Process for producing nickel cobalt aluminum composite hydroxide and process for producing positive electrode active material for non-aqueous electrolyte secondary batteries

Patent metadata

Field	Value
Publication number	US-10297825-B2
Application number	US-201515523587-A
Country	US
Kind code	B2
Filing date	Oct 20, 2015
Priority date	Oct 30, 2014
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

Disclose herein are processes for producing a nickel cobalt aluminum composite hydroxide and producing a positive electrode active material for non-aqueous electrolyte secondary batteries. Nucleation is performed by controlling an aqueous solution for nucleation containing a nickel-containing metal compound, cobalt-containing metal compound, ammonium ion supplier, and aluminum source so that the aqueous solution's pH for nucleation is 12.0 to 13.4, and then in a particle growth step, particle growth is performed in an aqueous solution for particle growth obtained by controlling the aqueous solution for nucleation obtained in the nucleation step so that the pH of aqueous solution for nucleation is 10.5 to 12.0. Further, in nucleation step, an aqueous solution containing aluminum and sodium is used as the aluminum source contained in aqueous solution for nucleation, and the mole ratio of sodium to aluminum in aqueous solution containing aluminum and sodium is adjusted to 1.5 to 3.0.

First claim

The invention claimed is:

1. A process for producing a nickel cobalt aluminum composite hydroxide by a crystallization reaction,
the nickel cobalt aluminum composite hydroxide being represented by a general formula 1: Ni 1−x−y Co x Al y (OH) 2+α (wherein 0<x≤0.3, 0.1≤y≤0.2, x+y<0.5, 0 ≤α≤0.5),
the process comprising:
a nucleation step in which nucleation is performed by controlling an aqueous solution for nucleation containing a nickel-containing metal compound, a cobalt-containing metal compound, an ammonium ion supplier, and an aluminum source such that a pH of the aqueous solution for nucleation is 12.0 to 13.4 as a pH measured on a basis of a liquid temperature of 25° C.; and
a particle growth step in which particle growth is performed in an aqueous solution for particle growth obtained by controlling the aqueous solution for nucleation obtained in the nucleation step such that a pH of the aqueous solution for particle growth is 10.5 to 12.0 as a pH measured on a basis of a liquid temperature of 25° C.,

wherein, in the nucleation step, an aqueous solution containing aluminum and sodium is used as the aluminum source contained in the aqueous solution for nucleation, and a mole ratio of sodium to aluminum in the aqueous solution containing aluminum and sodium is adjusted to 1.5 to 3.0.

2. The process for producing a nickel cobalt aluminum composite hydroxide according to claim 1 , wherein the aqueous solution containing aluminum and sodium is an aqueous sodium aluminate solution.

3. The process for producing a nickel cobalt aluminum composite hydroxide according to claim 1 , wherein in the nucleation step and the particle growth step, a reaction temperature is maintained at 20° C. or higher.

4. The process for producing a nickel cobalt aluminum composite hydroxide according to claim 1 , wherein in the nucleation step and the particle growth step, concentrations of ammonium ions in the aqueous solution for nucleation and the aqueous solution for particle growth are maintained in a range of 3 g/L to 25 g/L.

5. A process for producing a positive electrode active material for non-aqueous electrolyte secondary batteries, which comprises a lithium nickel cobalt aluminum composite oxide, from a nickel cobalt aluminum composite hydroxide and/or a nickel cobalt aluminum composite oxide,
the nickel cobalt aluminum composite hydroxide being represented by a general formula 1: Ni 1−x−y Co x Al y (OH) 2+α (wherein 0<x≤0.3, 0.1≤y≤0.2, x+y<0.5, 0 ≤α≤0.5), and
the lithium nickel cobalt aluminum composite oxide comprising a hexagonal lithium-containing composite oxide having a layered structure and being represented by a general formula 2: Li t Ni 1−x−y Co x Al y O 2 (wherein 0.95≤t≤1.15, 0<x≤0.3, 0.1≤y ≤0.2, x+y<0.5),
the process comprising:
a nucleation step in which nucleation is performed by controlling an aqueous solution for nucleation containing a nickel-containing metal compound, a cobalt-containing metal compound, an ammonium ion supplier, and an aluminum source such that a pH of the aqueous solution for nucleation is 12.0 to 13.4 as a pH measured on a basis of a liquid temperature of 25° C.;
a particle growth step in which particle growth is performed in an aqueous solution for particle growth obtained by controlling the aqueous solution for nucleation obtained in the nucleation step such that a pH of the aqueous solution for particle growth is 10.5 to 12.0 as a pH measured on a basis of a liquid temperature of 25° C.;
a mixing step in which a mixture is formed by mixing a lithium compound with the nickel cobalt aluminum composite hydroxide and/or the nickel cobalt aluminum composite oxide obtained by heat-treating a nickel cobalt aluminum composite hydroxide in an oxidizing atmosphere; and
a calcining step in which the mixture obtained in the mixing step is calcined,

wherein in the nucleation step, an aqueous solution containing aluminum and sodium is used as the aluminum source contained in the aqueous solution for nucleation, and a mole ratio of sodium to aluminum in the aqueous solution containing aluminum and sodium is adjusted to 1.5 to 3.0.

6. The process for producing a positive electrode active material for non-aqueous electrolyte secondary batteries according to claim 5 , wherein in the calcining step, the mixture obtained in the mixing step is calcined at a temperature of 700° C. to 950° C.

Assignees

• Sumitomo Metal Mining Co

Inventors

• Ryoshi Kazuomi
• Yamaji Koji
• Mori Kensaku

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• C01G53/04

  Oxides · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M2004/028

  Positive electrodes · CPC title