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

Patent metadata

Field	Value
Publication number	US-9406930-B2
Application number	US-201214366871-A
Country	US
Kind code	B2
Filing date	Dec 20, 2012
Priority date	Dec 20, 2011
Publication date	Aug 2, 2016
Grant date	Aug 2, 2016

Abstract

Provided is a lithium composite oxide having a uniform and suitable particle size and high specific surface area due to a hollow structure that can be produced on an industrial scale. A nickel composite hydroxide as a raw material thereof is obtained controlling the particle size distribution of the nickel composite hydroxide, the nickel composite hydroxide having a structure comprising a center section that comprises minute primary particles, and an outer-shell section that exists on the outside of the center section and comprises plate shaped primary particles that are larger than the primary particles of the center section, by a nucleation process and a particle growth process that are separated by controlling the pH during crystallization, and by controlling the reaction atmosphere in each process and the manganese content in a metal compound that is supplied in each process.

First claim

What is claimed is:

1. A production method for producing by a crystallization reaction nickel composite hydroxide that is expressed by a general formula (1): Ni x Co y Al z Mn t M s (OH) 2+a (x+y+z+t+s=1, 0≦y≦0.3, 0<z≦0.1, 0.001<t≦0.05, 0≦s≦0.05, 0≦a≦0.5, and M is at least one additional element that is selected from the group comprising Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W), comprising:
a nucleation process controlling a nucleation aqueous solution that includes a metal compound that includes metal elements at a composition ratio that is expressed by a general formula (a): Ni x Co y Al z Mn t M s (x+y+z+t+s=1, 0≦y≦0.8, 0≦z≦0.1, 0.1≦t≦0.8, 0≦s≦0.05, and M is at least one additional element that is selected from the group comprising Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W) and an ammonium ion donor so that the pH value at a reference liquid temperature of 25° C. becomes 12.0 to 14.0, and performing nucleation with supplying the metal compound and the ammonium ion donor in an oxidizing atmosphere having an oxygen concentration greater than 1% by volume; and
a particle growth process of controlling a particle growth aqueous solution that includes nuclei that were formed in the nucleation process so that the pH value at a reference liquid temperature of 25° C. becomes 10.5 to 12.0, and growing the nuclei with supplying the metal compound and the ammonium ion donor, and, at a time from the start of the particle growth process within a range of 1% to 15% of the total time from the start to end of the particle growth process, switching from the oxidizing atmosphere to a mixed atmosphere of oxygen and inert gas having an oxygen concentration of 1% by volume or less and replacing the supplied metal compound with a metal compound that includes metal elements at a composition ratio that is expressed by a general formula (b): Ni x Co y Al z Mn t M s (x+y+z+t+s=1, 0≦y≦0.3, 0≦z≦0.1, 0≦t<0.05, 0≦s≦0.05, and M is at least one additional element that is selected from the group comprising Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W), and continuing to grow the nuclei with supplying the metal compound and the ammonium ion donor;
and further comprising a process of coating an aluminum compound on the nickel composite hydroxide that is obtained in the particle growth process, at least in case that aluminum is not included in any of the metal compound that is included in the nucleation aqueous solution and the metal compound that is supplied in the particle growth process.

2. The production method for producing nickel composite hydroxide according to claim 1 , wherein the oxygen concentration of the oxidizing atmosphere is 10% by volume or greater.

3. The production method for producing nickel composite hydroxide according to claim 1 , wherein switching the atmosphere and the supplied metal compound in the particle growth process is performed in the range of 2% to 12.5% from the start of the particle growth process.

4. The production method for producing nickel composite hydroxide according to claim 1 , wherein an aqueous solution that is formed by adjusting the pH value of the nucleation aqueous solution after the nucleation process has ended is used as the particle growth aqueous solution.

5. The production method for producing nickel composite hydroxide according to claim 1 , wherein the oxygen concentration of the mixed atmosphere is 0.5% by volume or less.

6. The production method for producing nickel composite hydroxide according to claim 1 , wherein, in the particle growth process, part of the liquid component of the particle growth aqueous solution is removed.

