Lithium composite metal compound, positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, lithium secondary battery, and method for manufacturing lithium composite metal compound

Patent metadata

Field	Value
Publication number	US-11949101-B2
Application number	US-201917042695-A
Country	US
Kind code	B2
Filing date	Feb 28, 2019
Priority date	Mar 30, 2018
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

Provided are a lithium composite metal compound having excellent cycle characteristics in the case of being used as battery materials, a positive electrode active material for a lithium secondary battery using the same, a positive electrode using the same, and a lithium secondary battery using the same. The lithium composite metal compound is represented by Composition Formula (I), in which physical property values of pores that are obtained from measurement of nitrogen adsorption and desorption isotherms at a liquid nitrogen temperature satisfy requirements (1) and (2).

First claim

The invention claimed is:

1. A lithium composite metal compound represented by Composition Formula (I),
Li[Li x (Ni (1-y-z) Co y Mn z ) 1-x ]O 2   (I)

where M represents one or more elements selected from the group consisting of Mn, Fe, Cu, Ti, Mg, Al, W, B, Mo, Zn, Sn, Zr, Ga, Nb, and V, and −0.10≤x≤0.2, 0<y≤0.2, 0≤z≤0.2, and 0<y+z≤0.25 are satisfied,
wherein physical property values of pores that are obtained from measurement of nitrogen adsorption and desorption isotherms at a liquid nitrogen temperature satisfy requirements (1) and (2),
(1) a total pore volume determined from an amount of nitrogen adsorbed when a relative pressure (p/p o ) of an adsorption isotherm is 0.99 is 0.008 cm 3 /g or more and 0.012 cm 3 /g or less, and
(2) in a pore distribution determined from a desorption isotherm by a BJH method, a proportion of a volume of pores of 15 nm or less with respect to a total pore volume of 200 nm or less is less than 50%, and
wherein, in the pore distribution determined from the desorption isotherm by the BJH method, a minimum value of pore diameters at which a peak of a log differential pore volume is observed is 20 nm or more.

2. The lithium composite metal compound according to claim 1 ,
wherein a content of lithium carbonate is 0.3 mass % or less, and a content of lithium hydroxide is 0.2 mass % or less.

3. The lithium composite metal compound according to claim 1 ,
wherein, in the pore distribution determined from the desorption isotherm by the BJH method, a minimum value of pore diameters at which a peak of a log differential pore volume is observed is 10 nm or more.

4. The lithium composite metal compound according to claim 1 ,
wherein, in a hysteresis loop of the adsorption isothem and the desorption isotherm that are obtained from the measurement of the nitrogen adsorption and desorption isothems,
in a case where an area between the adsorption isotherm and the desorption isotherm at the relative pressures (p/p o ) in a range of 0.7 or more and 0.9 or less is denoted by S1, and
an area between the adsorption isotherm and the desorption isotherm at the relative pressures (p/p o ) in a range of 0.5 or more and 0.9 or less is denoted by S2, a ratio (S1/S2) of the S1 to the S2 is 0.8 or more.

5. The lithium composite metal compound according to claim 1 ,
wherein, in the pore distribution determined from the desorption isotherm by the BJH method,
a peak of a log differential pore volume is present at a pore diameter in a range of 10 nm or more and 40 nm or less.

6. The lithium composite metal compound according to claim 1 ,
wherein, in the pore distribution determined from the desorption isotherm by the BJH method, a peak value of a log differential pore volume at a pore diameter in a range of 3 nm or more and 5 nm or less is less than 0.005 cm 3 /(g·nm).

7. The lithium composite metal compound according to claim 1 ,
wherein, in the pore distribution determined from the desorption isotherm by the BJH method, a peak value of a log differential pore volume is not present at a pore diameter in a range of 3 nm or more and 5 nm or less.

8. A positive electrode active material for a lithium secondary battery, comprising:
the lithium composite metal compound according to claim 1 .

9. A positive electrode for a lithium secondary battery, comprising:
the positive electrode active material for a lithium secondary battery according to claim 8 .

10. A lithium secondary battery comprising:
the positive electrode for a lithium secondary battery according to claim 9 .

11. A method for manufacturing a lithium composite metal compound represented by Composition Formula (I), the method comprising:
Li[Li x (Ni (1-y-z) Co y Mn z ) 1-x ]O 2   (I)

where M represents one or more elements selected from the group consisting of Mn, Fe, Cu, Ti, Mg, Al, W, B, Mo, Zn, Sn, Zr, Ga, Nb, and V, and −0.10≤x≤0.2, 0<y≤0.2, 0≤z≤0.2, and 0<y+z≤0.25 are satisfied,
a step of calcining a mixture of a lithium compound and a transition metal compound to obtain a lithium composite metal compound;
a water washing step of removing the lithium compound remaining in the lithium composite metal compound by water washing; and
a step of drying the water-washed lithium composite metal compound,
wherein the drying step is performed in a rotary kiln supplied with a gas having a carbon dioxide concentration of 300 ppm or less, the water-washed lithium composite metal compound is heated at a temperature of 150° C. or higher and 300° C. or lower in the rotary kiln, and a ratio (B/A) of an aeration rate B (Nm 3 /hour) of a gas that is supplied from an outside to a moisture evaporation rate A (kg/hour) during drying is 2 Nm 3 /kg or more and 20 Nm 3 /kg or less, and
wherein, the aeration rate B is the aeration rate of the gas with a carbon dioxide concentration of 300 ppm or less.

Assignees

• Sumitomo Chemical Co
• Tanaka Chemical Corp

Inventors

• Inoue Masashi
• Maeda Yusuke

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

• C01G53/42 Primary

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

• H01M4/505

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

• H01M10/0525

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

• C01P2002/50

  Solid solutions · CPC title