Nickel-cobalt-manganese composite hydroxide and method for producing same

Patent metadata

Field	Value
Publication number	US-9941515-B2
Application number	US-201414898924-A
Country	US
Kind code	B2
Filing date	Jun 13, 2014
Priority date	Jun 19, 2013
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

Achieved is a nickel-cobalt-manganese composite hydroxide which is excellent in reactivity with a lithium compound, and excellent thermal stability and battery characteristics. The nickel-cobalt-manganese composite hydroxide is represented by a general formula: Ni 1-x-y-z Co x Mn y M z (OH) 2 (0<x≤⅓, 0<y≤⅓, 0≤z≤0.1, M represents one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Zr, Nb, Mo, and W), to serve as a precursor for a positive electrode active material of a non-aqueous electrolyte secondary battery, and the nickel-cobalt-manganese composite hydroxide has a specific surface area of 3.0 to 11.0 m 2 /g as measured by a nitrogen adsorption BET method, and a ratio I(101)/I(100) of peak intensity I(101) of plane (101) to peak intensity I(100) of plane (100) less than 0.300 through an X-ray diffraction measurement.

First claim

The invention claimed is:

1. A nickel-cobalt-manganese composite hydroxide represented by a general formula: Ni 1-x-y-z Co x Mn y M z (OH) 2 (0<x≤⅓, 0<y≤⅓, 0≤z≤0.1, M represents one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Zr, Nb, Mo, and W), to serve as a precursor for a positive electrode active material of a non-aqueous electrolyte secondary battery,
wherein the nickel-cobalt-manganese composite hydroxide has a specific surface area of 3.0 to 11.0 m 2 /g as measured by a nitrogen adsorption BET method, a ratio I(101)/I(100) of peak intensity I(101) of plane (101) to peak intensity I(100) of plane (100) less than 0.300 through an X-ray diffraction measurement, and a mesopore volume of 0.010 to 0.035 ml/g as measured by a nitrogen adsorption method.

2. The nickel-cobalt-manganese composite hydroxide according to claim 1 , wherein the nickel-cobalt-manganese composite hydroxide has an average particle size of 5 to 15 μm on a volumetric basis by a laser diffraction/scattering method.

3. A method for producing a nickel-cobalt-manganese composite hydroxide represented by a general formula: Ni 1-x-y-z Co x Mn y M z (OH) 2 (0<x≤⅓, 0<y≤⅓, 0≤z≤0.1, M represents one or more elements selected from Mg, Al, Ca, Ti, V, Cr, Zr, Nb, Mo, and W), to serve as a precursor for a positive electrode active material of a non-aqueous electrolyte secondary battery, the method comprising:
a crystallization step of mixing, in a reaction vessel, a mixed aqueous solution containing at least a nickel salt, a cobalt salt, and a manganese salt, and an aqueous solution containing an ammonium ion supplier, and supplying an aqueous solution of caustic alkali so that pH on the basis of a liquid temperature of 25° C. is kept in a range of 11 to 13, thereby providing a reaction solution, and crystallizing nickel-cobalt-manganese composite hydroxide particles in the reaction solution, while maintaining an oxygen concentration of an atmosphere in contact with an open side of the reaction solution at 0.2 volume % or less by supplying an inert gas into the reaction vessel;
an oxidation step of supplying an oxidant to slurry of the nickel-cobalt-manganese composite hydroxide particles formed in the crystallization step to oxidize the nickel-cobalt-manganese composite hydroxide particles, thereby making a ratio I(101)/I(100) of peak intensity I(101) of plane (101) to peak intensity I(100) of plane (100) through an X-ray diffraction measurement less than 0.300;
a solid-liquid separation step of applying solid-liquid separation and water washing to the oxidized nickel-cobalt-manganese composite hydroxide particles; and
a drying step of drying the nickel-cobalt-manganese composite hydroxide particles subjected to the solid-liquid separation.

4. The method for producing a nickel-cobalt-manganese composite hydroxide according to claim 3 , wherein the nickel-cobalt-manganese composite hydroxide particles are oxidized by supplying oxygen as the oxidant to the slurry with the pH of the slurry adjusted to 12.5 or more on the basis of 25° C. in the oxidation step.

5. The method for producing a nickel-cobalt-manganese composite hydroxide according to claim 3 , wherein the reaction solution has a temperature maintained in a range of 20 to 70° C., and an ammonium ion concentration maintained in a range of 5 to 20 g/L in the crystallization step.

6. The method for producing a nickel-cobalt-manganese composite hydroxide according to claim 3 , wherein the mixed aqueous solution, the aqueous solution containing the ammonium ion supplier, and the aqueous solution of caustic alkali are each continuously supplied to continuously overflow the reaction solution containing the nickel-cobalt-manganese composite hydroxide particles from the reaction vessel, and collect the nickel-cobalt-manganese composite hydroxide particles.

7. The method for producing a nickel-cobalt-manganese composite hydroxide according to claim 3 , wherein the nickel-cobalt-manganese composite hydroxide particles have surfaces coated with a hydroxide of an additive element M.

8. The method for producing a nickel-cobalt-manganese composite hydroxide according to claim 3 , wherein the nickel salt, the cobalt salt, and the manganese salt are at least one of a sulfate, a nitrate, or a chloride.

9. The method for producing a nickel-cobalt-manganese composite hydroxide according to claim 3 , wherein the ammonium ion supplier is at least one of ammonia, ammonium sulfate, or ammonium chloride.

10. The nickel-cobalt-manganese composite hydroxide according to claim 1 , wherein the nickel-cobalt-manganese composite hydroxide is produced by a method comprising:
a crystallization step of mixing, in a reaction vessel, a mixed aqueous solution containing at least a nickel salt, a cobalt salt, and a manganese salt, and an aqueous solution containing an ammonium ion supplier, and supplying an aqueous solution of caustic alkali so that pH on the basis of a liquid temperature of 25° C. is kept in a range of 11 to 13, thereby providing a reaction solution, and crystallizing nickel-cobalt-manganese composite hydroxide particles in the reaction solution, while maintaining an oxygen concentration of an atmosphere in contact with an open side of the reaction solution at 0.2 volume % or less by supplying an inert gas into the reaction vessel;
an oxidation step of supplying an oxidant to slurry of the nickel-cobalt-manganese composite hydroxide particles formed in the crystallization step to oxidize the nickel-cobalt-manganese composite hydroxide particles, thereby making a ratio I(101)/I(100) of peak intensity I(101) of plane (101) to peak intensity I(100) of plane (100) through an X-ray diffraction measurement less than 0.300;
a solid-liquid separation step of applying solid-liquid separation and water washing to the oxidized nickel-cobalt-manganese composite hydroxide particles; and
a drying step of drying the nickel-cobalt-manganese composite hydroxide particles subjected to the solid-liquid separation.

Assignees

• Sumitomo Metal Mining Co

Inventors

• Kamata Yasutaka
• Toya Hiroyuki

Classifications

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title

• C01P2002/50

  Solid solutions · CPC title

• C01P2002/52

  containing elements as dopants · CPC title

• C01P2006/12

  Surface area · CPC title

• C01P2004/84

  one phase coated with the other · CPC title