Precursor for lithium secondary battery positive electrode active materials, method for producing precursor for lithium secondary battery positive electrode active materials, and method for producing lithium composite metal compound

Patent metadata

Field	Value
Publication number	US-12172906-B2
Application number	US-201917298815-A
Country	US
Kind code	B2
Filing date	Dec 6, 2019
Priority date	Dec 7, 2018
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

A precursor for lithium secondary battery positive electrode active materials containing at least nickel, in which the following formula (1) is satisfied.

0.20≤ D min/ D max  (1)
(in the formula (1), Dmin is a minimum particle diameter (μm) in a cumulative particle size distribution curve obtained by measuring the precursor for lithium secondary battery positive electrode active materials with a laser diffraction-type particle size distribution measuring instrument, and Dmax is a maximum particle diameter (μm) in the cumulative particle size distribution curve obtained by the measurement with the laser diffraction-type particle size distribution measuring instrument.).

First claim

What is claimed is:

1. A precursor for lithium secondary battery positive electrode active materials, comprising:
nickel,
wherein the following formula (1) is satisfied,
0.20≤ D min/ D max  (1)

where, in the formula (1), Dmin is a minimum particle diameter (μm) in a cumulative particle size distribution curve obtained by measuring the precursor with a laser diffraction-type particle size distribution measuring instrument, and Dmax is a maximum particle diameter (μm) in the cumulative particle size distribution curve obtained by the measurement with the laser diffraction-type particle size distribution measuring instrument, and
wherein the following formula (5) is satisfied,
0.65≤α/β≤1.45  (5)

where, in the formula (5), α is a half width of a diffraction peak at 2θ=52.4±1° that is obtained by X-ray diffraction using a CuKα ray, and β is a half width of a diffraction peak at 2θ=73.9±1° that is obtained by X-ray diffraction using a CuKα ray.

2. The precursor according to claim 1 ,
wherein the precursor is represented by the following composition formula (A),
Ni 1-x-y Co x M y O z (OH) 2-α   (A)

where, in the composition formula (A), 0≤x≤0.45, 0≤y≤0.45, 0≤x+y≤0.9, 0≤z≤3, −0.5≤α≤2, and M is one or more metal elements selected from Zr, Al, Ti, Mn, Ga, In, and W.

3. The precursor according to claim 1 ,
wherein the following formula (4) is satisfied,
10μm≤ D 50≤30μm  (4)

where, in the formula (4), D50 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 50% from a small particle side in the cumulative particle size distribution curve, with a total cumulative volume being set to 100%, obtained by measuring the precursor with the laser diffraction-type particle size distribution measuring instrument.

4. The precursor according to claim 1 ,
wherein the following formulae (2) and (3) are satisfied,
( D 50− D 10)/ D 50≤0.35  (2) and

( D 90− D 50)/ D 50≤0.50  (3)

where, in the formulae (2) and (3), D10 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 10% from a small particle side in the cumulative particle size distribution curve, with a total cumulative volume being set to 100%, obtained by measuring the precursor with the laser diffraction-type particle size distribution measuring instrument, D50 is a value (μm) of a particle diameter at a point at which the cumulative volume reaches 50%, and D90 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 90%.

5. The precursor according to claim 1 ,
wherein a BET specific surface area is 2 m 2 /g or more and 80 m 2 /g or less.

6. A method for producing the precursor of claim 1 , the method comprising:
a slurry preparation step of supplying a metal-containing aqueous solution containing at least nickel and an alkaline aqueous solution to a reaction vessel to obtain a hydroxide-containing slurry; and
a classification step of classifying the hydroxide-containing slurry using a screen.

7. The method according to claim 6 ,
wherein the precursor is represented by the following composition formula (A),
Ni 1-x-y Co x M y O z (OH) 2-α   (A)

where, in the composition formula (A), 0≤x≤0.45, 0≤y≤0.45, 0≤x+y≤0.9, 0≤z≤3, −0.5≤α≤2, and M is one or more metal elements selected from Zr, Al, Ti, Mn, Ga, In, and W.

