Nickel manganese containing composite hydroxide and manufacturing method for producing same

Patent metadata

Field	Value
Publication number	US-2018316006-A1
Application number	US-201615764453-A
Country	US
Kind code	A1
Filing date	Sep 27, 2016
Priority date	Sep 30, 2015
Publication date	Nov 1, 2018
Grant date	—

Abstract

The present invention industrially provides: a non-aqueous electrolyte secondary battery having a high energy density and high cycling characteristics; a cathode active material for a non-aqueous electrolyte secondary battery having a high packing efficiency; and a nickel manganese containing composite hydroxide having a small particle size, a narrow particle size distribution, and a high sphericity. When producing the nickel manganese containing composite hydroxide by a crystallization reaction using material solution where metal compounds including nickel and manganese dissolve, a nucleation process is performed in a non-oxidizing atmosphere by stirring an aqueous solution for nucleation, that includes the quantity of the material solution corresponding to 0.6% to 5.0% of the whole amount of substance of metal element included in a metal compound used for the overall crystallization reaction.

First claim

1 . A nickel manganese containing composite hydroxide represented by a general formula of: Ni x Mn y M z (OH) 2 (x+y+z=1, 0.1≤x≤0.7, 0.1≤y≤0.5, 0.1≤z≤0.5; M is one or more of element that is selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W),
the nickel manganese containing composite hydroxide comprising secondary particles formed by an aggregation of primary particles, and
the secondary particles having a median diameter D50 within a range of 1 μm to 6 μm, an index [(D90−D10)/D50] which indicates a spread of a particle size distribution of less than 0.50, and a tap density according to JIS2512:2012 within a range of 1.60 g/cm 3 to (0.04×D50+1.60) g/cm 3 .

2 . A nickel manganese containing composite hydroxide according to claim 1 , wherein a Wadell's sphericity is within a range of 0.70 to 0.98.

3 . A manufacturing method for nickel manganese containing composite hydroxide represented by a general formula of: Ni x Mn y M z (OH) 2 (x+y+z=1, 0.1≤x≤0.7, 0.1≤y≤0.5, 0.1≤z≤0.5; M is one or more of element that is selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W), manufacturing the nickel manganese containing composite hydroxide by a crystallization reaction using a material solution where metal compound including nickel and manganese dissolve, the manufacturing method comprising steps of:
a nucleation process performed in a non-oxidizing atmosphere having an oxygen concentration of 5% by volume or less by stirring an aqueous solution for nucleation including a quantity of the material solution corresponding to 0.6% to 5.0% of the whole amount of substance of metal element included in the metal compound used for the overall crystallization reaction, while controlling an ammonium ion concentration of the aqueous solution for nucleation within a range of 3 g/L to 25 g/L, a pH of the aqueous solution for nucleation within a range of 12.0 to 14.0 at a solution temperature of 25° C. as a standard, and a stirring power requirement within a range of 6.0 kW/m 3 to 30 kW/m 3 , to generate nuclei, and
a particle growth process growing the nuclei by supplying the material solution to an aqueous solution for particle growth including the nuclei while controlling an ammonium ion concentration of the aqueous solution for particle growth within a range of 3 g/L to 25 g/L and a pH of the aqueous solution for particle growth within a range of 10.5 to 12.0 at a solution temperature of 25° C. as a standard.

4 . A cathode active material for a non-aqueous electrolyte secondary battery represented by a general formula of: Li a Ni x Mn y M z O 2 (0.95≤a≤1.15, x+y+z=1, 0.1≤x≤0.7, 0.1≤y≤0.5, 0.1≤z≤0.5; M is one or more of element that is selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W), and comprising a layered hexagonal lithium nickel manganese containing composite oxide,
the composite oxide comprising secondary particles formed by an aggregation of primary particles, and
the secondary particles having a median diameter D50 within a range of 1 μm to 6 m, an index of [(D90−D10)/D50] which indicates a spread of a particle size distribution of less than 0.50, and a tap density according to JIS2512:2012 is within a range of 1.89 g/cm 3 to (0.09×D50+1.80) g/cm 3 .

5 . A cathode active material for a non-aqueous electrolyte secondary battery according to claim 4 , wherein a Wadell's sphericity is within a range of 0.60 to 0.98.

6 . A manufacturing method of a cathode active material for a non-aqueous electrolyte secondary battery represented by a general formula of: Li a Ni x Mn y M z O 2 (0.95≤a≤1.15, x+y+z=1, 0.1≤x≤0.7, 0.1≤y≤0.5, 0.1≤z≤0.5; M is one or more of element that is selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W), and comprising a layered hexagonal lithium nickel manganese containing composite oxide, the composite oxide comprising secondary particles formed by an aggregation of primary particles, the manufacturing method comprising steps of:
mixing process to obtain a lithium mixture by mixing lithium compound to the nickel manganese containing composite hydroxide of claim 1 to have a ratio of a number of lithium atoms against a number of metal element other than lithium within a range of 0.95 to 1.15, and
a firing process of sintering the lithium mixture in an oxidizing atmosphere within a temperature range of 750° C. to 1000° C.

7 . A non-aqueous electrolyte secondary battery comprising a cathode material, wherein the cathode material comprises the cathode active material for a non-aqueous electrolyte secondary battery of claim 4 .

8 . A manufacturing method of a cathode active material for a non-aqueous electrolyte secondary battery represented by a general formula of: Li a Ni x Mn y M z O 2 (0.95≤a≤1.15, x+y+z=1, 0.1≤x≤0.7, 0.1≤y≤0.5, 0.1≤z≤0.5; M is one or more of element that is selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W), and comprising a layered hexagonal lithium nickel manganese containing composite oxide, the composite oxide comprising secondary particles formed by an aggregation of primary particles, the manufacturing method comprising steps of:
mixing process to obtain a lithium mixture by mixing lithium compound to the nickel manganese containing composite hydroxide of claim 2 to have a ratio of a number of lithium atoms against a number of metal element other than lithium within a range of 0.95 to 1.15, and
a firing process of sintering the lithium mixture in an oxidizing atmosphere within a temperature range of 750° C. to 1000° C.

9 . A non-aqueous electrolyte secondary battery comprising a cathode material, wherein the cathode material comprises the cathode active material for a non-aqueous electrolyte secondary battery of claim 5 .

Assignees

• Sumitomo Metal Mining Co

Inventors

• KANEDA Haruki
• Ando Takaaki
• Ushio Ryozo

Classifications

• C01P2004/32

  Spheres · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/0525

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