stirring and performing a crystallization reaction, a nickel composite hydroxide slurry is obtained while controlling the ratio of the average particle size per volume of secondary particles of nickel composite hydroxide that is generated inside the reaction vessel with respect to the average particle size per volume of secondary particles of nickel composite hydroxide that is finally obtained so as to be 0.2 to 0.6, after which, while keeping the amount of slurry constant and continuously removing only the liquid component, the crystallization reaction is continued until the average particle size per volume of secondary particles of the nickel composite hydroxide becomes 8.0 μm to 50.0 μm.

First claim

What is claimed is:

1. A nickel composite hydroxide that is a precursor to a cathode active material for a non-aqueous electrolyte secondary battery, and comprising secondary particles of nickel composite hydroxide that are formed by an aggregation of plural primary particles, the secondary particles having an average particle size per volume (MV) that is within a range of 9.0 μm to 50.0 μm, and (D90−D10)/MV that indicates a particle size distribution per volume that is less than 0.5.

2. The nickel composite hydroxide according to claim 1 wherein (D90−D10)/MV is 0.30 or more but less than 0.5.

3. The nickel composite hydroxide according to claim 1 that was obtained by a production method for producing a nickel composite hydroxide that is a precursor to a cathode active material for a non-aqueous electrolyte secondary battery;
the method producing the nickel composite hydroxide by supplying an aqueous solution that includes at least a nickel salt, a neutralizing agent and an ammonium ion donor to a reaction vessel while stirring, and performing a crystallization reaction, comprising:
a primary crystallization process of obtaining a nickel composite hydroxide slurry while performing control so that a ratio of an average particle size per volume (MV) of secondary particles of nickel hydroxide that are generated inside the reaction vessel with respect to an average particle size per volume (MV) of secondary particles of nickel composite hydroxide that will finally be obtained becomes 0.2 to 0.6; and
a second crystallization process of continuing the crystallization reaction until the average particles size per volume (MV) of secondary particles of the nickel composite hydroxide becomes 8.0 μm to 50.0 μm, while at the same time maintaining an amount of the slurry obtained in the primary crystallization process and continually removing only a liquid component of the slurry.

4. The nickel composite hydroxide according to claim 1 having a composition that is expressed by a general expression: Ni 1-x-y Co x M y (OH) 2+A (where 0≦x≦0.35, 0≦y≦0.35, 0≦A≦0.5, and M is at least one additional element that is selected from the group comprising Mn, V, Mg, Al, Ti, Mo, Nb, Zr and W).

5. The nickel composite hydroxide according to claim 4 having a composition that can be expressed by a general expression: Ni 1-x-y Co x M y (OH) 2+A (where 0≦x≦0.22, 0≦y≦0.15, x+y<0.3, 0≦A≦0.5, and M is at least one additional element that is selected from the group comprising Mn, V, Mg, Al, Ti, Mo, Nb, Zr and W).

6. The nickel composite hydroxide according to any one of claims 1 to 3 , wherein the average particle size per volume (MV) is in a range of 18.0 μm to 50.0 μm.

7. The nickel composite hydroxide according to any one of claims 1 to 3 , wherein the average particle size per volume (MV) is in a range of 8.0 μm to 20.0 μm, and the tap density is 1.9 g/cm 3 or more.

8. A production method for producing a cathode active material for a non-aqueous electrolyte secondary battery, comprising:
a mixing process of forming a lithium mixture by mixing the nickel composite hydroxides according to any one of claims 1 to 7 , or a nickel composite oxide that was obtained by roasting the nickel composite hydroxide in an oxidizing atmosphere at 300° C. to 1000° C. with a lithium compound; and
a calcination process of performing calcination of this lithium mixture in an oxidizing atmosphere at 650° C. to 1100° C.

9. A cathode active material for a non-aqueous electrolyte secondary battery comprising secondary particles of lithium nickel composite oxide that are formed by an aggregation of plural primary particles,
wherein the secondary particles have an average particle size per volume (MV) that is within a range of 8.0 μm to 50.0 μm, and (D90−D10)/MV that indicates the particle size distribution per volume that is less than 0.5, and
wherein the cathode active material is obtained by the production method of claim 8 .

Assignees

• Sumitomo Metal Mining Co
• Sumitomo Metal Mining Co

Inventors

• Yamauchi Mitsuru
• Ryoshi Kazuomi
• Mori Kensaku

Classifications

• C01P2002/50

  Solid solutions · CPC title

• H01M4/505

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

• C01P2004/61

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

• H01M4/131 Primary

  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