Positive electrode active material for non-aqueous electrolyte secondary battery and process for producing same, and non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-11990618-B2
Application number	US-202117515887-A
Country	US
Kind code	B2
Filing date	Nov 1, 2021
Priority date	Sep 20, 2016
Publication date	May 21, 2024
Grant date	May 21, 2024

Abstract

A positive electrode active material containing a lithium metal composite oxide composed of secondary particles formed by aggregated primary particles, comprising lithium, at least one metal element and at least one additive element, the lithium metal composite oxide having a crystal structure of layered rock salt structure and the metal element including nickel in a content of 60 to 90 atomic percent and the additive element including boron in content of more than 1.0 atomic percent and 6.0 atomic percent or less, the nickel content and the boron content each with respect to the sum of the metal element and the additive element, the porosity of the secondary particles being 8% or more and 20% or less; a non-aqueous electrolyte secondary battery containing the positive electrode active material; and a process for producing the positive electrode active material.

First claim

The invention claimed is:

1. A process for producing a positive electrode active material for non-aqueous electrolyte secondary battery containing lithium metal composite oxide comprising lithium, a metal element, and an additive element, and nickel content as the metal element is 60 to 90 atomic percent with respect to a sum of the metal element and the additive element, and boron content as the additive element is more than 1.0 atomic percent and 6.0 atomic percent or less with respect to the sum of the metal element and the additive element, wherein the process comprising:
a crystallization step including a step that mixed aqueous solution containing a metal salt element, which includes at least nickel salt, and a boron compound as the additive element, and aqueous solution containing ammonium ion are mixed to be reaction solution, and that pH of the reaction solution based on a liquid temperature of 25° C. is controlled to be in a range of 11.0 to 12.5 using alkaline aqueous solution, and that, at that time, aqueous solution containing ammonium ion and alkaline aqueous solution are supplied into the reaction solution to grow particles of nickel composite hydroxide;
a drying step for drying crystallized the nickel composite hydroxide after washing it;
and a calcining step for obtaining the lithium metal composite oxide by calcining in oxygen atmosphere a mixture obtained by mixing dried the nickel composite hydroxide and a lithium compound;
wherein, in the crystallization step, a position for supplying the aqueous solution containing ammonium ion and the alkaline aqueous solution is located between deepest part of stirring blade in the reaction solution and a position at one third of a distance between deepest part of the stirring blade and liquid surface of the reaction solution from deepest part of the stirring blade, in vertical direction, and located between outermost periphery of the stirring blade and an intermediate position of a center and outermost periphery of the stirring blade, in horizontal direction.

2. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , wherein the mixed aqueous solution further contains cobalt as the metal element.

3. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , wherein the boron content is 1.5 to 5 atomic percent with respect to the sum of the metal element and the additive element.

4. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , wherein, in the crystallization step, concentration of the sum of the metal element and the additive element in the mixed aqueous solution is 1.5 to 2.5 mol/L.

5. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , wherein, in the calcining step, a calcining temperature is 650 to 950° C.

6. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 1 , wherein, in the calcining step, lithium hydroxide, lithium carbonate, or these mixture are used as the lithium compound.

7. A process for producing a positive electrode active material for non-aqueous electrolyte secondary battery containing lithium metal composite oxide comprising lithium, a metal element, and an additive element, and nickel content as the metal element is 60 to 90 atomic percent with respect to a sum of the metal element and the additive element, and boron content as the additive element is more than 1.0 atomic percent and 6.0 atomic percent or less with respect to the sum of the metal element and the additive element, wherein the process comprising:
a crystallization step including a step that mixed aqueous solution containing a metal salt element, which includes at least nickel salt, and a boron compound as the additive element, and aqueous solution containing ammonium ion are mixed to be reaction solution, and that pH of the reaction solution based on a liquid temperature of 25° C. is controlled to be in a range of 11.0 to 12.5 using alkaline aqueous solution, and that, at that time, aqueous solution containing ammonium ion and alkaline aqueous solution are supplied into the reaction solution to grow particles of nickel composite hydroxide;
a drying step for drying crystallized the nickel composite hydroxide after washing it;
and a calcining step for obtaining the lithium metal composite oxide by calcining in oxygen atmosphere a mixture obtained by mixing dried the nickel composite hydroxide and a lithium compound;
wherein, in the crystallization step, a position for supplying the aqueous solution containing ammonium ion and the alkaline aqueous solution is located at liquid surface between outer periphery of liquid surface of the reaction solution and a position at one third of a distance between a center and outer periphery of liquid surface from outer periphery of liquid surface.

8. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 7 , wherein the mixed aqueous solution further contains cobalt as the metal element.

9. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 7 , wherein the boron content is 1.5 to 5 atomic percent with respect to the sum of the metal element and the additive element.

10. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 7 , wherein, in the crystallization step, concentration of the sum of the metal element and the additive element in the mixed aqueous solution is 1.5 to 2.5 mol/L.

11. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 7 , wherein, in the calcining step, a calcining temperature is 650 to 950° C.

12. The process for producing the positive electrode active material for non-aqueous electrolyte secondary battery according to claim 7 , wherein, in the calcining step, lithium hydroxide, lithium carbonate, or these mixture are used as the lithium compound.

Assignees

• Sumitomo Metal Mining Co

Inventors

• Suzuki Jun
• Yamaji Koji

Classifications

• 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

• H01M4/04

  Processes of manufacture in general · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M10/0525

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