8. The method according to claim 6 ,
wherein the precursor satisfies the following formula (4),
10μm≤ D 50≤30μm  (4)

where, in the formula (4), D50 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 50% from a small particle side in the cumulative particle size distribution curve, with a total cumulative volume being set to 100%, obtained by measuring the precursor with the laser diffraction-type particle size distribution measuring instrument.

9. The method according to claim 6 , further comprising:
a reflux step of supplying the slurry that has passed through the screen to the reaction vessel.

10. The method according to claim 6 ,
wherein a material of the screen is a polymer material.

11. The method according to claim 6 ,
wherein, in the classification step, a classification device includes a rotatable screw inside a fixed screen, and
the hydroxide-containing slurry is classified by rotating the screw at a circumferential velocity of 1.0 m/second or faster and 10.0 m/second or slower.

12. A method for producing the precursor of claim 1 , the method comprising:
a slurry preparation step of supplying a metal-containing aqueous solution containing at least nickel and an alkaline aqueous solution to a reaction vessel to obtain a hydroxide-containing slurry; and
a classification step of classifying the hydroxide-containing slurry with a liquid cyclone-type classification device,
wherein the classification step is carried out under a condition that a classification device inlet pressure is 0.01 MPa or more and 0.07 MPa or less.

13. The method according to claim 12 ,
wherein the precursor is represented by the following composition formula (A),
Ni 1-x-y Co x M y O z (OH) 2-α   (A)

where, in the composition formula (A), 0≤x≤0.45, 0≤y≤0.45, 0≤x+y≤0.9, 0≤z≤3, −0.5≤α≤2, and M is one or more metal elements selected from Zr, Al, Ti, Mn, Ga, In, and W.

14. The method according to claim 12 ,
wherein the precursor satisfies the following formula (4),
10μm≤ D 50≤30μm  (4)

where, in the formula (4), D50 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 50% from a small particle side in the cumulative particle size distribution curve, with a total cumulative volume being set to 100%, obtained by measuring the precursor with the laser diffraction-type particle size distribution measuring instrument.

15. The method according to claim 6 , further comprising:
a heating step of heating a precursor in an oxygen-containing atmosphere within a temperature range of 300° C. or higher and 900° C. or lower.

16. A method for producing a lithium composite metal compound, the method comprising:
a mixing step of mixing the precursor obtained by the method according to claim 6 and a lithium compound; and
a calcining step of calcining the obtained mixture in an oxygen-containing atmosphere at a temperature of 500° C. or higher and 1000° C. or lower.

17. The precursor according to claim 2 ,
wherein the following formula (4) is satisfied,
10μm≤ D 50≤30μm  (4)

where, in the formula (4), D50 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 50% from a small particle side in the cumulative particle size distribution curve, with a total cumulative volume being set to 100%, obtained by measuring the precursor with the laser diffraction-type particle size distribution measuring instrument.

18. The precursor according to claim 2 ,
wherein the following formulae (2) and (3) are satisfied,
( D 50 −D 10)/ D 50≤0.35  (2) and

( D 90− D 50)/ D 50≤0.50  (3)

where, in the formulae (2) and (3), D10 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 10% from a small particle side in the cumulative particle size distribution curve, with a total cumulative volume being set to 100%, obtained by measuring the precursor with the laser diffraction-type particle size distribution measuring instrument, D50 is a value (μm) of a particle diameter at a point at which the cumulative volume reaches 50%, and D90 is a value (μm) of a particle diameter at a point at which a cumulative volume reaches 90%.

Assignees

• Sumitomo Chemical Co
• Tanaka Chemical Corp

Inventors

• DEGURA Keiji
• Kobayashi Ryota
• Maeda Yusuke

Classifications

• C01G53/82

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

• H01M10/0525

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

• C01P2006/12

  Surface area · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title