Lithium-containing transition metal composite oxide, positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, lithium secondary battery, and method for manufacturing lithium-containing transition metal composite oxide

Patent metadata

Field	Value
Publication number	US-12176531-B2
Application number	US-202318490447-A
Country	US
Kind code	B2
Filing date	Oct 19, 2023
Priority date	Nov 30, 2017
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

This lithium-containing transition metal composite oxide includes secondary particles that are aggregates of primary particles into or from which lithium ions are dopable or dedopable, and satisfies the following conditions:
(1) the lithium-containing transition metal composite oxide is represented by Formula (I),

Li[Lix(Ni(1−y−z−w)CoyMnzMw)1−x]O2  (I)
(2) from X-ray photoelectron spectroscopy, a specific γ is calculated for each of the surface of the secondary particle and the inside of the secondary particle, and when the γ value of the surface of the secondary particle is referred to as γ1 and the γ value of the inside of the secondary particle is referred to as γ2, γ1 and γ2 satisfy the condition of Formula (II).

0.3≤γ1/γ2≤1.0  (II).

First claim

The invention claimed is:

1. A method for manufacturing a lithium-containing transition metal composite oxide including secondary particles that are aggregates of primary particles into or from which lithium ions are dopable or dedopable and represented by General Formula (I), the method comprising:
a mixing step of mixing a lithium compound and a metal composite compound containing at least nickel to obtain a mixture;
a baking step of baking the mixture to obtain a baked product; and
a washing step of washing the baked product,
wherein, in the mixing step, mixing is performed so that a molar ratio (Li/Me, a molar ratio of lithium to a total amount of metal elements excluding lithium) between lithium contained in the lithium compound and metal elements in the metal composite compound containing at least nickel exceeds 1, and
in the washing step, a temperature of a washing solution used for washing is set to −20° C. or higher and 40° C. or lower, and washing is performed in an amount of the washing solution used for washing such that a concentration of lithium carbonate in the washing solution in a case where it is assumed that a total amount of residual lithium carbonate contained in the baked product before washing is dissolved in the washing solution is 1/10 or more and 3 or less times a solubility of lithium carbonate in the washing solution at the temperature of the washing solution during the washing step,
Li[Li x (Ni( 1−y−z−w )Co y Mn z M w ) 1−x ]O 2   (I)

(in Formula (I), 0≤x≤0.2, 0<y≤0.5, 0≤z≤0.8, 0≤w≤0.1, and y+z+w<1 are satisfied, and M represents one or more metals selected from the group consisting of Mg, Ca, Sr, Ba, Zn, B, Al, Ga, Ti, Zr, Ge, Fe, Cu, Cr, V, W, Mo, Sc, Y, Nb, La, Ta, Tc, Ru, Rh, Pd, Ag, Cd, In, and Sn).

2. A method for manufacturing a lithium-containing transition metal composite oxide including secondary particles that are aggregates of primary particles into or from which lithium ions are dopable or dedopable and represented by General Formula (I), the method comprising:
mixing step of mixing a lithium compound and a metal composite compound containing at least nickel to obtain a mixture;
a baking step of baking the mixture to obtain a baked product; and
a washing step of washing the baked product,
wherein, in the mixing step, mixing is performed so that a molar ratio (Li/Me, a molar ratio of lithium to a total amount of metal elements excluding lithium) between lithium contained in the lithium compound and metal elements in the metal composite compound containing at least nickel exceeds 1, and
in the washing step, a temperature of a slurry containing the baked product and a washing solution used for washing is maintained at −20° C. or higher and lower than 10° C., and washing is performed in an amount of the washing solution used for washing such that a concentration of lithium carbonate in the washing solution in a case where it is assumed that a total amount of residual lithium carbonate contained in the baked product before washing is dissolved in the washing solution is 1/10 or more and 3 or less times a solubility of lithium carbonate in the washing solution at the temperature of the washing solution during the washing step,
Li[Li x (Ni(1−y−z−w)Co y Mn z M w ) 1−x ]O 2   (I)

(in Formula (I), 0≤x≤0.2, 0<y≤0.5, 0≤z≤0.8, 0≤w≤0.1, and y+z+w<1 are satisfied, and M represents one or more metals selected from the group consisting of Mg, Ca, Sr, Ba, Zn, B, Al, Ga, Ti, Zr, Ge, Fe, Cu, Cr, V, W, Mo, Sc, Y, Nb, La, Ta, Tc, Ru, Rh, Pd, Ag, Cd, In, and Sn).

3. A method for manufacturing a lithium-containing transition metal composite oxide including secondary particles that are aggregates of primary particles into or from which lithium ions are dopable or dedopable and represented by General Formula (I), the method comprising:
a mixing step of mixing a lithium compound and a metal composite compound containing at least nickel to obtain a mixture;
a baking step of baking the mixture to obtain a baked product; and
a washing step of washing the baked product,
wherein, in the mixing step, mixing is performed so that a molar ratio (Li/Me, a molar ratio of lithium to a total amount of metal elements excluding lithium) between lithium contained in the lithium compound and metal elements in the metal composite compound containing at least nickel exceeds 1, and
in the washing step, a temperature of a washing solution used for washing is set to −20° C. or higher and 40° C. or lower, washing is performed in an amount of the washing solution used for washing such that a concentration of lithium carbonate in the washing solution in a case where it is assumed that a total amount of residual lithium carbonate contained in the baked product before washing is dissolved in the washing solution is 1/10 or more and 3 or less times a solubility of lithium carbonate in the washing solution at the temperature of the washing solution, and a temperature of a slurry containing the baked product and the washing solution used for washing is maintained at −20° C. or higher and lower than 10° C.,
Li[Li x (Ni(1−y−z−w)Co y Mn z M w ) 1−x ]O 2   (I)

(in Formula (I), 0≤x≤0.2, 0<y≤0.5, 0≤z≤0.8, 0≤w≤0.1, and y+z+w<1 are satisfied, and M represents one or more metals selected from the group consisting of Mg, Ca, Sr, Ba, Zn, B, Al, Ga, Ti, Zr, Ge, Fe, Cu, Cr, V, W, Mo, Sc, Y, Nb, La, Ta, Tc, Ru, Rh, Pd, Ag, Cd, In, and Sn).

Assignees

• Sumitomo Chemical Co
• Tanaka Chemical Corp

Inventors

• Arimura Takashi
• Takamori Kenji
• Kageura Jun-Ichi
• Sato Yuichi
• Maeda Yusuke

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M10/0525

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

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/364

  as mixtures · CPC title