Aluminum-coated nickel cobalt containing composite hydroxide and method for manufacturing same, cathode active material for non-aqueous electrolyte secondary battery and method for manufacturing same, and non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-12195352-B2
Application number	US-202017083411-A
Country	US
Kind code	B2
Filing date	Oct 29, 2020
Priority date	Apr 28, 2015
Publication date	Jan 14, 2025
Grant date	Jan 14, 2025

Abstract

Provided is a cathode active material for a non-aqueous electrolyte secondary battery that improves the cycling characteristic and high-temperature storability without impairing the charge/discharge capacity and the output characteristics. A nickel cobalt containing composite hydroxide is obtained by using a batch type crystallization method in which a raw material aqueous solution that includes Ni, Co and Mg is supplied in an inert atmosphere to a reaction aqueous solution that is controlled so that the temperature is within the range 45° C. to 55° C., the pH value is within the range 10.8 to 11.8 at a reference liquid temperature of 25° C., and the ammonium-ion concentration is within the range 8 g/L to 12 g/L. An Al-coated composite hydroxide that is expressed by the general formula: Ni 1-x-y-z Co x Al y Mg z (OH) 2 (where, 0.05≤x≤0.20, 0.01≤y≤0.06, and 0.01≤z≤0.03) is obtained by mixing a slurry that includes the nickel cobalt containing composite hydroxide with a coating aqueous solution that includes Al to form a mixed aqueous solution, and coating the secondary particles with a coating film that includes Al or an Al compound. A cathode active material that is configured so that component elements that include Al are uniformly dispersed in the secondary particles is synthesized using the Al-coated composite hydroxide as a precursor.

First claim

What is claimed is:

1. A method for manufacturing a cathode active material for a non-aqueous electrolyte secondary battery that includes a lithium nickel cobalt composite oxide having a layered structure that is expressed by a general formula: Li u Ni 1-x-y-z Co x Al y Mg z O 2 (where 1.00≤u≤1.04, 0.05≤x≤0.20, 0.01≤y≤0.06, and 0.01≤z≤0.03) and that includes secondary particles having a solid structure that are formed by an aggregate of plural primary particles,
the average particle size of the secondary particles of the cathode active material being within the range 4 μm to 7 μm or less, the tap density of the cathode material being 2.0 g/mL or greater and 2.3 g/mL or less, and the specific surface area of the cathode active material being within the range 0.7 m 2 /g to 1.0 m 2 /g,
wherein the primary particles of the cathode active material have a rectangular parallelepiped shape, and the average particle size of the primary particles of the cathode active material is within the range 0.05 μm to 0.5 μm,
the average particle size of the primary particles of the cathode active material is the crystallite diameter which is found from the Scherer equation using results from x-ray diffraction measurements; and
the lithium nickel cobalt composite oxide having a crystal structure in which cobalt, magnesium and aluminum are uniformly dissolved in a matrix composed of LiNiO 2 ,
the method comprising:
a mixing step for obtaining a lithium mixture by mixing an aluminum-coated nickel cobalt composite hydroxide or a roasted material thereof as a precursor with a lithium compound, wherein
the aluminum-coated nickel cobalt composite hydroxide consists of: Ni 1-x-y-z Co x Al y Mg z (OH) 2 (where, 0.05≤x≤0.20, 0.01≤y≤0.06, and 0.01≤z≤0.03), and includes secondary particles, wherein
the secondary particles of the precursor have a structure in which a main part has a solid structure that is formed by an aggregate of plural primary particles and in which nickel, cobalt, and magnesium are uniformly dispersed, the main part coated by a coating film that includes aluminum or an aluminum compound;
the average particle size of the secondary particles of the precursor being within the range of 4 μm to 7 μm or less, the tap density of the precursor being 1.5 g/mL or greater, and the specific surface area of the precursor being within the range of 5.5 m 2 /g to 7.5 m 2 /g; and
the primary particles of the precursor have a rectangular parallelepiped shape, and the average particle size of the primary particles is within the range of 0.01 μm to 0.1 μm;
the average particle size of the primary particles of the precursor is the crystallite diameter which is found from the Scherer equation using results from x-ray diffraction measurements; and
a calcination step for obtaining a lithium nickel cobalt containing composite oxide by calcining the lithium mixture in an oxidizing atmosphere in which the oxygen concentration is 98% by volume or greater.

2. The method for manufacturing a cathode active material for a non-aqueous electrolyte secondary battery according to claim 1 , wherein a calcination temperature in the calcination step is within the range of 700° C. to 800° C.

3. The method for manufacturing a cathode active material for a non-aqueous electrolyte secondary battery according to claim 1 , further comprising an oxidation roasting step that oxidizes and roasts aluminum-coated nickel cobalt composite hydroxide to obtain a roasted material thereof before the mixing step.

4. The method for manufacturing a cathode active material for a non-aqueous electrolyte secondary battery according to claim 3 , wherein the oxidation roasting temperature in the oxidation roasting step is equal to or less than the calcination temperature, and is within the range of 600° C. to 800° C.

5. A cathode active material for a non-aqueous electrolyte secondary battery that includes a lithium nickel cobalt composite oxide having a layered structure that is expressed by a general formula: Li u Ni 1-x-y-z Co x Al y Mg z O 2 (where 1.00≤u≤1.04, 0.05≤x≤0.20, 0.01≤y≤0.06, and 0.01≤z≤0.03) and that includes secondary particles having a solid structure that are formed by an aggregate of plural primary particles,
the average particle size of the secondary particles being within the range of 4 μm to 7 μm or less, the tap density being 2.0 g/mL or greater and 2.3 g/mL or less, and the specific surface area being within the range of 0.7 m 2 /g to 1.0 m 2 /g,
wherein the primary particles have a rectangular parallelepiped shape, and the average particle size of the primary particles is within the range 0.2 μm to 0.5 μm, and the average particle size of the primary particles is the crystallite diameter which is found from the Scherer equation using results from x-ray diffraction measurements, and
the lithium nickel cobalt composite oxide having a crystal structure in which cobalt, magnesium and aluminum are uniformly dissolved in a matrix composed of LiNiO 2 .

6. A non-aqueous electrolyte secondary battery comprising a cathode, an anode, a separator, and a non-aqueous electrolyte, wherein the cathode comprises a cathode active material that is the cathode active material for a non-aqueous electrolyte secondary battery according to claim 5 .

Assignees

• Sumitomo Metal Mining Co

Inventors

• Honma Takehide
• Yamaji Koji
• Ushio Ryozo

Classifications

• H01M10/0525

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

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• C01G53/82 Primary

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

• H01M10/052

  Li-accumulators · CPC title

• C01G53/42

  containing alkali metals, e.g. LiNiO2 · CPC title