Nickel-manganese composite hydroxide particles, method for producing same, cathode active material for non-aqueous electrolyte secondary batteries, method for producing same, and non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-10236507-B2
Application number	US-201515115375-A
Country	US
Kind code	B2
Filing date	Jan 29, 2015
Priority date	Jan 31, 2014
Publication date	Mar 19, 2019
Grant date	Mar 19, 2019

Abstract

The object of the present invention is to improve the roundness of nickel-manganese composite hydroxide particles obtained by a crystallization process, and to improve the filling characteristic of cathode active material produced using the nickel-manganese composite hydroxide particles as a precursor. A reaction aqueous solution is formed by supplying a raw material aqueous solution including at least Ni and Mn, an aqueous solution including an ammonium-ion donor, and an alkali solution into a reaction tank, and mixing, then nickel-manganese composite hydroxide particles are crystallized. When doing this, the oxygen concentration inside the reaction tank is controlled to be 3.0% by volume or greater, the temperature of the reaction aqueous solution is controlled to be 35° C. to 60° C., and the nickel-ion concentration is controlled to be 1,000 mg/L or greater. As a result, nickel-manganese composite hydroxide particles are obtained that include secondary particles formed by an aggregation of plural primary particles and expressed by the general formula: Ni x Mn y M t (OH) 2+α (where 0.05≤x≤0.95, 0.05≤y≤0.95, 0≤t≤0.20, x+y+t=1, 0≤α≤0.5, and M is one or more elements selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W); and the average value of the roundness of cathode active material having a particle size that is 70% the average particle size or more is 0.82 or greater, and the tap density is 2.20 g/cm 3 or greater.

First claim

What is claimed is:

1. A method for producing nickel-manganese composite hydroxide particles comprising secondary particles formed by an aggregation of plural primary particles and expressed by a general formula: Ni x Mn y M t (OH) 2+α ,
where
0.05≤ x≤ 0.95,

0.05≤ y≤ 0.95,

0≤ t≤ 0.20,

x+y+t= 1, 0≤α≤0.5,and

M is one or more elements selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W; wherein
a reaction aqueous solution is formed by supplying a raw material aqueous solution including at least nickel and manganese, an aqueous solution including an ammonium-ion donor, and an alkali solution into a reaction tank and mixing; and
when crystallizing the nickel-manganese composite hydroxide particles, an oxygen concentration inside the reaction tank is controlled to be 3.0% by volume or less, a temperature of the reaction aqueous solution is controlled to be 35° C. to 60° C., and a nickel-ion concentration of the reaction aqueous solution is controlled to be 1,000 mg/L or more.

2. The method for producing nickel-manganese composite hydroxide particles according to claim 1 wherein the temperature of the reaction aqueous solution is 35° C. to 45° C.

3. The method for producing nickel-manganese composite hydroxide particles according to claim 1 , wherein the pH value at a reference liquid temperature of 25° C. is controlled to be within a range of 10.5 to 13.0, and an ammonium-ion concentration is controlled to be within a range of 5 g/L to 25 g/L.

4. The method for producing nickel-manganese composite hydroxide particles according to claim 1 , wherein at least one kind selected from among the group of sulfates, nitrates and chlorides is used as the nickel salt and manganese salt.

5. The method for producing nickel-manganese composite hydroxide particles according to claim 1 , wherein at least one kind selected from among the group of ammonia, ammonium sulfate, and ammonium chloride is used as the ammonium-ion donor.

6. The method for producing nickel-manganese composite hydroxide particles according to claim 1 , wherein a sodium hydroxide aqueous solution is used as the alkali solution.

7. The method for producing nickel-manganese composite hydroxide particles according to claim 1 , wherein the nickel-manganese composite hydroxide particles are recovered by causing the reaction aqueous solution inside the reaction tank to overflow.

8. Nickel-manganese composite hydroxide particles comprising secondary particles formed by an aggregation of plural primary particles and expressed by a general formula: Ni x Mn y M t (OH) 2+α ,
where
0.05≤ x≤ 0.95,

0.05≤ y≤ 0.95,

0≤ t≤ 0.20,

x+y+t= 1, 0≤α≤0.5,and

M is one or more elements selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W, and
the nickel-manganese composite hydroxide particles obtained from the method for producing nickel-manganese composite hydroxide particles according to claim 1 ; wherein
the average particle size of the secondary particles is 7.0 μm to 25.0 μm,
the index [(d90−d10)/the average particle size of the secondary particles] that indicates the spread of the particle-size distribution is 0.80 to 1.20,
of the nickel-manganese composite hydroxide particles, the average value of the roundness of nickel-manganese hydroxide particles having a particle size that is 70% the average particle size of the secondary particles or more is 0.82 or greater, and
the tap density of the nickel-manganese composite hydroxide particles is 2.20 g/cm 3 or greater.

9. A method for producing cathode active material for a non-aqueous electrolyte secondary battery, comprising:
a mixing process for obtaining a lithium mixture by mixing a lithium compound with the nickel-manganese composite hydroxide particles disclosed in claim 8 or heat-treated particles that are obtained by heat treating the nickel-manganese composite hydroxide particles disclosed in claim 8 ; and
a calcination process for performing calcination of the lithium mixture in an oxidizing atmosphere at 720° C. to 1,000° C.

10. A cathode active material for a non-aqueous electrolyte secondary battery comprising layered hexagonal crystalline lithium composite oxide particles expressed by a general formula: Li 1+α Ni x Mn y M t O 2 ,
where
−0.05≤ u≤ 0.50,

0.05≤ x≤ 0.95,

0.05≤ y≤ 0.95,

0≤ t≤ 0.20,

x+y+t= 1, and

M is one or more elements selected from among Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W,
wherein
the average particle size of the secondary particles is 7.0 μm to 25.0 μm,
the index [(d90−d10)/the average particle size of the secondary particles] that indicates the spread of the particle-size distribution is 0.80 to 1.20,
the average value of the roundness of cathode active material having a particle size that is 70% the average particle size of the secondary particles or more is 0.82 or greater, and
the tap density is 2.20 g/cm 3 or greater.

11. A non-aqueous electrolyte secondary battery comprising a cathode, an anode, a separator and a non-aqueous electrolyte, wherein
the cathode active material for a non-aqueous electrolyte secondary battery according to claim 10 is used as cathode material for the cathode.

Assignees

• Sumitomo Metal Mining Co

Inventors

• Yamaji Koji
• Honma Takehide
• Ushio Ryozo

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/043

  involving compressing or compaction · CPC title

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · 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