# US 12,113,213 B2 · Cathode active material for non-aqueous electrolyte secondary battery and manufacturing method for same, and non-aqueous electrolyte secondary battery

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- Number: US 12,113,213 B2
- Document ID: US12113213B2
- Status: Granted
- Kind: B2
- Application number: 14/907,087
- Filed: 2014-07-22
- Published: 2016-06-16
- Granted: 2024-10-08
- Earliest claimed: 2013-07-24
- Assignees: Sumitomo Metal Mining Co., Ltd.; Toyota Jidosha Kabushiki Kaisha
- Applicants: Sumitomo Metal Mining Co., Ltd.; Toyota Jidosha Kabushiki Kaisha
- Inventors: Hiroyuki Toya; Masahiro Morita; Hiroki Nagai; Yoshinari Makimura; Tetsuro Kobayashi
- Web page: https://patentgrep.com/patent/US12113213B2

## CPC

- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/502: containing lithium and cobalt
- H01M 4/366: {as layered products}
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2002/50: Solid solutions
- C01P 2002/74: by peak-intensities or a ratio thereof only
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/12: Surface area
- C01P 2006/40: Electric properties
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

A cathode active material for a non-aqueous electrolyte secondary battery has improved output characteristics in low-temperature environment use. A lithium mixture includes composite hydroxide particles and a lithium compound calcined in an oxidizing atmosphere under a temperature rising time from 650° C. to a calcination temperature set to 0.5-1.5 hours and the calcination temperature set to 850° C.-1000° C. and maintained for 1.0-5.0 hours. The material has the general formula (A): Li1+SNixCoyMnzM1O2 , where −0.05≤s≤0.20, x+y+z+t=1, 0.3≤x≤0.7, 0.1≤y≤0.4, 0.1≤z≤0.4, 0≤t≤0.05, and M is selected from Ca, Mg, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W. The material includes hexagonal lithium composite oxide particles. The ratio of the crystallite size at plane (104) to plane (003) is greater than 0 and less than 0.60.

## Claims

### Claim 1

A cathode active material for a non-aqueous electrolyte secondary battery expressed by a general formula (A):
Li1+aNixCoyMnzMtO2 , where 0.12<a≤0.20, x+y+z+t=1, 0.30≤x≤0.50, 0.30<y≤0.40, 0.15≤z≤0.40, 0.0003<t≤0.01, and M is one or more element selected from among Ca, Mg, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W, and includes layered hexagonal crystal lithium nickel cobalt manganese composite oxide particles;
the lithium nickel cobalt manganese composite oxide particles comprise spherical shaped secondary particles that are formed by an aggregation of plural primary particles, wherein the primary particles have a spherical shape;
wherein a ratio of an integrated width of a diffraction peak on plane (104) with respect to an integrated width of a diffraction peak on plane (003) of the Miller indices (hkl) in powder Xray diffraction that uses CuKα rays is 1.38 or greater and 1.49 or less; and
a ratio of a peak integrated intensity on plane (003) with respect to a peak integrated intensity on plane (104) of the Miller indices (hkl) in powder X-ray diffraction that uses CuKα rays is 1.23 or greater and 1.29 or less.

### Claim 2 (depends on 1)

The cathode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the integrated width ratio is within the range of 1.39 to 1.49.

### Claim 3 (depends on 1)

The cathode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein a volume-average particle size that is found by a laser diffraction and scattering method is within a range of 3 μm to 20 μm.

### Claim 4 (depends on 1)

The cathode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein a specific surface area is within a range of 0.3 m2m2/g to 2.5 m2/g.

### Claim 5 (depends on 1)

A manufacturing method for a cathode active material for a non-aqueous electrolyte secondary battery according to claim 1, the method comprising:
a crystallization process for obtaining composite hydroxide particles expressed by a general formula (B): NixCoyMnzMt(OH)2+α, where x+y+z+t=1, 0.30≤x≤0.70, 0.30<y≤0.40, 0.10≤z≤0.40, 0.0003<t≤0.01, and M is one or more element selected from among Ca, Mg, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W, the process comprising:
obtaining a mixed aqueous solution in which metal compound of nickel, cobalt, manganese and additional elements (M) are dissolved at the composition ratios expressed by the general formula (B),
adding an ammonium-ion donor to the mixed aqueous solution while stirring,
forming a reaction aqueous solution by adding a sodium hydroxide aqueous solution to the mixed aqueous solution, and
crystallizing the composite hydroxide particles from the reaction aqueous solution by using a batch-type crystallization method, wherein the composite hydroxide particles have a spherical shape and the batch type crystallization method comprises:
a nucleation stage, wherein a nuclei of composite hydroxide particles form, and
a particle growth stage, wherein the composite hydroxide particles grow around the nuclei,
wherein particles forming the nuclei in the nucleation stage and particles of the growth stage are clearly separated,
a mixing process for obtaining a lithium mixture by mixing a lithium compound with the nickel cobalt manganese composite hydroxide particles that are expressed by general formula (B) so that the ratio of the number of atoms of lithium with respect to the total number of atoms of metal elements other than lithium is more than 1:1.12 and 1:1.2 or less; and
a calcination process of performing calcination of the lithium mixture in an oxidizing atmosphere where a rate of temperature rise in at least the temperature range from 30° C. to 800° C. is 4° C./min to 9° C./min, the calcination temperature is 800° C. to 1000° C., the maintenance time at the calcination temperature is 4 hours or less, and time from the start of temperature rise to the end of the maintenance time is 4.0 hours to 6.9 hours.

### Claim 6 (depends on 5)

The manufacturing method for a cathode active material for a non-aqueous electrolyte secondary battery according to claim 5, further comprising
a heat-treatment process before the mixing process for heat treating the nickel cobalt manganese composite hydroxide particles to 105° C. to 400° C. to obtain heat-treated particles.

### Claim 7 (depends on 5)

The manufacturing method for a cathode active material for a non-aqueous electrolyte secondary battery according to claim 5, wherein lithium carbonate, lithium hydroxide or a mixture of these is used as the lithium compound.

### Claim 8 (depends on 5)

The manufacturing method for a cathode active material for a non-aqueous electrolyte secondary battery according to claim 5, wherein the oxygen concentration in the oxidizing atmosphere is 10% by volume to 100% by volume.

### Claim 9 (depends on 5)

The manufacturing method for a cathode active material for a non-aqueous electrolyte secondary battery according to claim 5, further comprising
a crushing process after the calcination process for crushing the lithium nickel cobalt manganese composite particles that were obtained in the calcination process.

### Claim 10 (depends on 1)

A non-aqueous electrolyte secondary battery comprising a cathode, an anode, a separator and a non-aqueous electrolyte, wherein the cathode comprises the cathode active material of claim 1.

### Claim 11 (depends on 10)

The non-aqueous electrolyte secondary battery according to claim 10, wherein an initial discharge capacity is 150 mAh/g or greater, and an output at −30° C. is 110 W or greater.