Cathode active material for lithium ion secondary battery, method for manufacturing cathode active material for lithium ion secondary battery, and lithium ion secondary
Provided is a cathode active material for a lithium ion secondary battery in which the secondary particles constituting the powder have a high breaking strength and a good coatability, and a method for manufacturing same. The cathode active material for a lithium ion secondary battery includes a primary particle of a lithium composite compound; and secondary particles formed by an aggregation of primary particles, wherein a ratio between an average particle size of the primary particles and an average particle size of the secondary particles is 0.006 or more and 0.25 or less, an amount of lithium carbonate is 0.4% by mass or less, and a breaking strength of the secondary particles is 30 MPa or more.
1. A cathode active material for a lithium ion secondary battery, comprising:
a primary particle of a lithium composite compound represented by the following formula (1); and
a secondary particle formed by an aggregation of primary particles of the lithium composite compound, wherein
a ratio (D 1 /D 2 ) between an average particle size (D 1 ) of the primary particles and an average particle size (D 2 ) of secondary particles is from 0.006 to 0.25 both inclusive,
the cathode active material for a lithium ion secondary battery has a specific surface area from 0.2 m 2 /g to 1.0 m 2 /g both inclusive,
an amount of lithium carbonate is from 0.08% by mass to 0.3% by mass both inclusive,
a breaking strength of the secondary particle is 40 MPa or more,
the secondary particle has an aspect ratio of from 0.6 to 1.0 both inclusive,
the secondary particles have an open pore volume ratio which is determined by a mercury intrusion method and which is 20% or less in a pore diameter range of from 0.1 μm to 0.5 μm both inclusive, and
the cathode active material for a lithium ion secondary battery has a moisture content of 250 ppm or less,
Li 1+a Ni x Co y M1 1−x−y−z M2 z O 2+α (1)
provided that (a) in the formula (1), M1 is Mn, (b) M2 is Ti, and (c) a, x, y, z, and α are numbers satisfying 0.02≤a≤0.2, 0.8≤x≤0.9, 0.03≤y≤0.15, 0≤z≤0.02, 0.05≤1−x−y−z≤0.1, and −0.2≤α≤0.2 respectively.
2. The cathode active material for a lithium ion secondary battery according to claim 1 , wherein
the secondary particle has an aspect ratio of from 0.92 to 0.95 both inclusive.
3. The cathode active material for a lithium ion secondary battery according to claim 1 , wherein the amount of the lithium carbonate is 0.08% by mass to 0.15% by mass both inclusive, and the breaking strength of the secondary particle is 60 MPa or more.
4. The cathode active material for a lithium ion secondary battery according to claim 1 , wherein the secondary particles have an open pore volume ratio which is determined by a mercury intrusion method and which is less than 7% in a pore diameter range of from 0.1 μm to 0.5 μm both inclusive.
5. A lithium ion secondary battery comprising a cathode comprising the cathode active material for a lithium ion secondary battery according to claim 1 .
6. A method for manufacturing a cathode active material for a lithium ion secondary battery, comprising:
a mixing step of producing a mixture by mixing lithium carbonate with compounds each containing a metal element shown in the following formula (1) other than Li; and
a firing step of producing a lithium composite compound represented by the following formula (1) by firing the mixture, wherein
the firing step includes
a first firing step of producing a first precursor by firing the mixture at firing temperature of from 200° C. to 400° C. both inclusive for from 0.5 hours to 5 hours both inclusive,
a second firing step of producing a second precursor by reacting 92% mass or more of the lithium carbonate by firing the first precursor at a firing temperature of from 450° C. and to 800° C. both inclusive for from 0.5 hours to 50 hours both inclusive in an oxidative atmosphere in which a carbon dioxide concentration is 5% or less,
a third firing step of producing the lithium composite compound by firing the second precursor at a firing temperature of from 755° C. to 900° C. both inclusive for from 0.5 hours to 50 hours both inclusive in an oxidative atmosphere in which a carbon dioxide concentration is 5% or less, and
a sealing step of sealing, after the third firing step, in a storage container the lithium composite compound having an amount of lithium carbonate from 0.08% by mass to 0.3% by mass both inclusive, and a moisture content of 250 ppm or less, and
wherein the atmosphere inside the storage container is an inert gas atmosphere, or a reduced-pressure atmosphere with a high vacuum degree,
Li 1+a Ni x Co y M1 1−x−y−z M2 z O 2+α (1)
provided that (a) in the formula (1), M1 is Mn, (b) M2 is Ti, and (c) a, x, y, z, and α are numbers satisfying 0.02≤a≤0.2, 0.8≤x≤0.9, 0.03≤y≤0.15, 0≤z≤0.02, 0.05≤1−x−y−z≤0.1, and −0.2≤α≤0.2 respectively.
7. The method for manufacturing a cathode active material for a lithium ion secondary battery according to claim 6 , further comprising:
a washing step of washing the lithium composite compound with water after the third firing step; and
a drying step of drying the lithium composite compound washed with water, wherein
the drying step being performed before the lithium composite compound having an amount of lithium carbonate of 0.3% or less by mass and a moisture content of 250 ppm or less is sealed in the storage container.
8. The method for manufacturing a cathode active material for a lithium ion secondary battery according to claim 7 , wherein the mixing step includes
a preparing step of preparing a mixed slurry through mixing by wet grinding, and
a granulating step of granulating the mixed slurry by spray drying.
9. The cathode active material for a lithium ion secondary battery according to claim 6 , wherein
the secondary particle has an aspect ratio of from 0.92 to 0.95 both inclusive.
10. A cathode active material for a lithium ion secondary battery prepared by the method according to claim 6 , wherein the amount of the lithium carbonate is 0.08% by mass to 0.15% by mass both inclusive, and the breaking strength of the secondary particle is 60 MPa or more.
11. The cathode active material for a lithium ion secondary battery according to claim 6 , wherein the secondary particles have an open pore volume ratio which is determined by a mercury intrusion method and which is less than 7% in a pore diameter range of from 0.1 μm to 0.5 μm both inclusive.
12. The method for manufacturing a cathode active material for a lithium ion secondary battery according to claim 6 , wherein the mixing step includes
a preparing step of preparing a mixed slurry through mixing by wet grinding, and
a granulating step of granulating the mixed slurry by spray drying.
13. A lithium ion secondary battery comprising a cathode comprising the cathode active material for a lithium ion secondary battery prepared by the method according to claim 6 .