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-2015037676-A1
Application number	US-201314380657-A
Country	US
Kind code	A1
Filing date	Feb 22, 2013
Priority date	Feb 23, 2012
Publication date	Feb 5, 2015
Grant date	—

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 production method for producing nickel composite hydroxide by supplying an aqueous solution that includes at least a nickel salt, a neutralizing agent and a complexing agent 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 secondary 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.

2 . The production method for producing nickel composite hydroxide according to claim 1 , wherein in the primary crystallization process, a pH of the slurry is controlled to be within a range of 10 to 13 at a reference liquid temperature of 25° C.

3 . The production method for producing nickel composite hydroxide according to claim 1 , wherein, in the secondary crystallization process, a concentration of a nickel ammine complex in the slurry is controlled to be within a range of 10 mg/L to 1500 mg/L.

4 . The production method for producing nickel composite hydroxide according to claim 1 , wherein, in the secondary crystallization process, the amount of the slurry is kept constant by using a cross-flow filtering apparatus.

5 . A nickel composite hydroxide 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 8.0 μm to 50.0 μm, and a (D90−D10)/MV that indicates a particle size distribution per volume that is less than 0.5.

6 . The nickel composite hydroxide according to claim 5 that was obtained by the production method of claim 1 .

7 . The nickel composite hydroxide according to claim 5 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).

8 . The nickel composite hydroxide according to claim 7 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).

9 . The nickel composite hydroxide according to claim 5 or claim 6 , wherein the average particle size per volume (MV) is in a range of 18.0 μm to 50.0 μm.

10 . The nickel composite hydroxide according to claim 5 or claim 6 , wherein the average particle size per volume (MV) is in a range of 8.0 μm to 20.0 μm, and a tap density thereof is 1.9 g/cm 3 or more.

11 . 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 5 to 10 , 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 the lithium mixture in an oxidizing atmosphere at 650° C. to 1100° C.

12 . A cathode active material for a non-aqueous electrolyte secondary battery 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 8.0 μm to 50.0 μm, and a (D90−D10)/MV that indicates a particle size distribution per volume that is less than 0.5.

13 . The cathode active material for a non-aqueous electrolyte secondary battery comprising secondary according to claim 12 that was obtained by the production method of claim 11 .

14 . A cathode active material for a non-aqueous electrolyte secondary battery 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 8.0 μm to 20.0 μm, (D90−D10)/MV that indicates a particle size distribution per volume that is less than 0.5, and a tap density of 2.2 g/cm 3 or more.

15 . The cathode active material for a non-aqueous electrolyte secondary battery according to claim 14 that was obtained by the production method of claim 11 .

16 . The cathode active material for a non-aqueous electrolyte secondary battery according to claim 14 or claim 15 , wherein a standard deviation of the average particle size of primary particles of the secondary particles is 10% or less.

17 . The cathode active material for a non-aqueous electrolyte secondary battery according to claim 14 or claim 15 , wherein when used in a cathode of a lithium coin cell battery 2032, a coulomb efficiency of the battery is 90% or more.

18 . The cathode active material for a non-aqueous electrolyte secondary battery according to any one of claims 12 to 15 , having a composition that is expressed by a general expression: Li 1+u Ni 1-x-y Co x M y O 2 (where −0.05≦u≦0.50, 0≦x≦0.35, 0≦y≦0.35, 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).

19 . The cathode active material for a non-aqueous electrolyte secondary battery according to claim 18 , having a composition that is expressed by a general expression: Li 1+u Ni 1-x-y Co x M y O 2 (where −0.05≦u≦0.20, 0≦x≦0.22, 0≦y≦0.3, 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).

20 . A non-aqueous electrolyte secondary battery having a cathode that is made from the cathode active material for a non-aqueous electrolyte secondary battery of any one of claims 12 to 19 .

Assignees

• Sumitomo Metal Mining Co

Inventors

• Yamauchi Mitsuru
• Ryoshi Kazuomi
• Mori Kensaku

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C01P2006/11

  Powder tap density · CPC title

• C01G53/40

  Complex oxides containing nickel and at least one other metal element · 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