Positive electrode active material precursor for nonaqueous electrolyte secondary battery and method for manufacturing positive electrode active material precursor for nonaqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-11949102-B2
Application number	US-202117455281-A
Country	US
Kind code	B2
Filing date	Nov 17, 2021
Priority date	Jan 6, 2016
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

A positive electrode active material precursor for a nonaqueous electrolyte secondary battery is provided that includes a nickel-cobalt-manganese carbonate composite represented by general formula Ni x Co y Mn z M t CO 3 (where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional element selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W) and a hydrogen-containing functional group. The ratio H/Me of the amount of hydrogen H to the amount of metal components Me included in the positive electrode active material precursor is less than 1.60. The positive electrode active material further includes a secondary particle formed by a plurality of primary particles that have been aggregated.

First claim

The invention claimed is:

1. A positive electrode active material precursor for a nonaqueous electrolyte secondary battery, the positive electrode active material precursor comprising:
a nickel-cobalt-manganese carbonate composite represented by general formula Ni x Co y Mn z M t CO 3 (where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional element selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W); and
a hydrogen-containing functional group, wherein H/Me representing a ratio of an amount of hydrogen (H) to an amount of metal components (Me) included in the positive electrode active material precursor is less than 1.60;
wherein a secondary particle of the positive electrode active material precursor is formed by a plurality of primary particles of the positive electrode active material precursor that have been aggregated.

2. The positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 1 , wherein
the secondary particle has an average particle diameter that is greater than or equal to 2 μm and less than or equal to 10 μm; and
an index [(d 90 -d 10 )/average particle diameter] indicating a particle size distribution range of the positive electrode active material precursor is less than or equal to 0.55.

3. The positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 1 , wherein
the additional element (M) in the general formula representing the nickel-cobalt-manganese carbonate composite includes molybdenum (Mo); and
a content ratio of molybdenum (Mo) in the metal components (Me) of the nickel-cobalt-manganese carbonate composite is greater than or equal to 0.5 at % and less than or equal to 5 at %.

4. A method for manufacturing a positive electrode active material precursor for a nonaqueous electrolyte secondary battery, wherein the positive electrode active material precursor includes: a nickel-cobalt-manganese carbonate composite represented by general formula Ni x Co y Mn z M t CO 3 (where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional element selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W); and a hydrogen-containing functional group, wherein H/Me representing a ratio of an amount of hydrogen (H) to an amount of metal components (Me) included in the positive electrode active material precursor is less than 1.60; wherein a secondary particle of the positive electrode active material precursor is formed by a plurality of primary particles of the positive electrode active material precursor that have been aggregated, the method comprising:
a nucleation step of forming nuclei in a mixed aqueous solution that is prepared by mixing together, under the presence of carbonate ions, an initial aqueous solution containing an ammonium ion supplier, an aqueous solution containing nickel as a metal component, an aqueous solution containing cobalt as a metal component, and an aqueous solution containing manganese as a metal component; and
a nucleus growth step of growing the nuclei formed in the nucleation step;
wherein a pH value of the mixed aqueous solution is controlled to be less than or equal to 7.5 at a reaction temperature of 40° C. as a standard temperature in the nucleation step, and
wherein the nucleation step and the nucleus growth step are performed in an atmosphere containing at least one of an inert gas and a carbon dioxide gas.

5. The method for manufacturing a positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 4 , wherein
an ammonium ion concentration in the mixed aqueous solution during the nucleus growth step is controlled to be greater than or equal to 0 g/L and less than or equal to 20 g/L.

6. The method for manufacturing a positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 4 , wherein the mixed aqueous solution is maintained at a temperature greater than or equal to 30° C. in the nucleation step.

7. The method for manufacturing a positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 4 , the method further comprising:
a nucleus disintegration step that is performed between the nucleation step and the nucleus growth step, the nucleus disintegration step including stopping addition of raw materials and only stirring the mixed aqueous solution.

8. The method for manufacturing a positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 4 , the method further comprising:
a coating step of coating the additional element on the positive electrode active material precursor that has been obtained in the nucleus growth step.

9. The method for manufacturing a positive electrode active material precursor for a nonaqueous electrolyte secondary battery according to claim 8 , wherein the coating step is at least one step selected from
a step of adding an aqueous solution containing the additional element to a first slurry in which the positive electrode active material precursor is suspended, and causing the additional element to precipitate on a surface of the positive electrode active material precursor;
a step of spray drying a second slurry in which the positive electrode active material precursor and a compound containing the additional element are suspended; and
a step of mixing together the positive electrode active material precursor and the compound containing the additional element by a solid phase method.

Assignees

• Sumitomo Metal Mining Co

Inventors

• Matsumoto Satoshi
• Ryoshi Kazuomi
• Uekusa Kikoo

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

• C01G51/50

  of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2 · CPC title

• C01G53/006

  Chemistry & Metallurgy · mapped topic

• C01G53/06

  Carbonates · CPC title