7. The production method for producing nickel composite hydroxide according to claim 1 , wherein, in the nucleation process and in the particle growth process, the ammonia concentration of the nucleation aqueous solution and the particle growth aqueous solution is maintained within the range of 3 g/L to 25 g/L.

8. The production method for producing nickel composite hydroxide according to claim 1 , further comprising a process of coating a compound of the one kind of additional element or more on the nickel composite hydroxide that was obtained in the particle growth process.

9. A nickel composite hydroxide that is expressed by a general formula (1): Ni x Co y Al z Mn t M s (OH) 2+a (x+y+z+t+s=1, 0≦y≦0.3, 0<z≦0.1, 0.001<t≦0.05, 0≦s≦0.05, 0≦a≦0.5, and M is at least one additional element that is selected from the group comprising Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W), comprising spherical shaped secondary particles that are formed by an aggregation of plural primary particles, with the secondary particles having an average particle size of 3 μm to 15 μm, and an index value [(d90−d10/average particle size] that indicates the spread of the particle size distribution of 0.55 or less;
the secondary particles comprising:
a center section comprising minute primary particles of a composite hydroxide that is expressed by a general formula (2): Ni x Co y Al z Mn t M s (OH) 2+a (x+y+z+t+s=1, 0≦y≦0.8, 0≦z≦0.1, 0.1≦t≦0.8, 0≦s≦0.05, 0≦a≦0.5, and M is at least one additional element that is selected from the group comprising Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W): and
an outer-shell section comprising plate shaped primary particles that are larger than the minute primary particles and that exists on the outside of the center section, and are constructed by composite hydroxide that is expressed by a general formula (3): Ni x Co y Al z Mn t M s (OH) 2+a (x+y+z+t+s=1, 0≦y≦0.3, 0≦z≦0.1, 0≦t<0.05, 0≦s≦0.05, 0≦a≦0.5, and M is at least one additional element that is selected from the group comprising Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W); and
aluminum existing in at least one of the center section and the outer-shell section, or existing as an aluminum compound on the surface of the secondary particles,
the minute primary particles having an average particle size of 0.01 μm to 0.3 μm, and the plate shaped primary particles having an average particle size of 0.3 μm to 3 μm, and
the ratio of the thickness of the outer-shell section with respect to the particle size of the secondary particles being 5% to 45%.

10. The nickel composite hydroxide according to claim 9 , wherein the aluminum is uniformly distributed inside the secondary particles and/or the aluminum compound uniformly coats the surface of the secondary particles.

11. The nickel composite hydroxide according to claim 9 , wherein the one kind of additional element or more is uniformly distributed inside the secondary particles and/or compound of the one kind of additional element or more uniformly coats the surface of the secondary particles.

12. A production method for producing a cathode active material for a non-aqueous electrolyte secondary battery comprising a lithium nickel composite oxide having a layered hexagonal crystal structure that comprises spherical shaped secondary particles that are formed from an aggregation of plural primary particles and expressed by a general formula (4): Li 1+u Ni x Co y Al z Mn t M s O 2 (where, −0.05≦u≦0.20, x+y+z+t+s=1, 0≦y≦0.3, 0<z≦0.1, 0.01<t≦0.05, 0≦s≦0.05, and M is selected from at least one kind of additional element that is selected from the group of Mg, Ca, Ti, V, Cr, Zr, Nb, Mo and W), comprising:
a heat treatment process of heating the nickel composite hydroxide of claim 9 at a temperature of 105° C. to 750° C.;
a mixing process of mixing a lithium compound into the heat treated nickel composite hydroxide or a nickel composite oxide obtained by the heat treatment process to form a lithium mixture; and
a calcination process of performing calcination of the lithium mixture obtained by the mixing process at a temperature of 700° C. to 800° C. in an oxidizing atmosphere

Assignees

• Sumitomo Metal Mining Co

Inventors

• Fukui Atsushi
• Toya Hiroyuki

Classifications

• C01G53/82 Primary

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

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• Y02P70/54

  Cross-Sectional Technologies · mapped topic

• H01M4/364 Primary

  as mixtures · CPC title

• C01G53/006

  Chemistry & Metallurgy · mapped topic