Positive-electrode active material for nonaqueous electrolyte secondary battery and method for producing the same, and nonaqueous electrolyte secondary battery
The present invention provides a cathode active material for a nonaqueous electrolyte secondary battery with a high capacity, high stability and excellent output characteristics and a method for producing the same, and a nonaqueous electrolyte secondary battery using the cathode active material. The cathode active material for a nonaqueous electrolyte secondary battery is represented by a general formula: Li t Ni 1-x-y-z Co x Al y Ti z O 2 wherein 0.98≤t≤1.10, 0<x≤0.30, 0.03≤y≤0.15, 0.001≤z≤0.03; and includes a hexagonal lithium-containing composite oxide with a layer structure of secondary particles having primary particles, in which a titanium-enriched layer is formed on a surface of the primary particles and/or a grain boundary between the primary particles. The titanium-enriched layer on the surface of the primary particles and/or a grain boundary between the primary particles serves as a lithium ion conductor, yielding smooth extraction and insertion of lithium ions. Accordingly, the secondary battery with a high capacity, high stability and excellent output characteristics can be produced when a positive electrode is formed with the lithium nickel composite oxide as a cathode active material.
1. A cathode active material for a nonaqueous electrolyte secondary battery represented by a general formula:
Li t Ni 1-x-y-z Co x Al y Ti z O 2
wherein 0.98≤t≤1.10, 0≤x≤0.30, 0.03≤y≤0.15, 0.001≤z≤0.03; and comprising a hexagonal lithium-containing composite oxide with a layer structure of secondary particles having primary particles,
wherein the cathode active material is made by firing the lithium-containing composite oxide at over 760° C. and not higher than 780° C. thereby forming an intermediate of a lithium titanium oxide and a lithium nickel dioxide in a grain boundary between the primary particles.
2. The cathode active material for a nonaqueous electrolyte secondary battery according to claim 1 , wherein a site occupancy of metal ions except lithium obtained by Rietveld refinement using X-ray diffraction of the lithium-containing composite oxide is 2% or less in a 3a site if each site of 3a, 3b and 6c in the lithium-containing composite oxide is represented by [Li] 3a [Ni 1-x-y-z Co x Al y Ti z ] 3b [O 2 ] 6c .
3. The cathode active material for a nonaqueous electrolyte secondary battery according to claim 1 , wherein a shape of the secondary particle is spherical or substantially spherical.
4. The cathode active material for a nonaqueous electrolyte secondary battery according to claim 1 , wherein an average particle diameter of the secondary particles is 3 to 8 μm, and a value represented by a expression of: [(d90−d10)/average particle diameter] as a marker indicating spreading of a particle size distribution is 0.60 or less.
5. A method for producing a cathode active material for a nonaqueous electrolyte secondary battery according to claim 1 , the method comprising the steps of:
heat treating a nickel cobalt aluminum composite hydroxide represented by a general formula:
Ni 1-x-y Co x Al y (OH) 2
wherein 0≤x≤0.30, 0.03≤y≤0.15;
mixing the nickel cobalt aluminum composite hydroxide and/or a nickel cobalt aluminum composite oxide, a lithium compound, and a titanium compound; and
firing the mixture at over 760 to 780° C. for 4 hours or more.
6. The mixture for producing a cathode active material for a nonaqueous electrolyte secondary battery according to claim 5 , wherein an average particle diameter of the composite hydroxide is 3 to 7 μm, and a value represented by a expression of: [(d90−d10)/average particle diameter] as a marker indicating spreading of a particle size distribution is 0.55 or less.
7. The method for producing a cathode active material for a nonaqueous electrolyte secondary battery according to claim 5 , wherein a washing process is carried out after the firing.
8. A method for producing a cathode active material for a nonaqueous electrolyte secondary battery according to claim 1 , the method comprising the steps of:
heat treating a nickel cobalt aluminum titanium composite hydroxide represented by a general formula:
Li t Ni 1-x-y-z Co x Al y Ti z (OH) 2
wherein 0≤x≤0.30, 0.03≤y≤0.15, 0.001≤z≤0.03;
mixing the nickel cobalt aluminum titanium composite hydroxide and/or a nickel cobalt aluminum titanium composite oxide, and a lithium compound; and
firing the mixture at over 760 to 780° C. for four hours or more.
9. A nonaqueous electrolyte secondary battery having a positive electrode formed with the cathode active material for a nonaqueous electrolyte secondary battery according to claim 1 .